TWI336085B - Composition of polymer thick film resistor and manufacturing method thereof - Google Patents

Description

丄336085 - _ , t ---- Zhongyin Yuexiu repair (more) replacement page IX, invention description: [Technology field of the invention] The invention relates to a resistor composition and a manufacturing method thereof, in particular About. A polymer thick film resistor composition and a manufacturing method thereof. [Prior Art] With the demand for high functionality of communication electronic products and the high frequency of signal transmission, the demand for passive components and active components has increased significantly. To improve the performance of passive components, reduce the number of passive components, and reduce the advantages of the board surface _ product's use of miniaturization technology, the passive components such as capacitors, resistors and inductors are gradually become embedded passive components, breaking into the circuit board. Medium to increase device density and reduce substrate area. The high-speed high-frequency transmission of signal transmission and the shortening of the transmission distance also have some problems to be improved, such as the rapid development of High Density Interconnection (HDI), when the density between components is improved, and the components are The parasitic effect between components is also obvious. Especially in the application of high-frequency transmission, it is more likely to cause problems such as noise and signal delay, electromagnetic interference (EMI); if you use buried capacitors, it will be reduced. Or reduce parasitic effects and significantly improve the performance of the product at high speeds and high speeds. It also reduces the number of solder joints (Soldei> Joint), and the number of micro-vias (Micrvia), and improves the yield of the product. The advantages of the buried resistor are that it can reduce the substrate area, reduce the cost, and effectively improve the function of the device. When a buried resistor is used, the resulting series inductance is smaller than that of the freestanding resistor. And in the rise time (Rise is very short -5 - 1336085 * 1 ' ...................... 妁% month / ί日修 (more) is replacing page In the case of using a separate resistor, the induced impedance is increased. With the built-in resistor, the inductance-impedance can be almost ignored due to the short transmission distance. However, when the transmission frequency exceeds ΙΟΟΜίίζ, the number of resistors is required. In order to reduce the assembly cost, improve the efficiency, reduce the use area and improve the reliability, it is necessary to replace the surface-adhesive (smt) resistor with a built-in resistor. The typical applications are: the opening of the digital resistance product. Receiver, LED current control, line termination, etc. Built-in resistors can be divided into two categories on the product, one is a thin film resistor and the other is a thick film resistor. The former can be electroplated (Electroplate) or sputtered ( Sputter) or chemical vapor deposition (CVD), the latter is based on traditional screen printing. Common thick film resistors in the application, depending on the choice of substrate and subsequent thermal reaction, can be divided into high temperature sintering And low temperature baking type. High temperature sintering type It refers to thick film after 500~90 (TC sintered, suitable for integration in ceramic substrate, and another thick film resistor suitable for PCB embedded technology is low temperature baking type] after recycling screen printing process Baked with hot air of 12〇~2〇η: or • Using UV irradiation, in addition to volatilizing the solvent, the thermosetting resin in the coating produces a pattern of cross-linking hardening, the so-called polymer thick film resistor ( Polymer Thick Film Resistor), referred to as PTF resistor. pTF resistor main • It is based on molecular resin, filled with conductive material, which is characterized by the use of general thick film printing, straight printing of the graphic on the dielectric layer or The etched copper line, and the baking temperature is in line with the general pcB process, small in size, light in weight and cheap, and has a large sheet resistance (Resistance) range, which can be from 15 Ω to 1 Μ Ω; but the disadvantage is variability (T〇 Lerance) is larger, about 10~5〇%, in order to improve this shortcoming and expand it • 6 - 1336085 . · 吖年r月 A曰修(more) is replacing page applicability, increasing the range of resistance values with Reduce error variability (< 5 %) is heavy Where ..

The development of embedded passive component technology has been for many years. In the patent, most of the exposers mostly use the patents on resistance process and low temperature co-fired multilayer ceramics (LTCC). The material formulation is only part of the resistance material formula. They are simply described as a mixture of a polymer resin (such as an epoxy resin) and a conductive powder (such as carbon black). It is not known that there are still quite a few important formulation techniques to be clarified, and it is not a conventional polymer resin (such as epoxy). The mixing of the resin and the conductive powder can be arbitrarily achieved.

