JP4110075B2 - Coating formation method using surface lubricant for dental acrylic soft material - Google Patents
Coating formation method using surface lubricant for dental acrylic soft material Download PDFInfo
- Publication number
- JP4110075B2 JP4110075B2 JP2003378463A JP2003378463A JP4110075B2 JP 4110075 B2 JP4110075 B2 JP 4110075B2 JP 2003378463 A JP2003378463 A JP 2003378463A JP 2003378463 A JP2003378463 A JP 2003378463A JP 4110075 B2 JP4110075 B2 JP 4110075B2
- Authority
- JP
- Japan
- Prior art keywords
- surface lubricant
- film
- acrylic soft
- methacrylate
- soft material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000314 lubricant Substances 0.000 title claims description 80
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 52
- 239000011248 coating agent Substances 0.000 title claims description 48
- 238000000576 coating method Methods 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 39
- 239000007779 soft material Substances 0.000 title claims description 32
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 239000001301 oxygen Substances 0.000 claims description 45
- 229910052760 oxygen Inorganic materials 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 43
- 239000002981 blocking agent Substances 0.000 claims description 37
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 229920000193 polymethacrylate Polymers 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 methacrylate ester Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 description 149
- 238000012360 testing method Methods 0.000 description 57
- 239000010408 film Substances 0.000 description 44
- 238000006116 polymerization reaction Methods 0.000 description 43
- 239000004014 plasticizer Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000002156 mixing Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- 210000000214 mouth Anatomy 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 10
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 9
- 238000010828 elution Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 210000004877 mucosa Anatomy 0.000 description 8
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 7
- 229930006711 bornane-2,3-dione Natural products 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 210000004400 mucous membrane Anatomy 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003190 viscoelastic substance Substances 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 210000002200 mouth mucosa Anatomy 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- DGPBVJWCIDNDPN-UHFFFAOYSA-N 2-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=CC=C1C=O DGPBVJWCIDNDPN-UHFFFAOYSA-N 0.000 description 1
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical compound CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- 208000006386 Bone Resorption Diseases 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Description
本発明は、歯科におけるアクリル系軟質材の耐久性を向上する表面滑沢剤の特性を最大限に発揮させるための被膜形成方法に関し、詳しくは、前記アクリル系軟質材として、義歯床用裏装材、咬合スプリント、ナイトガード、マウスガード等を例示でき、特に、義歯床用裏装材に対して好適に利用できる。 The present invention relates to a film forming method for maximizing the characteristics of the table MenNamera Sawa agent you improve the durability of the acrylic soft material in dentistry, particularly, as the acrylic soft material, denture A lining material, an occlusal splint, a night guard, a mouth guard, etc. can be illustrated, and can be suitably used particularly for a denture lining material.
義歯を長期に亘って使用した場合、生理的な骨吸収や顎堤粘膜の菲薄化等により、義歯床粘膜面と床下粘膜面との適合性が徐々に低下していく。そのような場合、義歯床用裏装材（以下裏装材という）と言われる材料で義歯床粘膜面を裏装し、適合性を改善することが一般的に行われている。 When a denture is used over a long period of time, the compatibility between the denture base mucosa surface and the subfloor mucosa surface gradually decreases due to physiological bone resorption and thinning of the ridge mucosa. In such a case, it is a common practice to improve the compatibility by lining the denture base mucosal surface with a material called denture base lining material (hereinafter referred to as lining material).
この場合、裏装材としては硬質の材料が主として用いられるが、高齢化が急速に進む今日では、軟質の裏装材がますますその重要性を増しつつある。すなわち、加齢により顎堤粘膜が菲薄となった総義歯患者においては、たとえ硬質の裏装材で義歯の適合性を改善したとしても、クッション作用の乏しい薄い顎堤粘膜が硬い義歯床に圧迫されることにより、どうしても咬合時に疼痛を生じることがある。このような患者に対しては、義歯床粘膜面を軟質の裏装材で裏装し、失われた粘膜を代用させることが有効と考えられる。 In this case, a hard material is mainly used as the lining material. However, today, a soft lining material is becoming more and more important as the aging process is rapidly progressing. In other words, in denture patients with thinning of the alveolar ridge mucosa due to aging, even if the denture compatibility is improved with a hard lining material, the thin alveolar mucosa with poor cushioning is pressed against the hard denture base. As a result, pain may be caused during occlusion. For such patients, it is considered effective to substitute the lost mucous membrane by lining the denture base mucosa surface with a soft lining material.
このような咬合時の疼痛緩和を目的とした義歯床用軟質裏装材としては、これまでにアクリル系、シリコーン系、ポリオレフィン系等の各種材料のものが開発され、すでに臨床の場で使用されているが、それらにはいずれも一長一短があり、未だ十分満足のいく材料は得られていない。 As soft lining materials for denture bases for the purpose of alleviating pain during occlusion, various materials such as acrylic, silicone, and polyolefin have been developed and used in clinical settings. However, they all have merits and demerits, and a satisfactory material has not yet been obtained.
（シリコーン系軟質裏装材）
シリコーン系軟質裏装材としては、主として付加重合タイプの常温重合型シリコーンが使用されている。この材料は、ベース、キャタリストの２種類のペーストを使用時に混和し、その混合物を義歯床粘膜面に盛り付け、患者の口腔内に装着して硬化させることにより裏装を行う。
(Silicone-based soft lining material)
As the silicone soft lining material, addition polymerization type room temperature polymerization type silicone is mainly used. This material is backed by mixing two types of pastes, base and catalyst, at the time of use, placing the mixture on the surface of the denture basement mucosa, setting it in the patient's mouth and allowing it to harden.
この２種類のペーストの混合は、通常ディスペンサーといわれる自動練和器で行なわれるため、手練りのように気泡が混入することがなく、比較的均一な材料が得られるとされている。 The mixing of these two types of pastes is usually carried out in an automatic kneader called a dispenser, so that it is said that bubbles are not mixed as in hand kneading and a relatively uniform material can be obtained.
しかし、シリコーン系の材料は、アクリル系の義歯床材料とは本質的に接着せず、各種接着剤の開発が行なわれてはいるものの、耐久性の面で十分な接着力を得るには至っておらず、使用時に義歯床辺縁部から剥離が生じるといった問題が指摘されている。 However, silicone-based materials do not inherently adhere to acrylic denture base materials, and although various adhesives have been developed, sufficient adhesive strength is obtained in terms of durability. In addition, there has been a problem that peeling occurs from the edge of the denture base at the time of use.
また、シリコーン系材料は分子構造的に“疎”であり、そのため汚れ等が付着しやすく、かつ、細菌が材料内部にまで進入し、材料を劣化させるという問題もある。さらに、切削面を研磨して滑沢にすることが本質的に不可能なため、切削面は粗となり、汚れ、細菌の付着なども必然的に多くなる。 In addition, the silicone-based material is “sparse” in terms of molecular structure, so that there is a problem that dirt or the like is easily attached, and bacteria enter the material and deteriorate the material. Furthermore, since it is essentially impossible to polish and smooth the cutting surface, the cutting surface becomes rough, and dirt, bacteria adhesion, and the like inevitably increase.
その上、シリコーン系材料は、硬化した材料の上に、新たに材料を追加した場合、互いに接着しないため、裏装面を部分的に削除して再修正するということが実質的に不可能となり、これが臨床上の大きな欠点となっている。 In addition, silicone-based materials do not adhere to each other when new materials are added on top of the cured material, making it virtually impossible to partially remove and re-modify the backing surface. This is a major clinical drawback.
（ポリオレフィン系軟質裏装材）
また、ポリオレフィン系軟質裏装材は、吸水性が非常に小さい。従って、口腔内で使用した場合の耐久性が極めて高いと言われていた。しかし、一方では油に対する耐性に劣り、油性食品等により着色するということが新たな問題となっている。
(Polyolefin soft lining material)
Polyolefin-based soft lining materials have very low water absorption. Therefore, it was said that the durability when used in the oral cavity is extremely high. However, on the other hand, it is inferior in resistance to oil, and coloring with oil-based foods or the like is a new problem.
また、ポリオレフィン系材料を用いた裏装は、間接的な技工操作によってのみしか行うことができず、かつ、その操作が極めて煩雑であることも本材料の普及を妨げる要因となっている。さらに、義歯床に対する接着力も十分とは言えず、煩雑な接着工程を必要とするわりには、剥離などの問題が残されたままとなっている。 In addition, backing using a polyolefin-based material can be performed only by an indirect technical operation, and the fact that the operation is extremely complicated is also a factor that hinders the spread of this material. Furthermore, it cannot be said that the adhesive force to the denture base is sufficient, but problems such as peeling remain while requiring a complicated bonding process.
（アクリル系軟質裏装材）
一方、アクリル系軟質裏装材は、一般的な義歯床用材料と同系統の材料であるため、義歯床に対する接着性は極めて良好であり、また、裏装材同士も強固に接着するため、部分的な追加修正も可能となる。さらに、アクリル系軟質裏装材は、材質的には粘弾性体であり、これはシリコーン系軟質裏装材の弾性体に比べより口腔粘膜に近似しており、そのため咬合時の緩圧作用にすぐれ、咀嚼機能がより向上すると言われている。
(Acrylic soft lining material)
On the other hand, the acrylic soft lining material is a material of the same system as a general denture base material, so the adhesion to the denture base is extremely good, and the lining materials are also firmly bonded to each other, Partial addition and modification are also possible. Furthermore, acrylic soft lining materials are viscoelastic in terms of material, which is closer to the oral mucosa than the elastic bodies of silicone soft lining materials. It is said that the chewing function is further improved.
このアクリル系軟質裏装材には、重合型とゲル化型の２種類があり、さらに重合型には常温重合型、加熱重合型、光重合型の３種類のものがあり、それぞれ直接法用、間接法用として使い分けがなされている。 There are two types of acrylic soft lining materials, polymerization type and gelation type. Furthermore, there are three types of polymerization types: room temperature polymerization type, heat polymerization type, and photopolymerization type. It is properly used for indirect methods.
＜常温重合型アクリル系軟質裏装材＞
常温重合型アクリル系軟質裏装材は、ポリメタクリル酸エステルとラジカル重合開始剤を主成分とする粉剤と、メタクリル酸エステル、可塑剤、ラジカル重合促進剤を主成分とする液剤とからなり、粉剤と液剤を混合することにより、ゲル化を経て常温下で重合反応が起こり、軟質・粘弾性の材料となる。本材料は口腔内温度下でも短時間で重合硬化するため、主として直接法用として使われている。
<Room-temperature polymerization type acrylic soft lining material>
The room temperature polymerization type acrylic soft lining material comprises a powder mainly composed of polymethacrylate and radical polymerization initiator, and a liquid composed mainly of methacrylate, plasticizer and radical polymerization accelerator. And a liquid agent are mixed, a polymerization reaction occurs at normal temperature through gelation, and a soft and viscoelastic material is obtained. Since this material is polymerized and cured in a short time even at an intraoral temperature, it is mainly used for direct methods.
＜加熱重合型アクリル系軟質裏装材＞
また、加熱重合型アクリル系軟質裏装材は、基本的には常温重合型アクリル系軟質裏装材と同じであるが、重合促進剤を含まないため、常温下では重合反応が起こらず、硬化させるためには加熱が必要となる。そのため、本材料は間接法での使用しか行えないが、加圧成形するため、気泡のない、緻密な材質となり、耐久性の面では常温重合型の材料よりも優れているといわれている。
<Heat-polymerized acrylic soft lining material>
In addition, the heat polymerization type acrylic soft backing material is basically the same as the room temperature polymerization type acrylic soft backing material. Heating is necessary to achieve this. For this reason, this material can only be used by the indirect method, but since it is pressure-molded, it becomes a dense material without bubbles and is said to be superior to the room temperature polymerization type material in terms of durability.
