CN1030785C - Aqueous dispersion of cationic polymer - Google Patents
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- CN1030785C CN1030785C CN 91108602 CN91108602A CN1030785C CN 1030785 C CN1030785 C CN 1030785C CN 91108602 CN91108602 CN 91108602 CN 91108602 A CN91108602 A CN 91108602A CN 1030785 C CN1030785 C CN 1030785C
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Abstract
An aqueous dispersion of a cationic polymer is obtained by reacting (a) I part by wt% of pellets or powder of an ethylene copolymer comprising 40 to 80% by weight of ethylene and 20 to 60% of at least one aminoalkyl acrylamide comonomer of formula: wherein R1 is hydrogen or methyl; R2 and R3 each is hydrogen or C1-4 alkyl; and n is an integer of 2 to 4, and optionally up to 20 wt% of a comonomer (e.g. an acrylate) and having a melt index (JIS K-6760) of 10 to 1,000 g/10 min, with (b) 0.5 - 2 parts hydrochloric acid in water, to form a quaternary salt, and addition-reacting this salt with an epihalohydrin compound at 20 - 100 DEG C, and optionally further reacting with 0.2 - 2 parts of an alkylolamine compound (e.g. diethanolamine). The dispersion provides a coating film having an improved electrical conductivity in an electrographic material, or when included in paper it simultaneously improves degree of sizing and wet strength thereof.
Description
The invention relates to by aqueous dispersion and add to the sized paper that a kind of slush pulp and drying obtain a kind of cationic polymer.
The aqueous dispersion of cationic polymer of the present invention is used to form a kind of softness films with antistatic or semiconductor waterproof.This filming can be by with this aqueous dispersion dipping or apply a matrix, for example paper and plastic sheeting and dry and form.
In a kind of important use, cationic polymeric dispersion of the present invention is coated to a kind of electric imaging record series of strata, wherein on electric imaging recording materials, form latent image by electric signal, described electric imaging recording materials include the carrier of an electric insulation, one conductive layer and a recording layer are arranged on it in order, and set has a kind of charged toner powder to obtain visible image above it.In this application, aqueous polymer dispersion of the present invention can be used from conductive layer so that the electric imaging recording materials with good film characteristics and writing function to be provided individually or with a kind of metal-oxide semiconductor (MOS) one.
In another kind was used, cationic polymeric dispersion of the present invention was useful as the additive in the papermaking.In more detail, in the forming process of sheet material, aqueous dispersion of the present invention can add under neutrality or the alkali condition with colloidality and wet strength on improving, thereby is applicable to corrugated board of producing paper container, waterproof enhancing or the like.In addition, cationic polymeric dispersion of the present invention is hopeful to utilize it to reduce the effect of surface resistivity or specific insulation and be applied to wrapping paper of dustproof paper, IC (integrated circuit) parts or the like; Utilize its heat-sealing ability to be applied on the heat seal paper or the like; And the characteristic of utilizing its set dyestuff or pigment is applied on the painted matrix that laminated decorative panel and coating paper use.
Provide several aqueous polymer dispersions as conductive agent or antistatic additive, carried out drying then with these aqueous dispersion dippings or coating insulating body (for example paper and plastic sheeting).In these aqueous dispersions, a kind of aqueous dispersion of known cationic styrene polymer becomes quaternary salt to obtain by making chloromethylated polystyrene with a kind of reactive tertiary amine, and this has description in as Japanese patent laid-open publication gazette 7871/73 and 34150/74.But,,, surface conductivity is caused harmful effect in the preservation process so matrix is easy to curl or film be easy to break owing to applying cationic styrene polymer and the dry shortage flexibility of filming that forms on the paper or on the plastic sheeting.
Be used at cationic polymer under the situation of conductive layer of electric imaging recording materials, described polymer mixes with a kind of metal-oxide semiconductor (MOS) etc., so that improve electric conductivity and reduce sheet resistance to dependence on temperature, this has introduction (term " OPI " refers to " not examining disclosed Japanese patent application " here) in as Japanese patent application (OPI) 9524/80 and 331/80.In this respect, when independent use cationic styrene polymer, it is not enough to the absorbability of inorganic filler.Consider that from the stability of record video under lower-temperature atmosphere the absorbability of metal-oxide semiconductor (MOS) is had special importance.
On the other hand, the aqueous dispersion of known cationic polymer by ethylene copolymer preparation includes and a kind ofly reacts the aqueous dispersion that obtains by the copolymer and a kind of acid that make ethylene/acrylic acid aminoalkyl ester compounds in water, and this introduces in Japanese patent application (OPI) 16542/72.This aqueous dispersion is good for the absorbability of inorganic filler such as metal-oxide semiconductor (MOS) (for example zinc oxide, tin oxide, titanium oxide etc.), after it is coated on the last also drying of matrix (as paper and plastic sheeting), provide one deck semiconductor not only soft but also water-fast or solvent to film.Although formed the filming of aqueous dispersion by the copolymer of ethylene/acrylic acid aminoalkyl ester compounds has these advantages, compare with filming of cationic styrene polymer, the former has higher surface resistivity.Aqueous dispersion on this conductive layer that is coated to the electrographic recording material does not reach enough writing functions, thereby uses in practice as yet.
Form the field at sheet material, disclosed series of strata are noticeable in the Japanese patent application (OPI) 98304/83 and 180697/83.According to these series of strata, in water, react and generate quaternary salt and then make it and show fontanel and carry out the aqueous dispersion that addition reaction obtains by in moisture pulp material, adding a kind of copolymer by making ethylene/acrylic acid aminoalkyl ester compounds and various organic or inorganic acid, can improve upward colloidality and wet strength simultaneously for alcohol.