With regard to current PTF material patents, RCA Corp. has developed PTF resistor formulations since 1984 (US Patent 4,479,890), but did not disclose the application of buried resistors. In addition, Advanced Products Inc. has been applying for a patent for a polymer thick film resistor material formulation since 1991 (U.S. Patent No. 5,049,313, US Pat. No. 5,200,264), which is incorporated herein by reference. Blocked polyisocyanate resin) The system is the main resin, mixed with the conductive powder in an appropriate ratio, and screen-printing method, can be cured at low temperature and in a short time, and its PTF has good material storage. Good flexibility, good solvent resistance and good adhesion. It has good stability under high temperature and short time. It is mainly for material reliability research, and it is not for resistance and dimensional stability. discuss. In the past, the method to solve the problem of dimensional stability of thick film resistors was nothing more than a change of method, and the other was to change the material formulation, which was proposed by Hui-min Huang, Chia-Tin Chung et al. Patent (US 1336085)

In the year of Li, the moon is repaired (more) is replacing I 1,11 '. One-K-η --- -- --- one J 6'03 0,553), which belongs to the latter, the man emphasizes The clothing of oxygen in the ring-shaped aliphatic structure is the main body, and after the system is formed by screen printing, it is necessary to first make the ^^ and: externally harden the external resistance of the resistor, and then heat it. Carry out the structure of .^ and (4) (4), “The thick film resistors that have been stabilized in size, as the steps of increasing the complexity of the process will increase the cost. In addition, Changxing Chemical also proposed the patent of resistive materials (CN1 567485) in 5 years. Li also emphasizes that it is a solvent-free system, and the completed thick film resistor has good dimensional stability and good rheological properties, but the resistance stability is still not perfect. • SUMMARY OF THE INVENTION The present invention is disclosed as having a good resistance value stability. The premixed polymer/nano powder blending material is based on the polymer epoxy resin, and the nano conductor is added and the pre-reaction process is carried out to improve the instability of the resistance value and take into account the PCB. Process feasibility and tree material characteristics. The polymer thick film t resistance of the present invention The material has high surface temperature, small error variability, and excellent film thickness stability, which can be applied to the application of buried 4 resistance materials. The materials used include (4)-epoxy resin system. a functional group epoxy resin having a functional group of 4 or more; (7) a conductive powder (for example, carbon black) having at least one particle size distribution, and • comprising a nano-powder powder; and (4) a polymer dispersant. The above polymer thick 貘 resistance composition can be produced by the following steps. First, a mixed epoxy resin system and at least one conductive powder, wherein the epoxy resin system comprises a high-functional epoxy resin having a functional group of 4 or more. And the epoxy resin system and the conductive powder are heated at a temperature of 1 〇〇 14 (rc for 3 Torr to H, for pre-reaction. After adding the hardener and the catalyst, the temperature is lowered, 丄------- __ Year y, K, f, repair (more) is replacing the page and adding polymer dispersant, after -·- on the process and t' the hair" material resistance slurry. Material formulation technology, that is, pre-adding 孰: a very important way to emphasize the Membrane

= The material has excellent electrical stability, and is more suitable for PCB processing. The means include: (1) selecting the appropriate epoxy resin composition, to = flat fuelability and adhesion; (7) filling the nanotype with epoxy resin and Only the conductive powder is adjusted to adjust its resistance value; and (7) the selection of the appropriate 7-molecular dispersant can improve the low-molecular-type dispersibility, and on the other hand, it can greatly improve the reliability of future product applications. The principle of the low-molecular dispersant can be effectively solved by the special polymer type dispersant, which can be easily attached to the surface of the inorganic powder and has excellent compatibility with the organic tree (4) and even some reactivity. Use the pre-reaction process to improve the resistance stability of the material.

The resistive slurry obtained has a high glass transition temperature (Tg > 150 < t), excellent resistance value stability and small error variability through screen printing technology and low temperature hardening temperature conditions ( Tolerance g 6%) of the resistance material. In particular, the application of resistive materials has been quite extensive, but the general process is still based on sinter sintering. It is difficult to apply on organic substrates or traditional PCB processes. If polymer/nanoconductor hybrid materials are used, polymers are used. The compatibility of the resin material with the substrate can be achieved by using a general substrate or PCB process to complete the fabrication of the buried resistor. In order to make the polymer/nanoconductor hybrid material have good characteristics, including electrical stability and thermal stability, it can be basically determined by the choice of resin system and screen printing technology; among them, low temperature hardening and high temperature stability are good. And the good adhesion between the steel layer and the dielectric layer and the substrate - 9 - month called repair (more) is to replace the purchase j, etc., must be achieved by the choice of resin system, and the required properties of the material 'is necessary # It is provided by the addition of nano-conductive powder, and the stability of electrical properties must be achieved through a special pre-reaction process, so that a polymer which combines both low-temperature processability and resistance stability of the resin can be produced. Nano conductor hybrid material. Since the demand for buried resistor substrates is mainly applied to high-frequency and high-speed electronic products, the demand for thermal properties and electrical properties is gradually increasing. Therefore, the disclosed pre-reactive polymer/nanoconductor hybrid materials are not only important. In addition to the accuracy of the value, it is also necessary to pay attention to both the thermal properties and the stability of the electrical properties. Therefore, the formulation of the material formulation ratio, the control of the process conditions, and the technology of screen printing are the focus of the present invention. [Embodiment] The raw material of the south molecular thick film resistor composition of the present invention may be selected as follows: 环气树脂 (a)