＜光重合型アクリル系軟質裏装材＞
また、光重合型アクリル系軟質裏装材は、メタクリル酸エステル、可塑剤、光重合開始剤等からなる１成分系の材料で、そのペースト状材料に可視光線を照射することにより、光重合反応が起こり、軟質・粘弾性の材料となる。
<Photopolymerization type acrylic soft lining material>
The photopolymerization type acrylic soft lining material is a one-component material composed of a methacrylic ester, a plasticizer, a photopolymerization initiator, etc., and a photopolymerization reaction is performed by irradiating the paste-like material with visible light. Occurs and becomes a soft and viscoelastic material.
この光重合型アクリル系軟質裏装材の中には、特開２００２−１１９５２３に開示されているような、常温＋光重合併用型の材料も含まれている。本材料は、ポリメタクリル酸エステル、重合開始剤、光重合開始剤を主成分とする粉剤と、メタクリル酸エステル、可塑剤、重合促進剤を主成分とする液剤とからなり、常温重合後の軟質・可塑性の材料に可視光線を照射することにより、軟質・粘弾性の材料となる。 In this photopolymerization type acrylic soft lining material, a material of room temperature + photopolymerization combination type as disclosed in JP-A-2002-119523 is also included. This material consists of a powder mainly composed of polymethacrylic acid ester, polymerization initiator and photopolymerization initiator, and a liquid composed mainly of methacrylic acid ester, plasticizer and polymerization accelerator. -When a plastic material is irradiated with visible light, it becomes a soft and viscoelastic material.
本材料は、口腔内で常温重合を起こすことにより、混合時のペースト状態から可塑性状態に変化させる点で従来の光硬化型材料と異なり、それにより、口腔内からの撤去が容易になり、また、撤去時の変形が少なくなることから、適合性は大幅に改善されると言われている。 This material differs from conventional photo-curing materials in that it changes from a paste state at the time of mixing to a plastic state by causing normal temperature polymerization in the oral cavity, which facilitates removal from the oral cavity. Because the deformation at the time of removal is reduced, the compatibility is said to be greatly improved.
＜常温ゲル化型材料＞
また、常温ゲル化型材料は、ポリメタクリル酸エステルを主成分とする粉剤と、可塑剤、エタノールを主成分とする液剤とからなり、粉液を混合することにより常温下でゲル化し、軟質・粘弾性体へと変化する。この材料は重合反応を伴わないため、塑性変形を起こしやすく、その性質を生かし、主として粘膜調整材（ティッシュコンディショナー）、あるいは機能印象材として使用されているが、暫間的な軟質裏装材としても使用されている。
<Room temperature gelling material>
The room temperature gelling material consists of a powder mainly composed of polymethacrylic acid ester, a plasticizer, and a liquid mainly composed of ethanol. It changes into a viscoelastic body. Since this material does not involve a polymerization reaction, it is prone to plastic deformation and is used mainly as a mucosal conditioner (tissue conditioner) or functional impression material, but as a temporary soft lining material. Has also been used.
このように、アクリル系軟質裏装材は、その種類が多いため応用範囲が広く、物性的にも他の軟質裏装材には無い多くの長所を有しているが、一方では長期にわたる耐久性が劣るという大きな欠点も有している。 In this way, acrylic soft lining materials have a wide range of applications because of their many types, and have many advantages over other soft lining materials in terms of physical properties. It also has a major drawback of inferiority.
すなわち、アクリル系軟質裏装材は、吸水性が大きいため汚れやすく、また、カンジダ菌等の口腔内細菌も付着しやすいと言われている。さらに、材料の軟化を意図して配合される可塑剤（一般的にはフタル酸エステル類）が使用中に徐々に溶出し、そのため材質的に硬化・劣化していくことも指摘されている。 That is, the acrylic soft lining material is said to be easily soiled due to its large water absorption, and is also said to easily adhere to oral bacteria such as Candida. Furthermore, it has been pointed out that plasticizers (generally phthalates) compounded with the intention of softening the material gradually elute during use, and therefore harden and deteriorate in terms of material.
さらにまた、軟質で、かつ流動変形しやすい性質を有しているため、材料内部に残留する気泡が徐々に表層へと移動し、その気泡が表面で潰れることにより材料表面が極めて粗となる。その結果、汚れ、細菌の付着がよりいっそう助長され、それが耐久性低下の大きな原因となっている。 Furthermore, since the material is soft and easily deformed by flow, bubbles remaining inside the material gradually move to the surface layer, and the surface of the material becomes extremely rough because the bubbles are crushed on the surface. As a result, dirt and bacterial adhesion are further promoted, which is a major cause of durability deterioration.
この気泡の浮き上がり現象は、市販の義歯洗浄剤の使用によって著しく促進されるため、そのような洗浄剤により化学的洗浄を行うことができない。このこともまた、アクリル系軟質裏装材の耐久性をさらに悪化させる要因となっている。 This bubble lifting phenomenon is significantly accelerated by the use of commercially available denture cleaners, and chemical cleaning cannot be performed with such cleaners. This is also a factor that further deteriorates the durability of the acrylic soft lining material.
（表面滑沢材）
このようなアクリル系軟質裏装材の有する問題点を改善するものとして、表面滑沢材なるものが開発され、その一部はすでに臨床応用がなされている。これらはそのほとんどがポリメタクリル酸エステルを低揮発性の有機溶剤、あるいはアクリル系モノマーに溶解させたものである。
(Surface lubricant)
In order to improve the problems of such acrylic soft lining materials, surface lubricants have been developed, and some of them have already been clinically applied. Most of these are polymethacrylates dissolved in a low-volatile organic solvent or acrylic monomer.
＜自然乾燥型＞
表面滑沢材を裏装材表面に塗布し、自然乾燥させることにより、裏装材の表面にポリメタクリル酸エステル等の連続した被膜を形成させ、表層に滑沢性を付与するというものである。
<Natural dry type>
By applying a surface lubricant to the surface of the lining material and allowing it to dry naturally, a continuous film such as polymethacrylate is formed on the surface of the lining material, thereby imparting lubricity to the surface layer. .
これにより裏装材表面の光沢度は向上し、表面がより滑らかとなるため、食物や細菌の付着が抑制できる。また、表層を比較的硬度の高い材料で被覆するため、外部からの機械的摩擦による摩耗を抑えるとともに、内部気泡の表層への浮き上がりをある程度抑えることができる。 Thereby, the glossiness of the surface of the lining material is improved and the surface becomes smoother, so that the adhesion of food and bacteria can be suppressed. Further, since the surface layer is coated with a material having a relatively high hardness, it is possible to suppress abrasion due to mechanical friction from the outside and to suppress the rising of internal bubbles to the surface layer to some extent.
しかし、この自然乾燥型のアクリル系軟質裏装材用表面滑沢材は、形成される被膜自体がポリメタクリル酸エステル等の線状高分子であり、それらはアクリル系軟質裏装材に含まれる可塑剤によって本質的に溶解・軟化されるものである。 However, in this natural drying type acrylic soft lining material, the formed coating itself is a linear polymer such as polymethacrylate, and they are included in the acrylic soft lining material. It is essentially dissolved and softened by the plasticizer.
そのため、従来型の表面滑沢材を可塑剤含有のアクリル系軟質裏装材に塗布した場合、塗布直後の段階では表面を滑沢にする効果、及び保護する効果は大きいものの、口腔内で長期間使用している間に、裏装材内部の可塑剤によって滑沢材被膜が徐々に可塑化、軟化されていき、初期の硬質の被膜は徐々に軟質の被膜へと変質していく。そのため表層を硬くて緻密な被膜で保護するという滑沢材本来の機能が徐々に失われ、表面の光沢度・滑沢度は低下し、汚れ等が付着しやすくなる。 Therefore, when a conventional surface lubricant is applied to a plasticizer-containing acrylic soft lining material, the effect of smoothing and protecting the surface is great immediately after application, but it is long in the oral cavity. During the period of use, the lubricant film is gradually plasticized and softened by the plasticizer inside the lining material, and the initial hard film gradually changes into a soft film. Therefore, the original function of the lubricant, which protects the surface layer with a hard and dense film, is gradually lost, the surface glossiness and lubricity are lowered, and dirt and the like are easily attached.
このように被膜自体が軟質へと変化するため、裏装材内部の気泡の表層への浮き上がりを阻止するというバリヤー機能も低下し、逆に被膜自体が気泡によって膨れたり、また、気泡により被膜が裏装材から剥離したり、さらにまた、気泡が破れて滑沢材表面が粗になったりする。さらに、被膜自体が可塑剤に可溶であるため、可塑剤の溶出を抑える効果は期待できず、経時的な裏装材の硬化抑制にはあまり役に立つものではなかった。このように従来の自然乾燥型の表面滑沢材には、耐久性の向上という観点からは問題点が多く、必ずしも満足のいくものではなかった。 Since the coating itself changes to soft in this way, the barrier function of preventing the bubbles inside the lining material from rising to the surface layer also decreases, and conversely, the coating itself swells due to bubbles, or the coating due to bubbles It peels off from the lining material, and furthermore, the bubbles are broken and the surface of the lubricant becomes rough. Furthermore, since the coating itself is soluble in the plasticizer, the effect of suppressing the elution of the plasticizer cannot be expected, and it was not very useful for suppressing the curing of the backing material over time. As described above, the conventional air-drying type surface lubricant has many problems from the viewpoint of improving the durability and is not always satisfactory.
＜光重合型＞
この表面滑沢材としては、前述の自然乾燥型の材料以外に、光重合型の材料も提案されており、例えば、特開平４−３６０８０９号公報には、特定構造を有する２〜６官能性単量体、揮発性溶剤、アシルフォスフィンオキサイドからなる光硬化性表面滑沢材が開示されており、また、特開平４−３６６１１２号公報には、特定構造を有する多官能性単量体、揮発性溶剤、α−アミノアセトフェノン系重合開始剤からなる可視光線重合硬化性組成物が開示されている。
<Photopolymerization type>
As this surface lubricant, in addition to the above-mentioned natural drying type material, a photopolymerization type material has also been proposed. For example, JP-A-4-360809 discloses 2-6 functionalities having a specific structure. A photocurable surface lubricant composed of a monomer, a volatile solvent, and acylphosphine oxide is disclosed, and JP-A-4-366112 discloses a polyfunctional monomer having a specific structure, A visible light polymerization curable composition comprising a volatile solvent and an α-aminoacetophenone polymerization initiator is disclosed.
しかし、これらはいずれも義歯、あるいは義歯床等の硬質の材料に使用することを前提としており、被膜は硬く、可撓性も極めて低いものである。そのため、これらの表面滑沢材を軟質材に使用した場合、軟質材本来の軟らかさを大きく損なうことになり、従って、本質的に軟質裏装材用の表面滑沢材として使用できるものではない。 However, these are all premised on the use of a hard material such as a denture or a denture base, and the coating is hard and very low in flexibility. Therefore, when these surface lubricants are used for soft materials, the softness inherent to the soft materials will be greatly impaired, and therefore they cannot be used as surface lubricants for soft lining materials. .