The inventor studies the practical application of above-mentioned technology.Yet, the aqueous dispersion that makes owing to the copolymer from ethylene/acrylic acid aminoalkyl ester compounds should add so that bring about the desired effect with sizable amount, so, compare with the general series of strata that adhesive and wet strength agent use, from the viewpoint of economy, the result who obtains is not gratifying for practical application.
Therefore, required to solve the incident variety of issue of aqueous dispersion that makes with traditional copolymer from ethylene/acrylic acid aminoalkyl ester compounds, the electric conductivity of filming that promptly obtains is not enough, and the function that gives colloidality and wet strength in sheet material forms simultaneously is not enough.
In sum, an object of the present invention is to provide a kind of aqueous dispersion of the cationic polymer that makes from ethylene copolymer, from function and economic viewpoint, it has actual benefit as the conductive layer of electric imaging recording materials or the additive of paper grade (stock).
According to the extensive studies result, found from the cationic polymeric dispersion that the novel copolymer of ethene and aminoalkyl acrylamide comonomer makes compare with traditional cationic polymeric dispersion demonstrate form conducting coating characteristic be improved significantly, and make colloidality and wet strength generation significantly improve effect simultaneously.
In first embodiment of the present invention, a kind of aqueous dispersion of cationic polymer is provided, it is to react in water to form quaternary salt by the ethylene copolymer of at least a aminoalkyl acrylamide comonomer that makes a kind of ethene that contains 40～80% (weight) and 20-60% (weight) and hydrochloric acid, by addition reaction the quaternary salt that obtains and the reaction of a kind of epihalohydrin compound are obtained then, described comonomer is represented with following formula (I) and is had a melt index (MI) of/10 minutes of 10～1000 grams (according to the method mensuration of JISK-6760).Formula (I) is expressed as
R in the formula
1Represent a hydrogen atom or a methyl; R
2And R
3Each represents a hydrogen atom or the alkyl with 1～4 carbon atom; N is an integer of 2～4.
In second embodiment of the present invention, improved a kind of by in above-mentioned cationic aqueous polymer dispersion, adding a kind of alcohol amine compound, heat-treating the aqueous dispersion of the cationic polymer that obtains then.
At first, according to aqueous dispersion of the present invention, it is characterized in that only having excellent absorption ability, and be the flexibility of filming that forms thus, eliminated hidden danger such as problems such as curling of film rhegma or matrix to inorganic filler such as metal-oxide semiconductor (MOS); And filming of forming thus has gratifying resistance to water and solvent resistance, so, compare in practicality more reliable with the aqueous dispersion of commercially available cationic styrene polymer.Moreover, the aqueous dispersion of first embodiment provides superior filming, and its surface resistivity is far below the surface resistivity of filming that traditional cationic polymeric dispersion obtained that makes by the copolymer from ethylene/acrylic acid aminoalkyl ester compounds.
Secondly,, it is characterized in that comparing the obvious behavior of going up colloidality and wet strength simultaneously that improved, so just can reach desirable efficacy levels in the practical application with the additive of decrement with the aqueous dispersion of aforementioned conventional according to aqueous dispersion of the present invention.
The preparation that can be used as the ethylene copolymer of raw material can be passed through radical polymerization 40～80% (weight) under High Temperature High Pressure, preferably ethene and 20～60% (weight), the preferably represented aminoalkyl acrylamide comonomer realization of at least a formula (I) of 25～50% (weight) of 50～75% (weight).
If the content of the chain link of the aminoalkyl acrylamide comonomer in the ethylene copolymer is lower than 20% (weight), the content that is to say the ethene chain link is higher than 80% (weight), then quaternary salt and table fontanel may have very poor hydrophily for the product that the addition reaction between the alcoholic compound obtains, and can not provide to contain all fine grain stable aqueous dispersion.On the other hand, if the content of ethene chain link is lower than 40% (weight), that is to say that the content of aminoalkyl acrylamide comonomer chain link surpasses 60% (weight), the aqueous dispersion that then obtains only forms and is not enough to water-fast and low excessively the filming of film-strength.When such film during as the conductive layer of electric imaging recording materials, writing with pencil or ball pen to be impossible, that is to say when such aqueous dispersion is used as the additive of paper, for last colloidality to improve effect not enough.
The viewpoint of the physical property of filming, the particularly film strength that forms from the viscosity of aqueous dispersion with by this aqueous dispersion is used for ethylene copolymer of the present invention and should has 10～1000 grams/10 minutes.Preferably 30～500 restrain/10 minutes melt index (MI) (measuring) according to JISK6760.
According to above-mentioned for example Japanese patent laid-open publication gazette 22523/67 and 5194/78 method, above-mentioned ethylene copolymer can be by the preparation of high-pressure free radical polymerisation.More particularly, the aminoalkyl acrylamide compound of ethene and formula (I) is fed a vessel type reactor of being furnished with agitator or barrel reactor continuously with a kind of free radical catalyst such as oxygen, organic peroxide, azo-compound etc. so that under the temperature of the pressure of 500～3000kg/cm and 100～300 ℃, carry out polymerization.Can use various types of chain-transferring agents, for example ethane, propane, propylene etc. are to adjust the molecular weight of polymer.
The object lesson that can be used for the aminoalkyl acrylamide comonomer of recommendation of the present invention has dimethylaminoethyl acrylamide, dimethyl aminopropyl acrylamide, dimethylamino butyl acrylamide, diethyl aminoethyl acrylamide, diethyl amino propyl group acrylamide, diethyl amino butyl acrylamide, di aminoethyl acrylamide, di aminopropyl acrylamide, N-(1, the corresponding methacrylamide derivatives of acrylamide or the like 1-dimethyl-3-dimethyl aminopropyl), and these acrylamide derivatives.These aminoalkyl acrylamide comonomers both can use separately.Also can two or more combine use.