(b) Diglycidyl ether 〇f bisphenol A epoxy (c) Tetrabr 〇 bisphenol-A-diglycidyl ether epoxy (Tetrabr〇m〇bisphenol A diglycidyl ether epoxy (d) Cyclic Aliphatic Epoxy Resin (Cycl〇aliphatic epoxy 1336085 ___^ The beginning of the year of the month of the month 丨 q day repair (more) is replacing the page;

_ --------------------------- J resin). For example, diCyCi〇pentadiene epoxy resin ° (e) contains a naphthalene epoxy resin. (1) Diphenylene epoxy resin. (g) Phenol Novolac epoxy resin (h) 4 cre-cresol Novolac epoxy resin Hardener (a) Diamine: H2N-Rj — NH2

Ri can be a square base, a fat base, a cyclo fat base or a silane containing fat

R2: X, ch2j S〇2, O, S, C(CH3)2 r3~Ri〇: h, ch3, c2h5, c3h7, C(CH3)3, ... (b) phenol resin

Phenol based resin, for example:

Naphthol based resin, for example

OH • 11- 1336085 . * 13⁄4 years & 4 months repair (more) replacement page

Dicyclopentadiene resin

4,4',4"Ethylene triphenylene (4,4',4"£1:11;711<16116 1;143卩11611〇1)

OH Tetra phenylolethane

HO OH Tetraxylenol ethane

Tetracresololethane -12- 1336085

Catalyst (a) Cationic catalyst boron trifluoride complex, such as rnh2.bf3, r2nh.bf3, R n.bf (b) anionic catalyst third-grade amine, metal hydroxide, monoepoxide An anion catalyst such as R3N, TMG, NCH2C-C(NH)-N(CH3)2, etc. (c) Imidazole 1-methyl spray. 1-methylimidazole l,2-:T*^0^(l,2-dimethylimidazole) 2_2-heptadecylimidazole 2-ethyl-4-mercaptopurine (2-ethyl- 4-methylimidazole) Dispersant The polymer type dispersant used in the present invention has good adhesion and dispersibility with an inorganic powder, and has excellent phase-to-valley method and dispersibility with an organic resin. Polymer dispersants which can be used include copolyester-branched amines and the like. It is mainly a highly conductive powder such as metal powder (such as gold, silver, copper, aluminum silver magnesium alloy, etc.), metal oxides (such as silver oxide, aluminum oxide, etc.), carbon black, graphite, and the like. -13· 1336085 · q抨竹]θΰίΐ. (More) Positive Replacement Page The following is a description of the technique of the present invention, the material content of which is shown in Table 1, wherein E.poxy 1 is a double-indole-diglycidyl (bisphenol-A diglycidyl ether), Epoxy 2 is tetrabromo disphenol-A diglcidyl ether, and Epoxy 3 is a cyclo aliphatic epoxy. Epoxy 4 is a multifunctional epoxy having the following chemical formula and having a functional group of 4 or more.

Table 1 Composition Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Pre-reaction without Epoxy 1 (g) 7.11 7.1 7.0 6.93 6.93 Epoxy 2 (g) 4.44 4.44 4.38 4.33 4.33 Epoxy 3 (g) 1.24 1.24 1.22 1.21 1.21 Epoxy 4 (g) 1.78 1.77 1.75 1.73 1.73 Hardener (g) 3.36 3.36 3.31 3.28 3.28 Catalyst (g) 0.0626 0.0625 0.062 0.061 0.061 Dispersant 1 (g) 0.513 0.513 0.51 0.51 0.51 Carbon black (g) 4.04 4.06 4.04 3.88 4.08 Silver (g) 0 0 0 29 30 The epoxy resin system accounts for 30~80% by weight of total solids.