また、最近では、アクリル系軟質裏装材用の光重合型表面滑沢材もいくつか提案されており、例えば特開平１０−１３９６１４号公報には、フッ素含有エラストマー、メタクリル系モノマー、光重合開始剤、及び有機溶剤からなるコーティング材組成物が開示されており、また、特開２００１−８９６９３号公報には、溶解度パラメーターが特定の範囲になるよう調整された共重合体、有機溶剤、メタクリル酸エステル、及び光重合開始剤からなるコーティング材組成物が開示されている。 Recently, several photopolymerization type surface lubricants for acrylic soft lining materials have also been proposed. For example, JP-A-10-139614 discloses fluorine-containing elastomers, methacrylic monomers, and photopolymerization starts. A coating material composition comprising an agent and an organic solvent is disclosed, and JP-A-2001-89693 discloses a copolymer, an organic solvent, and methacrylic acid whose solubility parameters are adjusted to a specific range. A coating material composition comprising an ester and a photopolymerization initiator is disclosed.
これらはいずれも裏装材に塗布することにより表面に滑沢性を付与し、着色、変色、菌の付着等を抑制することを意図したものであり、そのため、前者では非粘着性のフッ素含有エラストマーの被膜を形成させる方法、また、後者では特定の溶解度パラメーターを有する共重合体の被膜を形成させる方法を採用している。 All of these are intended to impart lubricity to the surface by applying to the lining material, and to suppress coloring, discoloration, adhesion of bacteria, etc. A method of forming an elastomer film, and the latter method of forming a copolymer film having a specific solubility parameter is adopted.
これらはいずれも軟質裏装材の耐久性の向上を目的としているが、その主眼とするところは、形成した被膜による吸水性の抑制、付着防止であり、そこには可塑剤に対する耐性を向上させるという意図は全く含まれておらず、その対策も講じられていない。従って、可塑剤含有のアクリル系軟質裏装材用の被膜材として使用した場合、前述した自然乾燥型の表面滑沢材と同様の問題点が残されたままとなり、十分満足できる結果を得ることはできない。 These are all aimed at improving the durability of the soft lining material, but the main point is to suppress water absorption and prevent adhesion by the formed coating, which improves the resistance to plasticizers. Is not included at all, and no countermeasures have been taken. Therefore, when used as a coating material for an acrylic soft lining material containing a plasticizer, the same problems as those of the natural drying type surface lubricant described above remain, and a sufficiently satisfactory result is obtained. I can't.
また、従来の光重合型表面滑沢材においては、表面が未重合になるという問題も含まれている。すなわち、光重合型材料は、光重合反応時に空気中の酸素による重合阻害を強く受け、そのため、空気と接する表面の重合度は低くなり、そのため保護被膜としての性能は著しく低下する。この酸素による重合阻害を防止する方法としては、
（１）酸素を含まない不活性ガス中で重合を行う。
（２）酸素を含まない水中に浸漬して重合を行う。
（３）酸素の存在下でも十分に重合反応が起こるよう、反応性を高くする
等の方法が提案されている。
Further, the conventional photopolymerization type surface lubricant includes a problem that the surface is not polymerized. That is, the photopolymerization type material is strongly affected by polymerization inhibition due to oxygen in the air during the photopolymerization reaction, and therefore, the degree of polymerization of the surface in contact with air is lowered, and therefore the performance as a protective coating is significantly lowered. As a method for preventing this oxygen-induced polymerization inhibition,
(1) Polymerization is performed in an inert gas containing no oxygen.
(2) Polymerization is performed by immersing in water not containing oxygen.
(3) A method has been proposed in which the reactivity is increased so that the polymerization reaction occurs sufficiently even in the presence of oxygen.
しかし、
（１）の方法は、それに応じた大掛かりな設備が必要となるため、実用的でなく、
（２）の方法は、光量の一部が水に吸収されるため重合効率の面でマイナスとなる。
（３）の方法は、材料の保存安定性が悪くなり、ポットライフの面で問題となる。
このように、光重合型表面滑沢材には、表面の重合阻害という大きな問題があり、その改善策が求められていた。
But,
The method (1) is not practical because it requires large-scale equipment corresponding to it.
The method (2) is negative in terms of polymerization efficiency because part of the light amount is absorbed by water.
The method (3) has a problem in terms of pot life due to poor storage stability of the material.
As described above, the photopolymerization type surface lubricant has a big problem of surface polymerization inhibition, and an improvement measure has been demanded.
この酸素による重合阻害を抑制する手段としては、光照射に先だって酸素遮断剤（エアーバリヤー）を塗布する方法も考案されており、同法は操作的に極めて簡便であり、また、薄い被膜で酸素を遮断できるので、光照射器の光量を減衰させる心配がない点からも有効な方法である。 As a means for suppressing this polymerization inhibition by oxygen, a method of applying an oxygen barrier (air barrier) prior to light irradiation has been devised, and this method is very easy to operate, and a thin film with oxygen This is an effective method from the point that there is no fear of attenuating the light quantity of the light irradiator.
しかしこの酸素遮断剤を塗布する方法は、硬質の裏装材、あるいは義歯床用材料等に採用されたものであり、この方法をそのまま軟質裏装材用の被膜材に応用することはできない。すなわち、従来の酸素遮断剤としては、アルギン酸ナトリウムを主成分とする水溶液、あるいは、ポリビニルアルコールのような水溶性ビニル系ポリマーを主成分とする水溶液が一般に使用されているが、アルギン酸ナトリウム水溶液の場合、形成される被膜は硬くて緻密なため表面光沢度は高く、その表面性状が被膜材にも反映されるため、被膜材表面の光沢度も非常に高いものとなる。 However, the method of applying this oxygen blocking agent is employed for hard lining materials, denture base materials, and the like, and this method cannot be directly applied to coating materials for soft lining materials. That is, as the conventional oxygen blocking agent, an aqueous solution containing sodium alginate as a main component or an aqueous solution containing a water-soluble vinyl polymer such as polyvinyl alcohol as a main component is generally used. The formed film is hard and dense, so the surface glossiness is high, and the surface properties are reflected in the coating material, so that the glossiness of the coating material surface is very high.
ところで一方では、アルギン酸ナトリウムの被膜にはほとんど伸び性がないため、乾燥による被膜形成時の収縮により裏装材自体に変形が生じ、その結果として被膜表面にも皺や変形が生じる。その結果、裏装面の適合性が悪くなり、装着感が著しく低下する。 On the other hand, since the coating film of sodium alginate has little stretchability, the lining material itself is deformed by shrinkage during the film formation by drying, and as a result, wrinkles and deformation are also generated on the coating surface. As a result, the conformity of the backing surface is deteriorated, and the wearing feeling is remarkably lowered.
さらに、ポリビニルアルコールのような水溶性ビニル系ポリマーの水溶液の場合、形成した被膜は軟らかく、かなりの伸び性を有するため、乾燥時の収縮による変形は極力抑えられる。しかし、被膜自体が軟質であるためその表面光沢度は低く、そのため必然的に被膜の表面光沢度も低くなり、被膜性能が低下する。
以上述べてきたように、歯科アクリル系軟質材には長期的な耐久性に劣るという欠点があるが、この欠点を解決できる表面滑沢材は未だに提供されていないのが実状である。
そこで、本発明は、歯科アクリル系軟質材の耐久性の向上、より具体的には、歯科アクリル系軟質材に含有されている可塑剤によって容易に可塑化、軟化されることがなく、かつ、可撓性に優れた被膜を形成できるような表面滑沢材を得、該表面滑沢材の特性を最大限に発揮させるための被膜形成方法を得ることを課題とするものである。
As described above, the dental acrylic soft material has the disadvantage that it is inferior in long-term durability, but the actual condition is that a surface lubricant that can solve this drawback has not yet been provided.
Therefore , the present invention improves the durability of the dental acrylic soft material , more specifically, it is not easily plasticized and softened by the plasticizer contained in the dental acrylic soft material, and flexible to obtain a surface lubricating material such as to form a film excellent, it is an object to obtain a film forming method for maximizing the characteristics of the surface lubricating material.
前記課題を解決するために、本発明の歯科アクリル系軟質材用表面滑沢材を用いた被膜形成方法は、歯科アクリル系軟質材用表面滑沢材が、
歯科アクリル系軟質材に、ポリメタクリル酸エステル、多官能性メタクリル酸エステル、光重合開始剤、及び有機溶剤を必須成分とし、
前記歯科アクリル系軟質材用表面滑沢材を塗布し、
自然乾燥させることにより、まず線状構造の一次被膜を形成させ、
前記一次被膜に酸素遮断剤を塗布したのち、
前記一次被膜に可視光線を照射し、光重合反応を起こさせることにより、架橋構造を有する二次被膜に変化させることを特徴とする（請求項１）。
また、前記ポリメタクリル酸エステルが、メタクリル酸メチルとメタクリル酸エチルの共重合体を含むことを特徴とする（請求項２）。
さらに、前記多官能性メタクリル酸エステルが、トリメタクリル酸トリメチロールプロパンを含むことを特徴とする（請求項３）。
In order to solve the above problems, the method for forming a film using the surface lubricant for a dental acrylic soft material according to the present invention is a surface lubricant for a dental acrylic soft material,
To dental acrylic soft material, polymethacrylic acid ester, polyfunctional methacrylic acid ester, photopolymerization initiator, and organic solvent as essential components,
Apply the dental acrylic soft material surface lubricant,
By natural drying, first, a primary film of a linear structure is formed,
After applying an oxygen blocking agent to the primary coating,
By irradiating visible light to the primary coating and causing a photopolymerization reaction, the primary coating is changed to a secondary coating having a crosslinked structure (Claim 1).
The polymethacrylic acid ester contains a copolymer of methyl methacrylate and ethyl methacrylate (claim 2).
Furthermore, the polyfunctional methacrylic acid ester contains trimethylolpropane trimethacrylate (Claim 3).
つぎに、前記酸素遮断剤が、アルギン酸ナトリウム、水溶性ビニル系ポリマー、界面活性剤を含む水溶液であることを特徴とする（請求項４）。 Next , the oxygen blocking agent is an aqueous solution containing sodium alginate, a water-soluble vinyl polymer, and a surfactant (Claim 4 ).
本発明の歯科アクリル系軟質材用表面滑沢材を用いた被膜形成方法を採用することにより、塗布された表面滑沢材が自然乾燥によって線状構造の一次被膜を形成し、一次被膜に酸素遮断材を塗布したのち、一次被膜に可視光線を照射することにより、高度に架橋した二次被膜に変化するため、形成された被膜は分子構造的に非常に緻密となり、また、架橋により高分子間の移動・拡散が極度に抑えられるため耐溶剤性が向上し、可塑剤に対する耐性も大幅に改善できる。 By employing a film forming method using the dental acrylic soft material for surface lubrication material of the present invention, the coated surface lubricant material to form a primary coating of linear structure by natural drying, oxygen primary film After the shielding material is applied, the primary coating is irradiated with visible light to change into a highly crosslinked secondary coating, so that the formed coating is very dense in molecular structure. Since the migration and diffusion between them is extremely suppressed, the solvent resistance is improved and the resistance to the plasticizer can be greatly improved.
その結果、可塑剤含有のアクリル系軟質材表面に塗布した場合、従来の自然乾燥型被膜材のように、形成された被膜が軟質材内部の可塑剤によって容易に可塑化・軟化されることがなく、長期に亘って硬質を維持し得る。そのため、表面は硬質材料特有の光沢度が長期間保持され、また、軟質材内部からの気泡の浮き上がりを阻止するバリヤー機能も向上する。 As a result, when applied to the surface of a plasticizer-containing acrylic soft material, the formed film can be easily plasticized and softened by the plasticizer inside the soft material, as in the case of a conventional air-drying type film material. And can remain rigid for a long time. Therefore, the surface has a glossiness peculiar to the hard material for a long time, and the barrier function for preventing the bubbles from rising from the inside of the soft material is improved.