In the comonomer of enumerating in the above, what recommended most is dimethyl aminopropyl acrylamide, dimethyl aminopropyl Methacrylamide, dimethylaminoethyl acrylamide and dimethylaminoethyl Methacrylamide.
In order to improve the pliability of filming that forms by this aqueous dispersion or to reduce heat-sealing temperature, ethylene copolymer also can include one or more comonomers except that ethene and aminoalkyl acrylamide compound, for example methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, vinylacetate, propionate, dimethylaminoethyl acrylate methyl base aminoethyl ester, acrylic acid dimethylaminoethyl ester or the like, its ratio can be up to 20% (weight).
The amount of hydrochloric acid that is used for the ethylene copolymer quaternization is between the ethylene copolymer of per 100 parts (moles) amino 50～200 parts, preferably 80～150 parts (mole).If the consumption of hydrochloric acid is lower than 50 parts, the quaternary salt that then obtains often has very poor hydrophily, and the addition compound product that obtains with epihalohydrin compound reaction subsequently can not provide the stable and low viscous all fine grain aqueous dispersion that contains.On the other hand, if the consumption of hydrochloric acid surpasses 200 parts, the aqueous dispersion that obtains thus forms films that often resistance to water and film strength are not enough.
In general; be pill or pulverous ethylene copolymer and hydrochloric acid and under 60～100 ℃ and atmospheric pressure, mixture stirred 30～120 minutes by in the water of 100 weight portions, adding 5～35 weight portions, can fully finish the quaternization of hydrochloric acid and ethylene copolymer and react.In some cases, ethylene copolymer still keeps its shape in the quaternization course of reaction, just with the aqueous hydrochloric acid solution swelling.Because the addition reaction that reaction system contains thing by follow-up and epihalohydrinization becomes and a kind ofly contains all fine grain aqueous dispersion, so this carrier can not have problems.
Then, hydrochloric acid quaternary salt and a kind of table fontanel of the ethylene copolymer that obtains thus carried out addition reaction for alcoholic compound, thereby form a kind of even and stable aqueous dispersion.
The epihalohydrin that participates in reaction comprises chloropropylene oxide, epibromohydrin or the like, and particularly best with chloropropylene oxide.According to the amino meter of per 100 parts (moles) contained in the ethylene copolymer, the consumption of epihalohydrin is 50～200 parts (moles), preferably 80～150 parts (mole).When the consumption of epihalohydrin compound is lower than 50 parts, can not obtain the stable and low viscous all fine grain aqueous dispersion that contains; If its consumption surpasses 200 parts, profit to aqueous dispersion only form can not be fully water-fast and low the filming of film strength, caused the problem in the actual use.
With the addition reaction of epihalohydrin compound generally can 20～100 ℃, be preferably in 40～90 ℃ and stir under carried out 30～300 minutes.Feeding manner to the epihalohydrin compound is not specifically limited, and it can just all drop at the beginning, or continuously, or drop into unceasingly.
If need, the cationic polymeric dispersion of the present invention that makes thus can have a kind of alcohol amine compound in the presence of heat-treat.What the sheet resistance that provides the aqueous dispersion that obtains by this heat treatment method was further reduced films.
Used alcohol amine compound comprise monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, dihydroxy-propylamine, two (dihydroxypropyl) amine, three (dihydroxypropyl) amine, or the like.In addition, can also use the polyamines-polyhydroxy-alcohol compound that obtains by the reaction of alkylene oxide and polyamines, for example the addition compound product of the addition compound product of oxirane (4 moles) and ethylenediamine, oxirane (4 moles) and propane diamine etc.In the middle of these alcohol amine compounds, best is diethanol amine.
In per 100 parts (moles) amino of existing in the ethylene copolymer is benchmark, and the addition of alcohol amine compound is 20 to 200 parts (mole), and is good with 50 to 150 parts (mole).Addition is lower than 200 parts and is not enough to produce the effect that the surface resistivity of filming that the desirable aqueous dispersion that makes gained makes reduces.On the other hand, if the consumption of alcohol amine compound surpasses 200 parts, then since in the resulting aqueous dispersion excessive compound have neither part nor lot in reaction, what make thus films not only evenly but also is hygroscopic, the result causes the humidity dependence of surface resistivity to rise.
Generally carry out (being advisable with 40 to 100 ℃) under temperature is 20 to 100 ℃ condition with the reaction of alcohol amine compound, the reaction time is 1 to 10 hour.
The solid content of cationic polymeric dispersion of the present invention is preferably in per 100 parts of (weight) water 5 to 50 parts (weight), and 10 to 40 parts (weight) is better.Said herein " solid content " is meant the content that removes the afterwards remaining nonvolatile matter that anhydrates by method dry in about 100 ℃ of hot-airs in aqueous dispersion.Solid content surpasses 50 parts aqueous dispersion owing to viscosity does not have flowability and its property used (as the performance that applies) poor too greatly on matrix.From the angle of production efficiency, transportation, selling price and the coating dry load in back, it also is worthless that solid content is lower than 5 parts aqueous dispersion.
In film-forming process, this aqueous dispersion is coated with on the butt body (as paper and plastic film), and under about 50 ℃ to 150 ℃ condition heat drying.