The carbon black accounts for 5 to 20% by weight of the total solids, and the polymer dispersant accounts for 0.5 to 5% by weight of the total solids. The hardener comprises from 3 to 20% by weight of the total solids. Further, in Examples 1 to 4, the silver flakes accounted for 0-60% by weight of the total solids. The conductive powder accounts for 5-65% by weight of the total solids. -14- 1336085 'The year of the year is revised (more) is replaced. The manufacturing procedure of the example in Table 1 is as follows, but the comparative example does not perform the pre-reaction system of the following step 3. 1. Epoxy Epoxy 1 ~4 and solvent were placed in a reaction flask and heated to 90-95 ° C to be mixed and allowed to cool. 2. Add an appropriate amount of highly conductive powder to the above solution, and then mix at a high speed to form a mixed solution. The amount of the highly conductive powder to be added is about 5 to 65% by weight based on the total solids.

3. The above mixed solution is pre-reacted at a high temperature of 00 to 140 ° C for about 30 minutes to 5 hours, and then lowered to 80 ° C, and an appropriate amount of a hardener and a catalyst are added to dissolve sufficiently, and then lowered to room temperature. 4. Take an appropriate amount of epoxy resin mixture solution and add appropriate amount of dispersant and other conductive powder (add as needed). 5. The obtained mixture is completely dispersed in three rolls to obtain a well-dispersed mixed resistance resin. 6. The above-mentioned mixed resistive paste is printed by a screen printing process to form a resistor at a position having a pattern.

7. After the measured electrical resistance is measured by electrical quantity, the resistance range obtained by the difference of the material composition is about 35 Ω~1.5kQ. 8. In the thermal property test, the Tg of the resistance component is in the range of 150 to 190 °C. In particular, first add an appropriate amount of epoxy resin to the reaction flask, and then add an appropriate amount of solvent BC (Diethylene Glycol Monobutyl ether) and Dimethyl formamide (DMF). Then, heating to 90 ° C ~ 95 ° C allows the epoxy resin to completely dissolve and cool. Adding an appropriate amount of conductive powder to the above solution, and then stirring at a high speed of -15 - 1336085 I. The 王 槔 ή ΐ 更 更 更 更 更 更 更 更 更 更 更 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 匀 匀 匀 匀 匀 匀After cooling, an appropriate amount of a hardener such as a bisamine or a phenol resin and a catalyst are added to fully dissolve and then lowered to room temperature. The polymer/conductive powder mixture solution prepared beforehand is added, and an appropriate amount of the polymer type dispersant (dispersant 丨) is added, and then if the conductivity is insufficient, an appropriate amount of the conductive powder (such as carbon black, particle size 1 粒径) may be added. ~i〇〇nm), silver plate (1~10 μηι) or other additives, uniformly stirred and dispersed by three rollers to form a polymer/conductive powder mixed slurry, and printed on a fixed pattern by wire mesh screen printing method The solvent is removed by heat baking and cross-linked to form a thick film resistor. The manufacturing process of the thick film resistor of the present invention can be summarized as shown in Fig. 1. The test results of the thick film resistor are shown in Table 2, wherein the glass transition temperature (Tg) is measured by a Thermo Mechanical Analyzer (TMA). Table 2 Characteristics Comparative Example 1 Example 1 Example 2 Example 3 Example Tg (°C) 171 172 175. 177 178 Resistance (Ω) 746-1041 827-898 768-832 39.17~42.69 3 8.05-41.95 Variability (+18.08, -15.38) (+3.67, -4.53) (+3.29, -4.66) (+5.32, -3.36) (+6.03, -3.82) Comparative Example 1 is a preheating reaction process in which the components are contained. The ratios of the first embodiment and the second embodiment are substantially the same, but the resistance value variability (Tolerance) after screen printing differs greatly because the preheating reaction process promotes the reaction of the nano powder with the epoxy moiety structure. A molecular structure having a large molecular weight and a relatively stable structure is formed. Further, in the third embodiment and the fourth embodiment, a formulation in which two kinds of conductive powders are added (in which the carbon black has a particle diameter of 10 to 100 nm and a silver plate has a particle diameter of 1 to 10 μm), both have undergone a pre-reaction process. Resistive material, • 16- 1336085 is called the year of the month (more) is replacing the page, „| ~-*-~~**"**~'·***' *·*^'* * 1 '* ' —. . In addition to the small resistance value, the resistance value variability is also small. From the above results, it is known that 'to obtain a polymer with high stability resistance' / conductive powder mixed material, its formulation It must contain at least one high-functional epoxy resin, a polymeric dispersant, and at least one conductive powder having a nanometer particle size, so as to obtain a kind of embedded electrical resistance material with real application value. The technical and technical features of the present invention have been disclosed above, but those skilled in the art can still make various modifications and modifications based on the teachings and disclosure of the present invention without departing from the spirit and scope of the present invention. It is to be understood that the invention is not to be construed as limited It is covered by the following patent application. [Simplified description of the drawings] Fig. 1 shows the fabrication and charging of the thick film resistor composition of the present invention. [Main component symbol description] None -17-