このように、本発明に使用する表面滑沢材は、アクリル系軟質材の表面に塗布した場合、その表面に長期に亘って緻密で滑沢な、かつ可撓性のある保護被膜を形成・維持できるため、アクリル系軟質材の耐久性が飛躍的に向上する。 Thus, when the surface lubricant used in the present invention is applied to the surface of an acrylic soft material, it forms a dense, smooth and flexible protective coating over the surface for a long time. Because it can be maintained, the durability of the acrylic soft material is dramatically improved.
その上、可視光線の照射に先だって酸素遮断剤を塗布することにより、極めて簡便な方法で、酸素による重合阻害を抑制することができ、被膜の性能を最大限に発揮させることが可能となる。
さらに、酸素遮断剤が、アルギン酸ナトリウム、水溶性ビニル系ポリマー、界面活性剤を含む水溶液であることにより、高い光沢性を保持し、伸び性を付与し、乾燥時の収縮に伴う変形を極力防止することができる。 In addition , by applying an oxygen blocking agent prior to irradiation with visible light, polymerization inhibition by oxygen can be suppressed by a very simple method, and the performance of the coating film can be maximized.
In addition, the oxygen blocking agent is an aqueous solution containing sodium alginate, water-soluble vinyl polymer, and surfactant, so it retains high gloss, imparts stretchability, and prevents deformation due to shrinkage during drying as much as possible. can do.
（ポリメタクリル酸エステル）
本発明に使用する歯科アクリル系軟質材用表面滑沢材には、歯科アクリル系軟質材に、ポリメタクリル酸エステルが必須成分として配合される。この成分は、一次被膜を形成させる上で極めて重要なものである。このポリメタクリル酸エステルとしては、ポリメタクリル酸メチル、ポリメタクリル酸エチル、及びメタクリル酸メチルとメタクリル酸エチルの共重合体が含まれる。これらは単独で使用しても、また、２種以上を併用しても良い。
(Polymethacrylate)
In the surface lubricant for a dental acrylic soft material used in the present invention , a polymethacrylic acid ester is blended as an essential component in the dental acrylic soft material . This component is extremely important in forming the primary film. Examples of the polymethacrylate include polymethyl methacrylate, polyethyl methacrylate, and a copolymer of methyl methacrylate and ethyl methacrylate. These may be used alone or in combination of two or more.
この中で、メタクリル酸メチルとメタクリル酸エチルの共重合体は、ポリメタクリル酸メチル、あるいはポリメタクリル酸エチル単独からなるホモポリマーを使用する場合の欠点を改善し、安定した一時被膜を形成することができるので特に好ましい。 Among these, the copolymer of methyl methacrylate and ethyl methacrylate improves the disadvantages when using a homopolymer composed of polymethyl methacrylate or polyethyl methacrylate alone, and forms a stable temporary film. Is particularly preferable.
すなわち、ポリメタクリル酸メチルは、有機溶剤に溶解した場合の粘度増加が大きく、そのため配合量を少なくせざるを得ないため、一回の塗布で十分な厚みの被膜を確保することが困難となる。また、溶解液は糸引きを起こしやすく、塗布性が著しく悪化する。また、形成された被膜は可撓性が低く、軟質裏装材用の被膜材としては硬くなりすぎる傾向がある。 That is, polymethyl methacrylate has a large increase in viscosity when dissolved in an organic solvent, and therefore the amount of the compound must be reduced, so that it is difficult to ensure a film having a sufficient thickness by a single application. . In addition, the solution tends to cause stringing and the applicability is significantly deteriorated. Further, the formed film has low flexibility and tends to be too hard as a film material for a soft lining material.
また、ポリメタクリル酸エチルは、有機溶剤に対する溶解性は良好で、かつ、粘度増加も少ないことから、溶解量を多くすることが可能となる。また、糸引き現象も少なく、塗布性に関しても問題はない。しかし、ポリメタクリル酸エチルは、可塑剤に対する溶解性がポリメタクリル酸メチルに比べ著しく大きく、そのため、可塑剤に対する耐性の向上を意図した本発明の材料には適当とはいえない。 In addition, polyethyl methacrylate has good solubility in an organic solvent and has a small increase in viscosity, so that the amount of dissolution can be increased. In addition, there is little threading phenomenon, and there is no problem with respect to coating properties. However, polyethyl methacrylate is significantly more soluble in plasticizers than polymethyl methacrylate, and is therefore not suitable for the material of the present invention intended to improve resistance to plasticizers.
一方、メタクリル酸メチルとメタクリル酸エチルの共重合体は、前記のホモポリマーの有する欠点を大幅に解消することができ、本発明の表面滑沢材には最も適している。すなわち、塗布性に関しては、ポリメタクリル酸エチルと同様糸引きも少なく良好であり、可塑剤に対する耐性も、メタクリル酸メチルに比べると劣るものの、本発明の目的には十分満足できるものとなり、また、被膜の可撓性も適度なものとなる。 On the other hand, a copolymer of methyl methacrylate and ethyl methacrylate can greatly eliminate the drawbacks of the homopolymer, and is most suitable for the surface lubricant of the present invention. That is, with respect to the coating properties, as well as polyethyl methacrylate, it is good with less stringing, and the resistance to the plasticizer is inferior to that of methyl methacrylate, but is sufficiently satisfactory for the purpose of the present invention, The flexibility of the coating is also appropriate.
ここで、メタクリル酸メチルとメタクリル酸エチルのモル比は、１対０．１〜１０の広い範囲で設定することができるが、１対０．２〜５の範囲にすることが好ましい。ここで、メタクリル酸エチルの配合比が多すぎると、形成された被膜の可塑剤に対する耐性が劣り、逆に少なすぎると、塗布性が悪くなるとともに、可撓性も低下する。なお、共重合体としては、ブロック共重合体、交互共重合体、グラフト共重合体、ランダム共重合体のいずれであってもよく、特に制限されるものではない。 Here, the molar ratio of methyl methacrylate to ethyl methacrylate can be set in a wide range of 1 to 0.1 to 10, but is preferably in the range of 1 to 0.2 to 5. Here, when there are too many compounding ratios of ethyl methacrylate, the tolerance with respect to the plasticizer of the formed film is inferior, and conversely, when too small, applicability will worsen and flexibility will also fall. The copolymer may be any of a block copolymer, an alternating copolymer, a graft copolymer, and a random copolymer, and is not particularly limited.
このポリメタクリル酸エステルの配合量は、表面滑沢材全体の５〜３０重量％の範囲に設定することが好ましい。ここで、ポリメタクリル酸エステルの配合量が多すぎると、表面滑沢材の粘度が高くなりすぎ、薄くて均一な塗布が困難となり、また、逆に少なすぎると、粘度が低くなりすぎて垂れが生じるとともに、十分な被膜厚さを確保することが困難となる。 The blending amount of the polymethacrylic acid ester is preferably set in the range of 5 to 30% by weight of the entire surface lubricant. Here, if the amount of polymethacrylic acid ester is too large, the viscosity of the surface lubricant becomes too high, making it difficult to apply evenly and thinly. On the other hand, if the amount is too low, the viscosity becomes too low and dripping. As a result, it becomes difficult to ensure a sufficient film thickness.
（多官能性メタクリル酸エステル）
また、本発明に使用する表面滑沢材には、多官能性メタクリル酸エステルが必須成分として配合される。この成分は、可視光線の照射により重合反応を起こし、線状構造の一次被膜を架橋構造の二次被膜に変化させるという、極めて重要な役割を演じるものである。
(Polyfunctional methacrylate)
Moreover, polyfunctional methacrylic acid ester is mix | blended as an essential component with the surface lubricant used for this invention. This component plays a very important role of causing a polymerization reaction by irradiation with visible light and changing the primary coating of the linear structure to the secondary coating of the crosslinked structure.
この多官能性メタクリル酸エステルとしては、ジメタクリル酸エチレングリコール、ジメタクリル酸トリエチレングリコール、ジメタクリル酸１，３−ブチレングリコール、ジメタクリル酸１，６−ヘキサンジオール等の二官能性メタクリル酸エステル、トリメタクリル酸トリメチロールプロパン等の三官能性メタクリル酸エステル、あるいはそれ以上の多官能性メタクリル酸エステルの使用が可能である。それらは単独で使用しても、また、２種以上を併用しても良い。 As this polyfunctional methacrylate, bifunctional methacrylate such as ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. It is possible to use a trifunctional methacrylate such as trimethylolpropane trimethacrylate or a polyfunctional methacrylate having higher functionality. They may be used alone or in combination of two or more.
これらの多官能性メタクリル酸エステルの中では、トリメタクリル酸トリメチロールプロパンが光重合性に優れるとともに、臭い、味がほとんどなく、かつ、口腔粘膜に対する刺激も少ないことから本発明の表面滑沢材には特に好ましい。 Among these polyfunctional methacrylic acid esters, trimethylolpropane trimethacrylate is excellent in photopolymerization, has almost no odor and taste, and has little irritation to the oral mucosa, so that the surface lubricant of the present invention. Is particularly preferred.
この多官能性メタクリル酸エステルの添加量は、前記ポリメタクリル酸エステル量の１／５〜５倍にすることが好ましい。ここで、添加量が１／５よりも少なくなれば、ラジカル重合によって十分な架橋構造が得られなくなるため耐可塑剤性が低下し、また、５倍よりも多くなれば、未重合モノマー量が多くなり、それが可塑剤的な作用をするため、被膜の硬度が低くなり、被膜機能が低下する。 The addition amount of the polyfunctional methacrylate is preferably 1/5 to 5 times the amount of the polymethacrylate. Here, if the addition amount is less than 1/5, a sufficient cross-linked structure cannot be obtained by radical polymerization, so that the plasticizer resistance is lowered. If the addition amount is more than 5 times, the amount of unpolymerized monomer is reduced. Since it increases and it acts as a plasticizer, the hardness of the coating is lowered and the coating function is lowered.
本発明に使用する表面滑沢材には、前記の多官能性メタクリル酸エステルの他に、反応性の向上、物理的性質の改善等の目的で一官能性メタクリル酸エステルを配合しても良く、その例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソブチル、メタクリル酸２−ヒドロキシエチル等があげられる。 The surface lubricant used in the present invention may contain a monofunctional methacrylic acid ester in addition to the polyfunctional methacrylic acid ester described above for the purpose of improving reactivity and improving physical properties. Examples thereof include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate and the like.
これらは単独で使用しても、また、２種以上を併用しても良い。ただし、添加量をあまり多くし過ぎると、多官能性メタクリル酸エステルによる架橋密度が低下し、耐可塑剤性が悪くなるので、その添加量はメタクリル酸エステル全体の５０％より少なくしなければならない。 These may be used alone or in combination of two or more. However, if the amount added is too large, the crosslink density due to the polyfunctional methacrylic acid ester is lowered and the plasticizer resistance is deteriorated. Therefore, the amount added must be less than 50% of the whole methacrylic acid ester. .