When with aqueous dispersion of the present invention during as the conductive layer of electric imaging recording materials, it can be mixed mutually with metal-oxide semiconductor (MOS), for example can mix with zinc oxide, cuprous oxide, indium oxide, tin oxide, titanium oxide, cobalt oxide, nickel oxide, tantalum pentoxide, vanadic anhydride, tungstic acid, molybdenum trioxide etc. or these metal oxides that are mixed with adulterant.Being used in combination these metal oxide semiconductor materials can further reduce the surface resistivity of resulting conductive layer effectively and reduce the dependence of packing density to humidity.
In order to make acrylic resin, vinyl chloride resin, butyral resin etc. have writing quality, sign performance or natural material sensation, the coating of using the pigment (as titanium oxide, calcium carbonate, starch, clay etc.) that wherein contains the microparticle shape usually is as the dielectric layer resin solution that imposes on the semiconductor laminated sheet material (making by aqueous dispersion of the present invention being coated in method dry then on paper or the plastic film).The thickness of this class coating is about 5 to 10 microns (dry state).Its surface resistivity is preferably about 10 under normal temperature and atmospheric pressure
12To 10
15Ω (ohm).
Also can add additive, for example dyestuff, pigment, stuffing, surfactant, antistatic additive, plasticizer, lubricant, dispersant, defoamer etc., and water-soluble resin, for example polyvinyl alcohol as required in the aqueous dispersion of the present invention.
According to the present invention, can obtain by aqueous dispersion being coated to subsequent drying on paper or the plastic film that one deck is thin, transparent, the filming of soft and tough.Dried coating is non-water-soluble, and moist and water are had goodish stability.Like this, the packing density that contains the electric imaging recording materials of aqueous dispersion of the present invention in the conductive layer be subjected to the little and record performance of the influence of humidity not in time passing and change.When with this aqueous dispersion during as antistatic additive, resulting film has lasting antistatic property.
In addition, in the sheet material forming process, use aqueous dispersion of the present invention the gluing performance and the wet strength of paper are significantly improved as additive.Both aqueous dispersion can have been joined as wet boundary effect (wet end) additive in this class is used also to make it be impregnated in the paper in the paper pulp.In the previous case, generally be that the cationic polymer that is scattered in the water is joined in the paper pulp by the consumption of per 100 parts of paper pulp (dry state weight) 0.1 to 5 part (weight), then the paper that forms in temperature be under 70 to 150 ℃ the condition heating several seconds to a few minutes make its drying.In this case, can be used in combination the water repellent, as wax, polysiloxanes and fluorocarbon resin etc.
Introduce the present invention in more detail by following embodiment more now, still it should be noted and to think that the present invention only limits to the content of embodiment.In these embodiments, all percentage, ratio (unless otherwise indicated) all by weight.
Embodiment 1
With 360 gram water, 100 gram ethene/dimethylaminopropyl acrylamide ratios is that 59: 41 and melt index (MI) are that JIS K-6760 mensuration (press in 300 grams/10 minutes, hereinafter identical) ethene/dimethylaminopropyl acrylamide copolymer particle and 36% aqueous hydrochloric acid solutions of 27 grams join in the glass flask of 1000 milliliters of volumes, add the hydrochloric acid be equivalent to per 100 parts (moles) (in copolymer) amino 100 parts (moles).Under stirring condition mixture was heated up 30 minutes to 100 ℃ from room temperature, also under refluxad continue to stir 60 minutes under this temperature, the result is that particle disappears, and obtains the water slurry of thickness.
Under stirring condition, be cooled to after 80 ℃, within 30 minutes, in water slurry, splash into 24 gram (be equivalent to per 100 parts of (mole) amino have added 100 parts (moles) in the copolymer) chloropropylene oxides.Under 80 ℃ of conditions, continue then to stir 270 minutes, obtain the even aqueous dispersion of light brown.Resulting aqueous dispersion is called dispersion A-1.Under 25 ℃ of conditions, the pH value of dispersion A-1 is 5.6, and viscosity is 49 centipoises.The granularity of the polymer beads that disperses is 0.1 micron or littler.The solid content of dispersion A-1 (defining the same) is 26%.
Embodiment 2
Under 80 ℃ and stirring condition, in the glass flask of 1000 milliliters of volumes, add dispersion A-1,28 gram (being equivalent to 100 parts (moles), is 100 minutes (mole) in the amino in the copolymer) diethanol amine of preparing among the 490 gram embodiment 1.Under this temperature, continue to stir 300 minutes, cool off then, obtain the even aqueous dispersion of light brown.The dispersion that obtains is called dispersion A-2.Under 25 ℃ of conditions, the pH value of dispersion A-2 is 6.9, and viscosity is 17 centipoises, and solid content is 30%.The granularity of the polymer beads that disperses is 0.1 micron or littler.
Embodiment 3 to 8
Prepare dispersion A-3 to A-8 by the method identical with embodiment 1 or 2, different is has replaced ethene/dimethylaminopropyl acrylamide copolymer of using among the embodiment 1 or 2 with various ethene copolymers (having listed composition and melt index (MI) separately in the table 1) particle.A-3 to A-8 contains the stable low viscosity aqueous dispersion that granularity is 1 micron or littler polymer beads.
Reference example 1 to 3
In order to estimate the performance of aqueous dispersion of the present invention the time as electrically-conducting paint or additive for paper making, by with implement 1 or 2 identical methods and prepared contrast aqueous dispersion R-1 to R-3, different is to have replaced ethene/dimethylaminopropyl acrylamide copolymer with the copolymer of being made up of ethene and a kind of acrylic acid aminoalkyl comonomer listed in the table 1.All dispersion R-1 to R-3 dispersion performances are all similar to the aqueous dispersion performance that makes by example 1 or example 2, that is to say that its viscosity is low, and the granularity of particle is 1 micron or littler.
Reference example 4
With 1.3 times of (mole) hydrochloric acid make with example 5 in the same ethene copolymer (dimethylaminopropyl acrylamide content 50%) used quaternized, preparing solid content by the method identical with embodiment 1 is 24% quaternary salt.Product is the water slurry shape solid-liquid mixture of thickness.Compare with embodiment 5, for the stable aqueous dispersions that obtains containing microparticle obviously should add chloropropylene oxide subsequently.
Reference example 5 and 6
Press the method operation of embodiment 1 or 2, the dimethylaminopropyl acrylic acid content of different the is ethene copolymer of initial usefulness is 15%, melt index (MI) is 100 grams/10 minutes, but because copolymer pellet can not complete obiteration, thereby fail to obtain uniform aqueous dispersion.
(table 1 is seen the literary composition back)
Embodiment 9
With rod coater #10 the dispersion A-2 by embodiment 2 preparation be applied to quantitatively be 84 grams/square metre nothing wood paper on, and on the hot air circulate drying machine in 100 ℃ of dryings 5 minutes, obtain not having the paper that curling (Curling-free) applied, have on it one deck dry weight be 1.2 the gram/square metre uniform semiconduction film.
With resistance instrument (the superinsulation instrument of making by Toa Derpa Kogyo K.K., the SM-10E type) be in temperature that 23 ℃, relative humidity (RH) are 30%, 50%, 70%, voltage is the sheet resistance of measuring the coated surfaces of this paper under 100 volts the condition, as shown in table 2, measured value is respectively 5 * 10
7Ohm, 8 * 10
6Ohm, 9 * 10
5Ohm.In relative temperature be under 50% the condition before the coating surface resistivity of paper be 4 * 10
13Ohm.
70: 30 ratios are coating agent of a kind of manufacturing dielectric layer " C " (methyl ethyl ketone solution of vinylacetate/vinyl chloride/vinyl alcohol ter-polymer resin that Sakata Shokai K.K. makes, solid content 28%) and " Softon by weight
1800 " (the registrar name of an article of the calcium carbonate fine powder that BihokuFunka Kogyo K.K. makes, 1.25 microns of particle mean sizes) mixes mutually to prepare a kind of dispersion.With rod coater #10 prepared dispersion is coated on the semiconduction film of paper of above-mentioned coating, undertaken air-dry by air blast, and in circulating hot air dryer in 5 parts of clocks of 100 ℃ of dryings, obtain the coating gross dry weight and be 6.0 grams/square metre electric imaging record-paper.
Electricity consumption imaging record test instrument (Matsushita Denso K.K. makes AO type electricity imaging plotter EP101) is under 30% the condition prepared electric imaging record-paper to be carried out the test of electric imaging record in relative humidity, can obtain the recording geometry of very clear lizard.
Embodiment 10 to 13
Have the paper that one deck is even and glossiness nothing of filming is curled and applied by the method manufacturing identical with embodiment 9, different is to use embodiment 3,4 respectively, and dispersion A-3, the A-4, A-5 or the A-7 that make in 5 or 7 have replaced dispersion A-2.As shown in table 2, the surface resistivity of resulting each paper that applied has all reached gratifying level.
By the method identical this paper that applied is coated one dielectric layer again, obtain electric imaging record-paper with embodiment 9.The various record-papers that obtain all have fabulous record effect.
Comparative example 1 and 2
Method by example 9 prepares the paper that applied, and different is to have replaced dispersion A-2 with the dispersion R-2 or the R-3 that prepare in reference example 2 or 3 respectively.As shown in table 2, the surface resistivity of the paper of prepared coating is higher.Like this, poor with the record effect of these electric imaging record-papers of making by the paper of the coating of the method manufacturing identical with embodiment 9, only obtain the pattern of unclear lizard generally, the some of them point disappears.
By above as can be known, with compare with the aqueous dispersion of ethylene/acrylic acid aminoalkyl ester copolymer, aqueous dispersion with the copolymer of ethene of the present invention/aminoalkyl acrylamide compound can obtain having filming of high electrical conductivity, thereby can obtain the electric preferably imaging record-paper of effect.
(table 2 is seen the literary composition back)
Embodiment 14
The 100 Powdered electroconductive zinc oxide of adding 25 grams (the Honjo ChemcalK.K. manufacturings in dispersion A-1 that in embodiment 1, make, 1.5 microns of particle mean sizes, see Japan Patent 1,029,615 and 1,029, No. 616), and with mixture in stirring at room 30 minutes, obtain wherein being distributed with equably the gray mixture of Zinc oxide particles.With rod coater #10 with the gained mixture be coated in quantitatively be 84 grams/square metre nothing wood paper on, and in 110 ℃ hot-air dry 3 minutes, obtain having on it one deck dry weight be 7.6 grams/square metre the paper of the even white coating of filming.Under the condition identical, measure the surface resistivity of this paper that applied, be respectively in relative humidity that measurement result is respectively 2 * 10 under 30,50 and 70% the condition with embodiment 9
6, 7 * 10
5With 5 * 10
5Ohm, the resistivity of the paper that this explanation applied is lower, and less to the dependence of humidity.
Under stirring condition, coating agent (the toluene solution of the acrylic resin that Nagase Kasei Kogyo K.K. makes that 100 grams is used to prepare dielectric layer " 50C ", solid content 50%), 50 grams among the embodiment 9 used same calcium carbonate and 180 gram toluene mix mutually, prepare a kind of uniform dispersion separately.With rod coater #10 this dispersion is coated with on the paper of the coating of preparing in front, and in 110 ℃ hot-air dry 5 minutes, obtain total coating dry weight and be 13.1 grams/square metre electric imaging record-paper.