（光重合開始剤）
つぎに、本発明に使用する表面滑沢材には、光重合開始剤が必須成分として配合される。ここで使用できる光重合開始剤としては、ベンジル、２，３−ペンタンジオンのような鎖状α−ジケトン化合物、カンファーキノン等の脂環式α−ジケトン化合物、アントラキノン、ナフトキノン等の多核キノン、２−メチル−１，４−ナフトキノン、１，２−ベンズアントラキノン等の多核キノン誘導体等があげられる。これらは、単独で使用しても、２種以上を併用しても良い。
(Photopolymerization initiator)
Next, a photopolymerization initiator is blended as an essential component in the surface lubricant used in the present invention. Examples of the photopolymerization initiator that can be used here include chain α-diketone compounds such as benzyl and 2,3-pentanedione, alicyclic α-diketone compounds such as camphorquinone, polynuclear quinones such as anthraquinone and naphthoquinone, 2 -Polynuclear quinone derivatives such as methyl-1,4-naphthoquinone and 1,2-benzanthraquinone. These may be used alone or in combination of two or more.
この光重合開始剤の添加量は、メタクリル酸エステル量の０．５〜１０重量％の範囲であることが好ましい。ここで、添加量が０．５重量％より少なくなると、可視光線を照射した場合、ラジカル重合反応が十分に起こらなくなり、一方１０重量％より多くしても、増量の効果はほとんど無く、逆に形成された被膜の黄変が著しくなる等の弊害が生じる。 The addition amount of the photopolymerization initiator is preferably in the range of 0.5 to 10% by weight of the amount of methacrylic acid ester. Here, when the addition amount is less than 0.5% by weight, the radical polymerization reaction does not occur sufficiently when irradiated with visible light. On the other hand, even if the addition amount exceeds 10% by weight, there is almost no effect of increasing the amount. Detrimental effects such as significant yellowing of the formed film occur.
（還元剤）
なお、本発明に使用する表面滑沢材には、前記の光重合開始剤の他に、光重合反応をより効率的に行うために、還元剤を配合しても良く、その例として、２−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ビスメタクリロイルオキシエチル−Ｎ−メチルアミン、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸ブチル等の第３級アミン、ジメチルアミノベンズアルデヒド、テレフタルアルデヒド等のアルデヒド類、２−メルカプトベンズオキシザール、デカンチオール等のチオール基を有する化合物等をあげることができる。
(Reducing agent)
In addition to the photopolymerization initiator, the surface lubricant used in the present invention may contain a reducing agent in order to perform the photopolymerization reaction more efficiently. -Tertiary amines such as dimethylaminoethyl methacrylate, N, N-bismethacryloyloxyethyl-N-methylamine, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, dimethylaminobenzaldehyde, terephthalaldehyde, etc. Examples thereof include compounds having a thiol group such as aldehydes, 2-mercaptobenzoxal, and decanethiol.
（有機過酸化物）
さらに、本発明に使用する表面滑沢材には、光重合反応の促進、及び光重合後のポストキュアを意図して有機過酸化物を配合することもできる。本発明に使用できる有機過酸化物としては、ベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ブチルパーオキシベンゾエート、ビス−ｔ−ブチルパーオキシイソフタレート等のパーオキシエステル類、ラウロイルパーオキサイド、ジクミルパーオキサイド等のジアシルパーオキサイド類、メチルエチルケトンパーオキサイド等のケトンパーオキサイド類、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド類等があげられる。
(Organic peroxide)
Furthermore, the surface lubricant used in the present invention can be mixed with an organic peroxide for the purpose of promoting photopolymerization reaction and post-curing after photopolymerization. Examples of the organic peroxide that can be used in the present invention include diacyl peroxides such as benzoyl peroxide and 2,4-dichlorobenzoyl peroxide, and peroxides such as t-butyl peroxybenzoate and bis-t-butyl peroxyisophthalate. Examples thereof include oxyesters, diacyl peroxides such as lauroyl peroxide and dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, and hydroperoxides such as t-butyl hydroperoxide.
（ラジカル重合禁止剤、紫外線吸収剤、色素）
また、本発明に使用する表面滑沢材には、必要に応じてハイドロキノン、ハイドロキノンモノメチルエーテル等のラジカル重合禁止剤、２−ヒドロキシ−４−メトキシベンゾフェノン等の紫外線吸収剤を配合してもよく、また、色素を配合して着色しても良い。
(Radical polymerization inhibitor, UV absorber, dye)
Moreover, the surface lubricant used in the present invention may be blended with a radical polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, or an ultraviolet absorber such as 2-hydroxy-4-methoxybenzophenone, if necessary. Moreover, you may mix and color a pigment | dye.
（有機溶剤）
さらに本発明に使用する表面滑沢材には、有機溶剤を必須成分としている。この成分は、表面滑沢材の塗布性、乾燥時間等に大きく影響するものである。
この有機溶剤としては、前記のポリメタクリル酸エステルを溶解し、かつ沸点が１５０℃以下の、比較的揮発性の高いものから選定すればよく、例えば、塩化メチレン、アセトン、酢酸エチル、酢酸ブチル、酢酸イソブチル、メチルエチルケトン、トルエン等が含まれる。これらは単独で使用しても、あるいは２種以上を併用しても良い。
(Organic solvent)
Furthermore , the surface lubricant used in the present invention contains an organic solvent as an essential component. This component greatly affects the coating properties of the surface lubricant, the drying time, and the like.
The organic solvent may be selected from those that dissolve the polymethacrylic acid ester and have a boiling point of 150 ° C. or less and that are relatively volatile. For example, methylene chloride, acetone, ethyl acetate, butyl acetate, Examples include isobutyl acetate, methyl ethyl ketone, toluene and the like. These may be used alone or in combination of two or more.
有機溶剤の配合量は、使用するポリメタクリル酸エステルの種類等によって異なるが、最終的な表面滑沢材の粘度が１〜５０００センチポイズの範囲になるように設定すればよい。ここで、表面滑沢材の粘度が低すぎると、塗布した場合に垂れが生じ、また、高すぎると薄く均一な塗布が困難となる。 The blending amount of the organic solvent varies depending on the type of polymethacrylic acid ester to be used, but may be set so that the final viscosity of the surface lubricant is in the range of 1 to 5000 centipoise. Here, when the viscosity of the surface lubricant is too low, dripping occurs when it is applied, and when it is too high, thin and uniform application becomes difficult.
（被膜形成方法）
本発明の歯科アクリル系軟質材用表面滑沢材を用いた被膜形成方法は、表面滑沢材の塗布後、自然乾燥によりまず線状構造の一次被膜を形成し、次に一次被膜に酸素遮断剤を塗布したのちその一次被膜に可視光線を照射し、ラジカル重合反応を起こさせることにより、３次元網目構造を有する二次被膜に変化させることを特徴としている。
(Film formation method)
The method of forming a film using the surface lubricant for a dental acrylic soft material of the present invention is to first form a primary film having a linear structure by natural drying after the surface lubricant is applied, and then to block oxygen to the primary film. After the agent is applied, the primary film is irradiated with visible light to cause a radical polymerization reaction, thereby changing to a secondary film having a three-dimensional network structure.
（酸素遮断剤）
この可視光線を照射するにあたっては、一次被膜面に直接可視光線を当てることが考えられるが、被膜性能を最大限に発揮させるために、酸素遮断剤を塗布する。
(Oxygen blocker)
The In irradiation with visible light, it is conceivable Rukoto against direct visible light into primary film surface, in order to exhibit a film for maximum performance, you applied oxygen barrier agent.
本発明では、酸素遮断剤として、アルギン酸ナトリウムと水溶性ビニル系ポリマーの混合系を主成分とした水溶液を使用する。この酸素遮断剤を使用することにより、アルギン酸ナトリウム本来の高い光沢性を保持し、かつ水溶性ビニル系ポリマーにより伸び性を付与することにより、乾燥時の収縮に伴う変形を極力防止することが可能となる。 In the present invention, an aqueous solution mainly composed of a mixed system of sodium alginate and a water-soluble vinyl polymer is used as an oxygen blocking agent. By using this oxygen-blocking agent, it is possible to keep the high gloss inherent in sodium alginate and to prevent deformation due to shrinkage during drying as much as possible by imparting extensibility with a water-soluble vinyl polymer. It becomes.
なお、ここで使用できる水溶性ビニル系ポリマーとしては、ポリビニルアルコール、ポリビニルピロリドン等があげられる。このアルギン酸ナトリウムと水溶性ビニル系ポリマーの配合比は、１対０．１〜１０の広い範囲で設定することができるが、特に１対０．２〜５の範囲に設定することが好ましい。ここで、アルギン酸ナトリウムの量が多すぎると、十分に光沢のある被膜が形成されず、表面滑沢材の表面光沢度も低下する。逆に少なすぎると、被膜の伸びが低下し、乾燥時の収縮に伴う軟質裏装材の変形が大きくなる。 Examples of the water-soluble vinyl polymer that can be used here include polyvinyl alcohol and polyvinyl pyrrolidone. The blending ratio of the sodium alginate and the water-soluble vinyl polymer can be set in a wide range of 1 to 0.1 to 10, but is preferably set to a range of 1 to 0.2 to 5. Here, when there is too much quantity of sodium alginate, a sufficiently glossy film will not be formed and the surface glossiness of a surface lubricant will also fall. On the other hand, if the amount is too small, the elongation of the coating film decreases, and the deformation of the soft lining material accompanying the shrinkage during drying increases.
アルギン酸ナトリウムと水溶性ビニル系ポリマーの合計量は、酸素遮断剤全量に対し１〜１０％の範囲に設定することが好ましい。ここで、配合量が１％より少ないと、連続した乾燥被膜を形成することができなくなり、また、１０％より多くなると、水溶液の粘度が高くなりすぎて薄く均一に塗布することが困難となる。 The total amount of sodium alginate and the water-soluble vinyl polymer is preferably set in the range of 1 to 10% with respect to the total amount of the oxygen blocking agent. Here, if the blending amount is less than 1%, it becomes impossible to form a continuous dry film, and if it exceeds 10%, the viscosity of the aqueous solution becomes too high and it becomes difficult to apply thinly and uniformly. .
（界面活性剤）
本発明に使用する酸素遮断剤には、前記の成分以外に、表面滑沢材に対する濡れ性を改善するため、界面活性剤を必須成分としている。この界面活性剤としては、イオン系、非イオン系のいずれのものでも良い。
(Surfactant)
In addition to the above components, the oxygen blocking agent used in the present invention contains a surfactant as an essential component in order to improve the wettability with respect to the surface lubricant. This surfactant may be either ionic or nonionic.
イオン系としては、アニオン系、カチオン系、両性系のいずれであっても良い。アニオン系としては、テトラデセンスルホン酸ナトリウム等のアルキルスルホン酸塩、あるいはラウリル硫酸ナトリウム等のアルキル硫酸塩、またカチオン系としては、塩化ジステアリルジメチルアンモニウム等のアルキルアンモニウム塩、あるいは塩化セチルピリジニウム等のピリジニウム塩、また両性系としては、ラウリルジメチルアミノ酢酸ベタイン等のアルキルベタイン誘導体が含まれる。 The ionic system may be an anionic system, a cationic system, or an amphoteric system. As an anionic system, an alkyl sulfonate such as sodium tetradecene sulfonate, or an alkyl sulfate such as sodium lauryl sulfate, and as a cationic system, an alkyl ammonium salt such as distearyldimethylammonium chloride, or cetylpyridinium chloride, etc. Pyridinium salts and amphoteric systems include alkylbetaine derivatives such as lauryldimethylaminoacetic acid betaine.