When under the condition identical, carrying out electric imaging record test, obtain recording figure forming very clearly, without any the phenomenon of a disappearance with embodiment 9.
Embodiment 15
Mica " MEC-500 " (the Teikoku Kako K.K. manufacturing that in the dispersion A-5 that 100 grams make by embodiment 5, adds 18 grams electric conductivity sheet, transparent, the particle mean size of mica particles is that 10 microns, specific surface are 19 meters squared per gram, scribble tin oxide and antimony oxide on it), under room temperature, stirred 30 minutes subsequently, wherein be evenly distributed with the gray mixture of mica particles.With rod coater #10 this mixture is coated on the surface that the corona treatment of the polyethylene terephthalate film " E-5101 " (manufacturing of Toyobo Co., Ltd) of one 75 micron thickness crosses, and in 120 ℃ hot-air dry 2 minutes, obtain having one deck dry weight and be 8.5 grams/square metre, the stack membrane of filming glossiness, transparent, that cohesiveness is very high.Measure by the method identical with embodiment 9, be respectively in relative humidity under 30,50 and 70% the condition, this surface resistivity of filming is respectively 9 * 10
5, 5 * 10
5With 3 * 10
5Ohm.This resistivity that this stack membrane is described is lower, and less to the dependence of humidity.
Adopt the method identical on laminated film, to form a dielectric layer, thereby obtain to be used for the semitransparent layer press mold that telecommunication is write down with embodiment 14, on this film the dry gross weight of coating be 14.7 restrain/square metre, its mist degree is 76%.With embodiment 9 the same terms under carry out telecommunication record test, consequently obtain a kind of very clear pattern that does not have any some extinction tests.
Embodiment 16 to 18
The dispersion A-1 that consumption is as shown in table 3, it is that 410 milliliters and N-BKP/L-BKP ratio are that 1/1 concentration is in 1.0% the slush pulp that A-5 or A-7 add to a kind of its Canadian standard fluid rate of discharge, with 200 rev/mins rotating speed this is mixed then and stirs 2 minutes.By means of TAPPI standard tablet press machine above-mentioned slurry is laminated, and in 110 ℃ of down dry regular hours (1 or 10 minute), just can to obtain quantitatively be 80 grams/square metre paper.Wet breaking length and degree of sizing thereof as the wet strength evaluation criterion of this paper can be measured as follows, and it the results are shown in table 3.
1) degree of sizing:
Be to measure according to St ckigt method under 65% the condition in 25 ℃ and relative humidity.
2) wet breaking length (measuring) according to the P8113 of Japanese Industrial Standards
Under 20 ℃, place water dipping after 60 minutes on paper, measure its wet tensile (strength), according to this measurement result and following equation just can calculate breaking length "
Comparative example 3 and 4
Adopt the method identical with embodiment 16 and 18 to prepare the paper sample, different is to replace aqueous dispersion of the present invention with the dispersion R-1 or the R-2 that prepare in reference example 1 or 2.Adopt the method identical with embodiment 16 to 18 to measure the degree of sizing of paper and the breaking length that wets, gained the results are shown in table 3.
Compare with 18 result with embodiment 16, obviously, aqueous dispersion of the present invention can improve degree of sizing and wet strength more effectively than the prepared aqueous dispersion of copolymer by ethylene/acrylic acid aminoalkyl ester compounds.
The comparative example 5
Adopt the method identical with embodiment 16 and 18 to prepare the paper sample, different is with " Sumirez resin
#675 " (polyamide-chloropropylene oxide type wet-strength resins that Sumitomo chemistry Co., Ltd generates, content is 25% the aqueous solution) replace aqueous dispersion of the present invention.Adopt the method identical with embodiment 16 to 18 to measure degree of sizing and the breaking length that wets, its result is in table 3.Table 3 shows, adds wet strengthening resin and can not produce any gluing effect.
(table 3 is seen the literary composition back)
Embodiment 19 and 20
With quantitatively be 80 grams/square metre hand-built not sized paper (30 centimetres of 10 cm x) impregnated in (result of dilution makes polymer concentration reach numerical value shown in the following table 4) among 500 milliliters of diluted dispersion A-5 or A-8, in 110 ℃ hot-air dry 5 minutes then.In the weight of sized paper not is that the polymer recovery of benchmark is shown in table 4.Adopt the method identical with embodiment 16 and 18 to measure the degree of sizing and the wet breaking length of impregnated paper, measurement result is shown in table 4.Table 4 has shown the influence of various factors to degree of sizing and wet strength generation.
(table 4 is seen the literary composition back)
As mentioned above, the aqueous dispersion of the present invention that the copolymer that is obtained by ethene and aminoalkyl acrylamide comonomer makes, when it being coated on matrix and through super-dry, can obtain the paint film that one deck electric conductivity is improved significantly, thereby, be enough to be used as just like the polymer that is applicable to telecommunication recording materials conducting shell.
In addition, aqueous dispersion of the present invention also can be used as wet boundary effect (wet end) additive or paper impregnating agent and improves degree of sizing and wet strength simultaneously.
With reference to specific embodiments of the present invention and to the detailed description that the present invention did, various not deviate from essence of the present invention and do not exceed the improvement of the scope of the invention and revise all be conspicuous for the person skilled in art.
Table 1
Annotate: 1) dimethylaminopropyl acrylamide
| Embodiment number | Ethene copolymer | Hydrochloric acid content (with the mol ratio of amino) | Chloropropylene oxide amount (with amino mol ratio) | Hydramine | Aqueous dispersion | |||||||
| (co-monomer content, weight %) | Melt index (MI) (restraining/10 fens) | Kind | Consumption (with the mol ratio of amino) | Solid content (wt%) | ????pH | Viscosity (25 ℃) (centipoise) | Uniformity | Sample number | ||||
| 12345678 reference examples 123456 | ??PAA 1)??″ ????″ ????″ ????″ ????PMA 2)??″ ????″ ????EM 3)?????????? ?″ ???EA 4)?PAA ?″ ???″ | ????(41) ?????″ ?????????″ ??????????(35) ????(50) ????(39) ????″ ?????????(28) ????(39) ????″ ?????????(35) ????(50) ????(15) ????″ | ???300 ????″ ?????????″ ????????280 ????55 ????270 ????″ ?????????96 ????300 ????″ ?????????250 ????55 ????100 ????″ | ????1.0 ????″ ?????????″ ????????″ ?????????1.3 ????1.0 ????″ ?????????1.2 ????1.0 ????″ ?????????″ ?????????1.3 ????1.0 ????″ | ????1.0 ?????″ ???????????″ ?????????″ ?????????1.5 ????1.0 ????″ ?????????1.2 ????1.0 ???????? ????″ ?????????″ ?????????0 ????1.0??? ????″ | ?- ?DEA 5)?MEA 6)?DEA ?- ?- ?DEA ?- ?- ?DEA ?″ ?- ?- ?DEA | ????- ????1.0 ????″ ????????2.0 ????- ????- ????2.0 ????- ????- ????1.0 ????2.0 ????- ????- ????1.0 | ????26 ????30 ????25 ????25 ????27 ????22 ????25 ????17 ????25 ????30 ????25 ????24 ????20 ????22 | ????5.6 ????6.9 ????7.1 ????7.3 ????6.7 ????6.5 ????6.8 ????6.7 ????5.5 ????7.1 ????7.3 ????4.4 ????6.6 ????7.0 | ????49 ????17 ????32 ????20 ????35 ????31 ????20 ????84 ????42 ????9 ????52 ????870 ????- ????- | Good poor poor | ?A-1 ?A-2 ?A-3 ?A-4 ?A-5 ?A-6 ?A-7 ?A-8 ?R-1 ?R-2 ?R-3 ?- ?- ?- |
2) dimethylaminopropyl MAAm
3) dimethylaminoethyl methacrylate
4) acrylic acid dimethylamino ethyl ester
5) diethanol amine
6) monoethanolamine
Table 2
| Embodiment number | Aqueous dispersion | Apply low surface resistivity | Electricity imaging record effect (30%RH, 23 ℃) | |||
| Sample number | Coating heavy (doing) (gram/square metre) | 30％RH | ?50％RH | ?70％RH | ||
| Embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 Comparative Examples 1 Comparative Examples 2 | ?A-2 ?A-3 ?A-4 ?A-5 ?A-7 ?R-2 ?R-3 | ????1.2 ????1.0 ????1.2 ????1.7 ????1.3 ????1.2 ????1.0 | ?5×10 7?7×10 7?7×10 7?8×10 7?6×10 7?4×10 8?5×10 8 | ?8×10 6?1×10 6?9×10 6?7×10 6?9×10 6?5×10 7?6×10 7 | ?9×10 5?2×10 6?9×10 5?8×10 5?1×10 6?6×10 6?7×10 6 | Good poor |
The dense polymer recovery degree of sizing of table 4 embodiment sample polymer breaking length sequence number sequence number degree % (weight) rate % (weight) (second) (km) 19 A-5 0.1 0.1 41 0.79 that wet
1.0????????????1.1?????????92?????????2.58
2.0????????????2.4?????????102????????3.73??20????A-8?????0.1????????????0.1?????????45?????????0.71
1.0????????????1.2?????????97?????????2.42
2.0 2.7 105 3.57 contrasts do not have--0 0.24 embodiment
Table 3
| The embodiment sequence number | Aqueous dispersion | Drying time: 1 minute | Drying time: 10 minutes | |||
| The sample sequence number | Addition % (weight) | Degree of sizing (second) | Wet breaking length (km) | Degree of sizing (second) | Wet breaking length (km) | |
| Embodiment 16 embodiment 17 embodiment 18 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples | ????A-1 ????A-5 ????A-7 ????R-1 ????R-2 ?Sumirec ?Resin 675 do not have | ????0.4 ????0.8 ????2.0 ????0.4 ????0.8 ????2.0 ????0.4 ????0.8 ????2.0 ????0.4 ????0.8 ????2.0 ????0.4 ????0.8 ????2.0 ????0.4 ????0.8 ????2.0 ????- | ????59 ????88 ????97 ????54 ????86 ????100 ????51 ????82 ????101 ????43 ????72 ????90 ????40 ????69 ????88 ????0 ????0 ????0 ????0 | ????1.80 ????2.57 ????3.82 ????1.74 ????2.64 ????3.91 ????1.76 ????2.46 ????3.72 ????1.45 ????2.20 ????3.26 ????1.52 ????2.33 ????3.48 ????0.78 ????1.08 ????0.24 ????0.24 | ????65 ????90 ????99 ????56 ????97 ????104 ????53 ????89 ????104 ????49 ????81 ????92 ????43 ????75 ????90 ????0 ????0 ????0 ????0 | ????1.86 ????2.62 ????3.86 ????1.82 ????2.65 ????3.97 ????1.79 ????2.51 ????3.94 ????1.51 ????2.23 ????3.39 ????1.55 ????2.37 ????3.51 ????1.32 ????1.92 ????2.70 ????0.25 |
Annotate: * is a benchmark in paper pulp weight.