また、非イオン系としては、ポリオキシエチレンオクチルフェニルエーテルのようなポリオキシエチエン誘導体、セスキオレイン酸ソルビタンのようなソルビタン誘導体が含まれる。 In addition, examples of the nonionic system include polyoxyethylene derivatives such as polyoxyethylene octylphenyl ether and sorbitan derivatives such as sorbitan sesquioleate.
これら界面活性剤の添加量は、酸素遮断剤全体の０．０１〜１％の範囲に設定することが好ましく、ここで、添加量が０．０１％より少なくなると、濡れ性を改善するための十分な効果が得られず、１％より多くなると、塗布時に泡が立ちやすくなり、気泡の少ない被膜の形成が困難となる。 The addition amount of these surfactants is preferably set in the range of 0.01 to 1% of the total oxygen blocking agent. Here, when the addition amount is less than 0.01%, the wettability is improved. If a sufficient effect cannot be obtained and the amount exceeds 1%, bubbles are likely to be formed at the time of application, and it is difficult to form a film with few bubbles.
（防腐剤、酸化防止剤、色素）
その他、本発明の酸素遮断剤には、必要に応じてパラオキシ安息香酸エステル等の防腐剤、亜硫酸水素ナトリウム等の酸化防止剤を配合してもよく、また、色素を配合して着色しても良い。
(Preservatives, antioxidants, pigments)
In addition, the oxygen-blocking agent of the present invention may be blended with a preservative such as paraoxybenzoic acid ester or an antioxidant such as sodium hydrogen sulfite as necessary, or may be colored with a pigment. good.
（自然乾燥）
本発明に使用する表面滑沢材は、裏装材表面に塗布し、自然乾燥させた後に可視光線を照射するが、この場合、塗布から可視光線照射までの時間には特に制限はなく、表面滑沢材表面が手指で触れてもべとつかない状態であればよい。
(Natural drying)
The surface lubricant used in the present invention is applied to the surface of the lining material, and is naturally dried and then irradiated with visible light. In this case, the time from application to visible light irradiation is not particularly limited. It is sufficient that the surface of the lubricant is not sticky even if it is touched with fingers.
また、酸素遮断剤の使用に当り、表面滑沢材表面がべとつかない状態になってから塗布すればよい。表面がべとつく状態で酸素遮断剤を塗布すると、表面滑沢材表面に塗布時のはけ跡が付くので注意が必要である。 In addition, when the oxygen blocking agent is used , it may be applied after the surface lubricant surface is not sticky. Care must be taken if an oxygen blocking agent is applied with the surface sticky, as the surface lubricant will have marks on the surface.
（常温＋光重合型）
本発明に使用する表面滑沢材は、前述した常温重合型、加熱重合型、光重合型等のあらゆるタイプのアクリル系軟質裏装材に使用可能であるが、表面滑沢材が光重合型であるため、光重合型の裏装材と組み合わせて使うことが有利である。特に常温＋光重合併用型のアクリル系軟質裏装材に対して使用した場合、一回の可視光線照射で裏装材と表面滑沢材の両方を一度に重合硬化させ得るので、操作効率の面で極めて有益となる。
(Normal temperature + photopolymerization type)
The surface lubricant used in the present invention can be used for all types of acrylic soft lining materials such as the aforementioned room temperature polymerization type, heat polymerization type, and photopolymerization type, but the surface lubricant is a photopolymerization type. Therefore, it is advantageous to use in combination with a photopolymerization type lining material. In particular, when used for acrylic soft lining materials of room temperature + photopolymerization combined type, both the lining material and the surface lubricant can be polymerized and cured at one time with a single visible light irradiation. It becomes extremely useful in terms of the aspect.
（光重合型）
現在、光重合型裏装材としては、一成分系のペースト状のものが一般的であり、その場合、義歯床粘膜面に材料を盛り上げ、口腔内に装着して筋圧形成した後に、口腔内より撤去し、可視光線照射を行う。この際、口腔内から取り出した時点では材料はペースト状のままであり、わずかな力でも変形が生じるという、極めて不安定な状態にある。そのため、口腔内から撤去後の裏装面に直接表面滑沢材を塗布することができず、従って、まず裏装材のみに可視光線を照射して重合させ、その後、表面滑沢材を塗布して再照射するという、２段照射法を採用せざるを得ない。
(Photopolymerization type)
At present, as a photopolymerization type lining material, a one-component paste is generally used. In this case, after the material is raised on the mucosal surface of the denture base and attached to the oral cavity to form muscle pressure, Remove from inside and irradiate with visible light. At this time, when the material is taken out from the oral cavity, the material remains in a paste state, and the material is in an extremely unstable state in which deformation occurs even with a slight force. Therefore, the surface lubricant cannot be applied directly to the lining surface after removal from the oral cavity. Therefore, only the lining material is irradiated with visible light and polymerized, and then the surface lubricant is applied. Then, the two-stage irradiation method of irradiating again must be adopted.
一方、常温＋光重合併用型の裏装材の場合、口腔内での重合反応によりモチ状の状態が得られるため、口腔内から撤去後の裏装材表面に表面滑沢材を直接塗布することができ、その後一回の可視光線の照射で裏装材、表面滑沢材の両者を同時に硬化させることが可能となる。この場合、操作時間が大幅に短縮できることのほか、裏装材と表面滑沢材の界面で共重合が起こり、接着界面の一体化が実現するため、接着強度向上の面からも有利となる。 On the other hand, in the case of a room temperature + photopolymerization type lining material, a mochi-like state is obtained by the polymerization reaction in the oral cavity, so the surface lubricant is directly applied to the lining material surface after removal from the oral cavity Then, both the backing material and the surface lubricant can be simultaneously cured by a single irradiation with visible light. In this case, not only can the operation time be greatly shortened, but also copolymerization occurs at the interface between the backing material and the surface lubricant, and integration of the adhesive interface is realized, which is advantageous from the viewpoint of improving the adhesive strength.
（常温ゲル化型）
また、本発明に使用する表面滑沢材は、常温ゲル化型軟質裏装材、すなわち粘膜調整材（機能印象材）に対しても効果的に使用することができる。この場合、裏装後の表面に直ちに塗布してもかまわないが、表面滑沢材によって粘膜調整材の特性である流動変形性が阻害されることが懸念されるため、粘膜調整、あるいは機能印象採得が終了した時点で塗布した方が良い。この方法を採用することにより、動的な機能印象面をそのまま軟質裏装材として長期に亘って使用することが可能となり、臨床上極めて有益となる。
(Normal temperature gelation type)
In addition, the surface lubricant used in the present invention can also be effectively used for a normal temperature gelled soft lining material, that is, a mucous membrane adjusting material (functional impression material). In this case, it may be applied immediately to the surface after lining, but there is concern that the surface lubricant may impair the flow deformability, which is a characteristic of the mucosa adjusting material. It is better to apply at the time when the collection is completed. By adopting this method, the dynamic functional impression surface can be used as a soft lining material for a long period of time, which is extremely useful clinically.
（従来方法）
従来の方法では、機能印象採得後の材料は、そのすべてを削り取り、間接的な方法で新たな軟質、あるいは硬質の裏装材に置き換えることが必要であった。それは、従来の粘膜調整材（機能印象材）が材質的に極めて不安定で、長期の使用に耐え得なかったからである。すなわち、粘膜調整材は、口腔内で使用される間に材料内部から可塑剤が徐々に溶出することにより劣化し、また、材料内部の気泡が徐々に表面に浮上することにより表面が非常に粗となり、汚れや細菌が付着しやすくなる。
(Conventional method)
In the conventional method, it is necessary to scrape all of the material after obtaining the functional impression and replace it with a new soft or hard lining material by an indirect method. This is because the conventional mucous membrane adjusting material (functional impression material) is extremely unstable in terms of material and cannot withstand long-term use. In other words, the mucosa-adjusting material deteriorates when the plasticizer gradually elutes from the inside of the material while it is used in the oral cavity, and the surface is very rough because bubbles inside the material gradually rise to the surface. It becomes easy to adhere dirt and bacteria.
しかし、本発明に使用する表面滑沢材を塗布し、表面に硬くて緻密な、かつ、高度に架橋した３次元網目構造を有する被膜を形成させることにより、粘膜調整材の耐久性が飛躍的に向上し、そのため機能印象採得後もそのまま軟質裏装材として長期に亘って使用することが可能となる。 However, by applying the surface lubricant used in the present invention to form a hard, dense and highly crosslinked film having a three-dimensional network structure on the surface, the durability of the mucosal preparation material is dramatically improved. Therefore, even after obtaining a functional impression, it can be used as a soft lining material for a long time.
つぎに、本発明の歯科アクリル系軟質材用表面滑沢材を用いた被膜形成方法の具体的実施例について説明する。ただし、本発明は、ここに示した実施例に限定されるものではない。本実施例においては、以下に示す４種類のアクリル系軟質材に表面滑沢材を被膜する場合を示す。 Next, specific examples of the method for forming a coating film using the surface lubricant for dental acrylic soft material of the present invention will be described. However, the present invention is not limited to the embodiments shown here. In a present Example, the case where a surface lubricant material is coat | covered on four types of acrylic soft materials shown below is shown.
（試験片作製）
つぎのようにして試験片を作製した。
（常温重合型）
ブチルフタリルブチルグリコレート７５部、メタクリル酸メチル７部、メタクリル酸イソブチル６部、メタクリル酸ｎ−ブチル５部、メタクリル酸２−ヒドロキシエチル４部、流動パラフィン２部、Ｎ，Ｎ−ジメチルパラトルイジン１部をビーカーに入れ、攪拌・混合して液剤を調製した。
(Test piece preparation)
A test piece was prepared as follows.
(Normal temperature polymerization type)
75 parts of butylphthalyl butyl glycolate, 7 parts of methyl methacrylate, 6 parts of isobutyl methacrylate, 5 parts of n-butyl methacrylate, 4 parts of 2-hydroxyethyl methacrylate, 2 parts of liquid paraffin, N, N-dimethylparatoluidine One part was put into a beaker, and stirred and mixed to prepare a liquid.
平均粒子径３０μｍ、平均分子量２５万のポリメタクリル酸エチル粉末９９．４部、ベンゾイルパーオキサイド０．５部、アエロジルＲ９７２の０．１部をボールミルに入れ、１０分間混合して粉剤を調製した。 99.4 parts of polyethyl methacrylate powder having an average particle size of 30 μm and an average molecular weight of 250,000, 0.5 part of benzoyl peroxide, and 0.1 part of Aerosil R972 were placed in a ball mill and mixed for 10 minutes to prepare a powder.
粉剤２部に対し、液剤１．８部を混合した材料を、内寸２０×２０×３ｍｍのテフロン（登録商標）製型に充填し、上面をテフロン（登録商標）板で圧接した。
２０分間放置した後、型から取り出し、２０×２０×３ｍｍの試験片を得た。
A material obtained by mixing 1.8 parts of the liquid agent with 2 parts of the powder was filled into a Teflon (registered trademark) mold having an inner size of 20 × 20 × 3 mm, and the upper surface was press-contacted with a Teflon (registered trademark) plate.
After leaving for 20 minutes, it was removed from the mold to obtain a test piece of 20 × 20 × 3 mm.
（加熱重合型）
ブチルフタリルブチルグリコレート７５部、メタクリル酸メチル２０部、メタクリル酸２−ヒドロキシエチル５部をビーカーに入れ、攪拌・混合して液剤を調整した。
(Heat polymerization type)
75 parts of butyl phthalyl butyl glycolate, 20 parts of methyl methacrylate and 5 parts of 2-hydroxyethyl methacrylate were put into a beaker, and stirred and mixed to prepare a liquid agent.