Claims (4)
1. the paper by a kind of cationic polymeric dispersion is added to a kind of slush pulp and obtains through super-dry, wherein cationic polymeric dispersion is then to carry out addition reaction with the epihalohydrin compound by the quaternary salt that the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid solution is generated to make, amino in wherein per 100 parts of (mole) copolymers, add hydrochloric acid 50-200 part (mole), add epihalohydrin 50-200 part (mole); The slush pulp of per 100 parts (weight) (dry back) adds cationic polymer 0.1-5 part (weight); This ethylene copolymer contains the aminoalkyl acrylamide shown in 40 to 80% (weight) ethene and at least a molecular formula of 20-60% (weight) (I):
R in the formula
1Represent hydrogen atom or methyl; R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; N is 2 to 4 integer, and the melt index of the above-mentioned ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
2. the paper by a kind of cationic polymeric dispersion being added in a kind of slush pulp and obtaining through super-dry, wherein cationic polymeric dispersion is to carry out addition reaction by quaternary salt and a kind of epihalohydrin compound that the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid solution is generated, following this addition compound product reacts with alcohol amine compound again and makes, amino in wherein per 100 parts of (mole) copolymers adds hydrochloric acid 50-200 part (mole); Add epihalohydrin 50-200 part (mole); After the slush pulp drying of per 100 parts (weight), add cationic polymer 0.1-5 part (weight): the amino in wherein per 100 parts of (mole) copolymers adds hydramine 20-200 part (mole); This ethylene copolymer contains the ethene of 40 to 80% (weight) and the aminoalkyl acrylamide comonomer shown at least a molecular formula of 20 to 60% (weight) (I):
R in the formula
1Represent hydrogen atom or methyl; R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; N represents 2 to 4 integer, and the melt index of the above-mentioned ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
3. flood the paper that sized paper not obtains by aqueous dispersion with a kind of cationic polymer, wherein cationic polymeric dispersion is to make by making a kind of ethylene copolymer and the aqueous hydrochloric acid solution quaternary salt that generates of reaction and epihalohydrin compound carry out addition reaction, amino in wherein per 100 parts of (mole) copolymers adds hydrochloric acid 50-200 part (mole); Add epihalohydrin 50-200 part (mole); The slush pulp of per 100 parts (weight) (dry back) adds cationic polymer 0.1-5 part (weight); Here used ethylene copolymer contains 40 to 80% (weight) ethene and 20 to 60% (weight) are at least a by the aminoalkyl acrylamide comonomer shown in the molecular formula (1):
R in the formula
1Represent hydrogen atom or methyl; R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; N is 2 to 4 integer, and the melt index of the above-mentioned ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
4. flood the paper of not gluing and the paper that obtains through super-dry by aqueous dispersion with a kind of cationic polymer, cationic polymeric dispersion wherein is to carry out addition reaction by quaternary salt and a kind of epihalohydrin compound that the reaction of a kind of ethylene copolymer and aqueous hydrochloric acid solution is generated, amino in wherein per 100 parts of (mole) copolymers adds hydrochloric acid 50-200 part (mole); Add epihalohydrin 50-200 part (mole); The slush pulp of per 100 parts (weight) (dry back) adds cationic polymer 0.1-5 part (weight): its addition compound product and react with a kind of hydramine and to make the amino in wherein per 100 parts of (mole) copolymers, adding hydramine 20-200 part (mole); Here used ethylene copolymer contains 40 to 80% (weight) ethene and 20 to 60% (weight) are at least a by the aminoalkyl acrylamide comonomer shown in the molecular formula (I),
R in the formula
1Represent hydrogen atom or methyl; R
2And R
3Represent hydrogen atom separately or contain the alkyl of 1 to 4 carbon atom; N is 2 to 4 integers, and the melt index of this ethylene copolymer of measuring according to the K-6760 of Japanese Industrial Standards is 10 to 1000 grams/10 minutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26890086 | 1986-11-11 | ||
| JP268900/86 | 1986-11-11 | ||
| CN87107768A CN1024670C (en) | 1986-11-11 | 1987-11-11 | Aqueous dispersion of cationic polymer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107768A Division CN1024670C (en) | 1986-11-11 | 1987-11-11 | Aqueous dispersion of cationic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059005A CN1059005A (en) | 1992-02-26 |
| CN1030785C true CN1030785C (en) | 1996-01-24 |
Family
ID=25742382
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108602 Expired - Fee Related CN1030785C (en) | 1986-11-11 | 1987-11-11 | Aqueous dispersion of cationic polymer |
| CN91108599A Pending CN1059342A (en) | 1986-11-11 | 1987-11-11 | The method for preparing cationic polymeric dispersion |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108599A Pending CN1059342A (en) | 1986-11-11 | 1987-11-11 | The method for preparing cationic polymeric dispersion |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1030785C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010354B (en) * | 2004-06-17 | 2010-06-16 | 凯米拉公司 | Cationic polymers containing 2-hydrocyethyl-methacrylic as promoters for ASA sizing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084345C (en) * | 1999-08-05 | 2002-05-08 | 石油勘探开发科学研究院油田化学研究所 | Process for preparing high-molecular cationic polymer |
-
1987
- 1987-11-11 CN CN 91108602 patent/CN1030785C/en not_active Expired - Fee Related
- 1987-11-11 CN CN91108599A patent/CN1059342A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010354B (en) * | 2004-06-17 | 2010-06-16 | 凯米拉公司 | Cationic polymers containing 2-hydrocyethyl-methacrylic as promoters for ASA sizing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059005A (en) | 1992-02-26 |
| CN1059342A (en) | 1992-03-11 |
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