平均粒子径３０μｍ、平均分子量３０万のポリメタクリル酸メチル粉末９９．４部、ベンゾイルパーオキサイド０．５部、アエロジルＲ９７２の０．１部をボールミルに入れ、１０分間混合して粉剤を調製した。 A powder was prepared by placing 99.4 parts of polymethyl methacrylate powder having an average particle size of 30 μm and an average molecular weight of 300,000, 0.5 part of benzoyl peroxide, and 0.1 part of Aerosil R972 in a ball mill and mixing for 10 minutes.
粉剤２部に対し、液剤１．４部を混合したモチ状材料を、内寸２０×２０×３ｍｍの石膏型の中に加圧填入し、１００℃の沸騰水中で１時間加熱した。
常温まで冷却した後、型から取り出し、２０×２０×３ｍｍの試験片を得た。
A mochi-like material obtained by mixing 1.4 parts of the liquid with 2 parts of the powder was press-filled into a gypsum mold having an internal size of 20 × 20 × 3 mm and heated in boiling water at 100 ° C. for 1 hour.
After cooling to room temperature, it was removed from the mold and a 20 × 20 × 3 mm test piece was obtained.
（常温＋光重合併用型）
ブチルフタリルブチルグリコレート７９部、メタクリル酸メチル８部、メタクリル酸イソブチル８部、メタクリル酸２−ヒドロキシエチル４部、Ｎ，Ｎ−ジメチルパラトルイジン１部をビーカーに入れ、攪拌・混合して液剤を調製した。
(Normal temperature + photopolymerization combined type)
79 parts of butylphthalyl butyl glycolate, 8 parts of methyl methacrylate, 8 parts of isobutyl methacrylate, 4 parts of 2-hydroxyethyl methacrylate and 1 part of N, N-dimethylparatoluidine are placed in a beaker and stirred and mixed to form a solution. Was prepared.
平均粒子径３０μｍ、平均分子量２５万のポリメタクリル酸メチル粉末９９．４部、ベンゾイルパーオキサイド０．５部、カンファーキノン０．３部、アエロジルＲ９７２の０．１部をボールミルに入れ、１０分間混合して粉剤を調製した。 99.4 parts of polymethyl methacrylate powder having an average particle diameter of 30 μm and an average molecular weight of 250,000, 0.5 part of benzoyl peroxide, 0.3 part of camphorquinone and 0.1 part of Aerosil R972 are placed in a ball mill and mixed for 10 minutes. Thus, a powder was prepared.
粉剤２部に対し、液剤１．８部を混合した材料を、内寸２０×２０×３ｍｍのテフロン（登録商標）製型に充填し、上面をテフロン（登録商標）板で圧接した。
２０分間放置した後、型から取り出し、２０×２０×３ｍｍの試験片を得た。
A material obtained by mixing 1.8 parts of the liquid agent with 2 parts of the powder was filled into a Teflon (registered trademark) mold having an inner size of 20 × 20 × 3 mm, and the upper surface was press-contacted with a Teflon (registered trademark) plate.
After leaving for 20 minutes, it was removed from the mold to obtain a test piece of 20 × 20 × 3 mm.
（常温ゲル化型）
ブチルフタリルブチルグリコレート８５部、エチルアルコール１２部、メタクリル酸イソブチル３部をビーカーに入れ、攪拌・混合して液剤を調製した。
(Normal temperature gelation type)
85 parts of butyl phthalyl butyl glycolate, 12 parts of ethyl alcohol and 3 parts of isobutyl methacrylate were placed in a beaker, and stirred and mixed to prepare a liquid.
平均粒子径３０μｍ、平均分子量２５万のポリメタクリル酸エチル粉末９９．９部、アエロジルＲ９７２の０．１部をボールミルに入れ、１０分間混合して粉剤を調製した。 A powder was prepared by placing 99.9 parts of polyethyl methacrylate powder having an average particle size of 30 μm and an average molecular weight of 250,000 in a ball mill and 0.1 part of Aerosil R972 for 10 minutes.
粉剤２部に対し、液剤１．４部を混合した材料を、内寸２０×２０×３ｍｍのテフロン（登録商標）製型に充填し、上面をテフロン（登録商標）板で圧接した。
２０分間放置した後、型から取り出し、２０×２０×３ｍｍの試験片を得た。
A material obtained by mixing 1.4 parts of the liquid agent with 2 parts of the powder was filled in a Teflon (registered trademark) mold having an inner size of 20 × 20 × 3 mm, and the upper surface was press-contacted with a Teflon (registered trademark) plate.
After leaving for 20 minutes, it was removed from the mold to obtain a test piece of 20 × 20 × 3 mm.
（試験方法）
次に、ここで実施した試験方法を示す。
（光沢度試験）
塗布直後、及び３７℃水中に１ヶ月浸漬後の被膜面の光沢度につき、堀場製作所製光沢計（グロスチェッカーＩＧ・３３０）を用いて測定した。
(Test method)
Next, the test method implemented here is shown.
(Glossiness test)
The glossiness of the coated surface immediately after coating and after immersion for 1 month in 37 ° C. water was measured using a gloss meter (Gloss Checker IG • 330) manufactured by Horiba.
（気泡の数測定試験）
塗布した試験片を、水２００ｍＬ中に義歯洗浄剤（酵素、漂白剤、発泡剤、界面活性剤等を含有する中性タイプの錠剤）を１錠入れた液に浸漬し、そのまま２４時間放置した。同様の操作を３回繰り返し、トータル７２時間の浸漬を行った後、被膜表面に浮き上がった気泡の数を測定した。
(Bubble number measurement test)
The applied test piece was immersed in a solution containing a denture cleaning agent (neutral type tablet containing enzyme, bleach, foaming agent, surfactant, etc.) in 200 mL of water and left as it was for 24 hours. . The same operation was repeated three times, and after immersion for a total of 72 hours, the number of bubbles floating on the coating surface was measured.
（可塑剤溶出量算出試験）
塗布した試験片をデシケータ内に保管し、恒量となるまで乾燥した。
恒量となった試験片を３７℃の蒸留水中に１週間浸漬し、再度、デシケータ内で恒量となるまで乾燥した。
次式により、試験片の可塑剤溶出量を算出した。
可塑剤溶出量（Ｗｔ％）＝（ｍ１−ｍ２）／ｍ１
ここで、ｍ１：水に浸漬する前の試験片の重さ（ｇ）
ｍ２：水中に１週間浸漬後、乾燥した試験片の重さ（ｇ）
(Plasticizer elution amount calculation test)
The applied test piece was stored in a desiccator and dried to a constant weight.
The test piece which became constant weight was immersed in 37 degreeC distilled water for 1 week, and it dried until it became constant weight in the desiccator again.
The plasticizer elution amount of the test piece was calculated by the following formula.
Plasticizer elution amount (Wt%) = (m 1 −m 2 ) / m 1
Here, m 1 : Weight of test specimen before being immersed in water (g)
m 2 : Weight (g) of a test piece dried after being immersed in water for 1 week
（義歯床の適合性試験：浮き上がり量測定試験）
治具を用いた間接法で上顎総義歯の内面を２ｍｍ厚となるように、前述した常温ゲル化型軟質裏装材を用いて裏装した。裏装面に表面滑沢材を塗布し、３分間自然乾燥させた後、さらに酸素遮断剤を塗布し、亀水化学工業株式会社製の歯科技工用可視光線重合器（商品名リベースライト２＝中心波長４７０ｎｍ、ランプ定格１００Ｖ２７Ｗ２本）で１０分間光照射した。
(Compatibility test of denture base: lift-up measurement test)
The inner surface of the maxillary complete denture was backed by the indirect method using a jig so as to have a thickness of 2 mm using the above-described room temperature gelation type soft backing material. A surface lubricant is applied to the lining surface, and after naturally drying for 3 minutes, an oxygen blocking agent is further applied, and a visible light polymerizer (trade name Rebase Light 2 = The light was irradiated for 10 minutes at a center wavelength of 470 nm and a lamp rating of 100V27W.
光照射後、水洗して酸素遮断剤を除去し、義歯を裏装時に使用した石膏作業模型に戻した。
口蓋後縁中央部の模型からの浮き上がり量を測定し、その浮き上がり量によって、義歯床の適合性を評価した。
After light irradiation, it was washed with water to remove the oxygen blocking agent, and the denture was returned to the gypsum work model used for lining.
The amount of lift from the model at the center of the palate trailing edge was measured, and the suitability of the denture base was evaluated based on the amount of lift.
酢酸エチル７８部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝２：３）１２部、トリメタクリル酸トリメチロールプロパン９．６部、カンファーキノン０．４部を攪拌・混合して表面滑沢材を調製した。 78 parts of ethyl acetate, 12 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 2: 3), 9.6 parts of trimethylolpropane trimethacrylate, and 0.4 part of camphorquinone A surface lubricant was prepared by stirring and mixing.
水９４．４部に重合度１７００のポリビニルアルコール４部、アルギン酸ナトリウム１．４部、ラウリル硫酸ナトリウム０．２部を攪拌・混合して酸素遮断剤を調製した。 An oxygen blocking agent was prepared by stirring and mixing 94.4 parts of water with 4 parts of polyvinyl alcohol having a polymerization degree of 1700, 1.4 parts of sodium alginate, and 0.2 part of sodium lauryl sulfate.
前述した常温重合型試験片の表面に前記表面滑沢材を一回塗布し、３分間大気中で自然乾燥させた。
次に、前記の酸素遮断剤を１回塗布し、直ちに前記可視光線重合器で１０分間光照射した。
可視光線の照射後、水洗して酸素遮断剤を除去し、前述した方法で光沢度試験、気泡の数測定試験、及び可塑剤溶出量算出試験を実施した。試験結果を表１にまとめて示す。
The surface lubricant was applied once to the surface of the above-mentioned room temperature polymerization type test piece, and was naturally dried in the air for 3 minutes.
Next, the oxygen blocking agent was applied once and immediately irradiated with light in the visible light polymerization vessel for 10 minutes.
After irradiation with visible light, it was washed with water to remove the oxygen blocking agent, and a glossiness test, a bubble number measurement test, and a plasticizer elution amount calculation test were performed by the methods described above. The test results are summarized in Table 1.
酢酸エチル７８部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝２：３）１２部、ジメタクリル酸エチレングリコール９．６部、カンファーキノン０．４部を攪拌・混合して表面滑沢材を調製した。 Stirring 78 parts of ethyl acetate, 12 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 2: 3), 9.6 parts of ethylene glycol dimethacrylate, and 0.4 part of camphorquinone -A surface lubricant was prepared by mixing.
前述した加熱重合型試験片の表面に前記表面滑沢材を一回塗布し、３分間大気中で自然乾燥させた。
次に、実施例１で使用した酸素遮断剤を１回塗布し、直ちに前記可視光線重合器で１０分間可視光線を照射した。
可視光線の照射後、水洗して酸素遮断剤を除去し、前述した方法で光沢度試験、気泡の数測定試験、及び可塑剤溶出量算出試験を実施した。試験結果を表１にまとめて示す。
The surface lubricant was applied once to the surface of the heat polymerization test piece described above, and was naturally dried in the air for 3 minutes.
Next, the oxygen blocking agent used in Example 1 was applied once and immediately irradiated with visible light for 10 minutes in the visible light polymerization device.
After irradiation with visible light, it was washed with water to remove the oxygen blocking agent, and a glossiness test, a bubble number measurement test, and a plasticizer elution amount calculation test were performed by the methods described above. The test results are summarized in Table 1.
酢酸エチル７７．６部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝２：３）１２部、ジメタクリル酸トリエチレングリコール９．６部、カンファーキノン０．４部、メタクリル酸ジメチルアミノエチル０．４部を攪拌・混合して表面滑沢材を調製した。 77.6 parts of ethyl acetate, 12 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 2: 3), 9.6 parts of triethylene glycol dimethacrylate, 0.4 of camphorquinone A surface lubricant was prepared by stirring and mixing 0.4 parts of dimethylaminoethyl methacrylate.
前述した常温＋光重合併用型試験片の表面に前記表面滑沢材を一回塗布し、３分間大気中で自然乾燥させた。
次に、実施例１で使用した酸素遮断剤を１回塗布し、直ちに前記可視光線重合器で１０分間可視光線を照射した。
可視光線の照射後、水洗して酸素遮断剤を除去し、前述した方法で光沢度試験、気泡の数測定試験、及び可塑剤溶出量算出試験を実施した。試験結果を表１にまとめて示す。
The surface lubricant was applied once to the surface of the above-mentioned normal temperature + photopolymerization combined type test piece, and was naturally dried in the air for 3 minutes.
Next, the oxygen blocking agent used in Example 1 was applied once and immediately irradiated with visible light for 10 minutes in the visible light polymerization device.
After irradiation with visible light, it was washed with water to remove the oxygen blocking agent, and a glossiness test, a bubble number measurement test, and a plasticizer elution amount calculation test were performed by the methods described above. The test results are summarized in Table 1.
酢酸エチル７７．６部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝１：１）１２部、トリメタクリル酸トリメチロールプロパン９．０部、メタクリル酸２−ヒドロキシエチル１．０部、カンファーキノン０．４部を攪拌・混合して表面滑沢材を調製した。 77.6 parts of ethyl acetate, 12 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 1: 1), 9.0 parts of trimethylolpropane trimethacrylate, 2-hydroxy methacrylate A surface lubricant was prepared by stirring and mixing 1.0 part of ethyl and 0.4 part of camphorquinone.
前述した常温ゲル化型試験片の表面に前記表面滑沢材を一回塗布し、３分間大気中で自然乾燥させた。
次に、実施例１で使用した酸素遮断剤を１回塗布し、直ちに前記可視光線重合器で１０分間可視光線を照射した。
可視光線の照射後、水洗して酸素遮断剤を除去し、前述した方法で光沢度試験、気泡の数測定試験、及び可塑剤溶出量算出試験を実施した。試験結果を表１にまとめて示す。
［比較例１］
The surface lubricant was applied once to the surface of the aforementioned normal temperature gelled test piece and allowed to air dry in the air for 3 minutes.
Next, the oxygen blocking agent used in Example 1 was applied once and immediately irradiated with visible light for 10 minutes in the visible light polymerization device.
After irradiation with visible light, it was washed with water to remove the oxygen blocking agent, and a glossiness test, a bubble number measurement test, and a plasticizer elution amount calculation test were performed by the methods described above. The test results are summarized in Table 1.
[Comparative Example 1]
酢酸エチル８６部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝２：３）１４部を攪拌・混合して表面滑沢材を調製した。 A surface lubricant was prepared by stirring and mixing 86 parts of ethyl acetate and 14 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 2: 3).
前述した常温重合型試験片の表面に前記表面滑沢材を一回塗布し、１０分間大気中で自然乾燥させた後、前述した方法で光沢度試験、気泡の数測定試験、及び可塑剤溶出量算出試験を実施した。試験結果を表１にまとめて示す。
［比較例２］
The surface lubricant is applied once to the surface of the above-mentioned room temperature polymerization type test piece, and after naturally drying in the air for 10 minutes, the gloss test, the bubble number measurement test, and the plasticizer elution are performed by the above-described methods. A quantity calculation test was conducted. The test results are summarized in Table 1.
[Comparative Example 2]
実施例１と同様の方法で試験片を作製し、実施例１と同様の方法で試験を実施した。ただし、ここでは酸素遮断剤を塗布することなく、光照射を行った。試験結果を表１にまとめて示す。 A test piece was prepared in the same manner as in Example 1, and the test was conducted in the same manner as in Example 1. However, light irradiation was performed without applying an oxygen blocking agent here. The test results are summarized in Table 1.
酢酸エチル７８部、平均分子量５０万のメタクリル酸メチルとメタクリル酸エチルの共重合体（モル比＝２：３）１２部、トリメタクリル酸トリメチロールプロパン８．１部、メタクリル酸２−ヒドロキシエチル１．５部、カンファーキノン０．４部を攪拌・混合して表面滑沢材を調製した。 78 parts of ethyl acetate, 12 parts of a copolymer of methyl methacrylate and ethyl methacrylate having an average molecular weight of 500,000 (molar ratio = 2: 3), 8.1 parts of trimethylolpropane trimethacrylate, 2-hydroxyethyl methacrylate 1 5 parts and 0.4 part of camphorquinone were stirred and mixed to prepare a surface lubricant.
前記表面滑沢材を用い、実施例１と同様の方法で試験片を作製し、光沢度試験を行った。
また、前記表面滑沢材及び実施例１と同様の酸素遮断剤を用いて義歯床の適合性試験を行った。試験結果を表１にまとめて示す。
［比較例３］
Using the surface lubricant, a test piece was prepared in the same manner as in Example 1, and a gloss test was conducted.
In addition, a denture base compatibility test was performed using the surface lubricant and the same oxygen blocking agent as in Example 1. The test results are summarized in Table 1.
[Comparative Example 3]
水９７．１部、アルギン酸ナトリウム２．７部、ラウリル硫酸ナトリウム０．２部を溶解して酸素遮断剤を調製した。この酸素遮断剤を用い、実施例５と同様にして光沢度試験、及び適合性試験を実施した。試験結果を表１にまとめて示す。
［比較例４］
97.1 parts of water, 2.7 parts of sodium alginate, and 0.2 parts of sodium lauryl sulfate were dissolved to prepare an oxygen blocking agent. Using this oxygen-blocking agent, a gloss test and a compatibility test were conducted in the same manner as in Example 5. The test results are summarized in Table 1.
[Comparative Example 4]
水９１．８部、重合度１７００のポリビニルアルコール８部、ラウリル硫酸ナトリウム０．２部を溶解して酸素遮断剤を調製した。この酸素遮断剤を用い、実施例５と同様にして光沢度試験、及び適合性試験を実施した。試験結果を表１にまとめて示す。 An oxygen blocking agent was prepared by dissolving 91.8 parts of water, 8 parts of polyvinyl alcohol having a polymerization degree of 1700, and 0.2 parts of sodium lauryl sulfate. Using this oxygen-blocking agent, a gloss test and a compatibility test were conducted in the same manner as in Example 5. The test results are summarized in Table 1.
（試験結果）
実施例１〜４に示したように、常温重合型、加熱重合型、光重合型、常温ゲル化型のいずれのアクリル系軟質裏装材に対しても、本発明の表面滑沢材を使用し、本発明の方法で被膜形成させた場合、表面の光沢度は非常に高くなり、かつこの光沢は３７℃の水中に１ヶ月間浸漬した後でもほとんど低下することがない。また、被膜自体が硬質を保持するため、気泡の浮き上がりを阻止するバリヤー効果も極めて高くなる。さらに、耐可塑性が向上するため、可塑剤の溶出量も少なくなる。 As shown in Examples 1 to 4, the surface lubricant of the present invention is used for any acrylic soft lining material of room temperature polymerization type, heat polymerization type, photopolymerization type, and room temperature gelation type. However, when a film is formed by the method of the present invention, the glossiness of the surface becomes very high, and this gloss hardly decreases even after being immersed in water at 37 ° C. for one month. In addition, since the coating itself retains hardness, the barrier effect for preventing the bubbles from rising is extremely high. Furthermore, since the plastic resistance is improved, the amount of plasticizer eluted is also reduced.
一方、比較例１は、自然乾燥型の表面滑沢材を使用した場合の例であるが、形成された被膜が、可塑剤によって徐々に軟化されていくため、初期の光沢度は高いにもかかわらず、水中１ヶ月浸漬後の光沢度は著しく低くなり、また、気泡の浮き上がりも多くなる。また、可塑剤の溶出量も多くなる。 On the other hand, Comparative Example 1 is an example in the case of using a natural drying type surface lubricant, but since the formed coating is gradually softened by the plasticizer, the initial glossiness is high. Regardless, the glossiness after immersion in water for one month is remarkably low, and the bubbles rise more. In addition, the amount of plasticizer eluted increases.
比較例２は、酸素遮断剤を塗布しなかった場合の例であるが、表面の重合が阻害されるため、水中浸漬により表面光沢度は低くなり、また、被膜自体の硬さも低下するため、気泡の浮き上がりを阻止する作用も低下する。また、可塑剤の溶出量も若干多くなる。 Comparative Example 2 is an example in the case where the oxygen blocking agent was not applied, but since surface polymerization is inhibited, surface glossiness is reduced by immersion in water, and the hardness of the coating itself is also reduced. The effect of preventing the bubbles from rising is also reduced. In addition, the amount of plasticizer eluted is slightly increased.
実施例５は、実施例１と同じ酸素遮断剤を使用した場合であるが、表面の光沢度は高く、義歯の適合性試験を実施した場合、浮き上がり量は非常に少なく、適合性は極めて良好である。 In Example 5, the same oxygen blocking agent as in Example 1 was used, but the glossiness of the surface was high, and when the denture compatibility test was performed, the amount of lift was very small and the compatibility was very good. It is.
比較例３は、酸素遮断剤としてアルギン酸ナトリウム系のものを使用した例であるが、この場合、表面光沢度は非常に高くなるが、裏装材表面に変形が生じるため、裏装後の義歯床の適合性が悪くなる。 Comparative Example 3 is an example in which a sodium alginate-based oxygen blocking agent is used. In this case, the surface glossiness is very high, but deformation occurs on the lining material surface. The conformity of the floor is poor.
比較例４は、酸素遮断剤としてポリビニルアルコール系のものを使用した例であるが、この場合、浮き上がり量が少なく、裏装後の義歯床の適合性は良好であるが、表面滑沢材の光沢度はかなり劣ったものとなる。 Comparative Example 4 is an example using a polyvinyl alcohol-based oxygen-blocking agent. In this case, the amount of lifting is small, and the denture base after the lining has good compatibility. The glossiness is considerably inferior.
Claims (4)
自然乾燥させることにより、まず線状構造の一次被膜を形成させ、
前記一次被膜に酸素遮断剤を塗布したのち、
前記一次被膜に可視光線を照射し、光重合反応を起こさせることにより、架橋構造を有する二次被膜に変化させることを特徴とする歯科アクリル系軟質材用表面滑沢材を用いた被膜形成方法。 To the dental acrylic soft material, apply a surface lubricant for a dental acrylic soft material having polymethacrylate, polyfunctional methacrylate, photopolymerization initiator, and organic solvent as essential components,
By natural drying, first, a primary film of a linear structure is formed,
After applying an oxygen blocking agent to the primary coating,
A method for forming a coating film using a surface lubricant for a dental acrylic soft material, wherein the primary coating film is irradiated with visible light to cause a photopolymerization reaction, thereby changing to a secondary coating film having a crosslinked structure. .
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