Claims (1)

1336085 捌 捌 日 日 修 ( 3 3 ( 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 095 An oxy-resin system comprising an epoxy resin having a functional group of 4 or more; at least one conductive powder having an average particle diameter of 10 to 100 nm; a hardener; and a polymer dispersant; The oxygen resin system is characterized in that the polymer has a thick film resistance composition having a glass transition temperature of at least 150 ° C, wherein the polymer dispersant is selected from the group consisting of a copolyester-melamine and a polyester. A polymer thick film resistor composition, wherein the epoxy resin comprises the following chemical structure: 3. The polymer thick film resistor composition according to claim 1, wherein the epoxy resin system further comprises at least a bisphenol A type epoxy resin, a cyclic aliphatic epoxy resin, a naphthalene ring-containing epoxy resin, and a diphenyl ring. Oxygen resin or phenolic epoxy resin. 4. The polymer thick film resistor composition according to claim 1, wherein the epoxy resin system further comprises bisphenol-A-diglycidyl ether epoxy resin, tetrabromobisphenol-A-diglycidyl ether epoxy resin, and A cyclic aliphatic epoxy resin. 5. The polymer thick film resistor composition according to claim 1, wherein the epoxy resin system accounts for 30 to 80% by weight of the total solid content. 6. According to claim 1, the south molecular thick film resistor composition 'where the conductive powder is called 曰 曰 repair (more} positive replacement page contains two or more particle size distributions. 7. According to claim one The polymer consists of a thick film resistor, wherein the conductive powder is selected from the group consisting of silver powder, carbon black and graphite. 8. According to the composition of the polymer, the thick film resistor composition is 'the conductive powder accounts for 5 - 65% by weight. 9. According to the composition of the thick-film resistance of the molecule, wherein the conductive powder system is carbon black. 10. According to the two-layer thick film resistance composition of the item 9, wherein the carbon black accounts for The solid content is 5 to 20% by weight. 11. According to the composition of the thick film resistor of the invention, wherein the conductive powder further comprises a silver sheet, and the average particle diameter is in the range of (4). The composition of the polymer thick film resistor, wherein the silver sheet accounts for 0-60% by weight of the total solids. 13. According to the composition of the thick film resistor of the polymer, the polymer component accounts for the total a solid weight of 0.5 to 5% by weight. a film resistance composition, wherein the hardener accounts for 3-20% by weight of the total solids. 15. The polymer thick film resistor composition according to claim 14, wherein the hardener is selected from the group consisting of diamines, eucalyptus waxes and acid anhydrides. The group consisting of 16. The polymer thick film resistor composition according to claim i, wherein the epoxy resin system and the conductive powder system are first mixed, and pre-reacted at a temperature of 1 〇〇 14 14 for 30 minutes to 5 17. According to the request item r polymer thick film resistor composition, which can be applied to printed circuit boards or embedded resistive components for 1C substrates by screen printing process. -2 - Japanese repair (more) replacement page I3360S5 1 8. According to the resolving item 1 of the ancient eight-worker; eight-back knife thick film resistor composition, which additionally contains a catalyst. 19. According to claim 18, the polymer thick film resistance composition, wherein the catalyst is selected From the group consisting of a ionic catalyst, an anionic catalyst, and a scent. 2 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ At least one conductive powder, wherein the epoxy resin is The polymer thick film resistor has a glass transition temperature of at least 150 and comprises an epoxy resin having a functional group of 4 or more; heating the epoxy resin system and the conductive powder for pre-reaction; adding a hardening After the agent is cooled, and a polymer dispersant is added to form a resistive paste. 21. The method for fabricating a polymer thick film resistor composition according to claim 20, wherein the epoxy resin system and the conductive powder system are heated at a temperature of 30 The pre-reaction is carried out in minutes to 5 hours. 22. The method for producing a polymer thick film resistor composition according to claim 20, further comprising the step of forming a thick film resistor by screen printing the resistive paste. 23. The method according to claim 20, wherein the conductive powder is added again after the temperature is lowered. 24. The method of fabricating a polymer thick film resistor composition according to claim 21, wherein the epoxy resin system comprises the following chemical structure: 25. The method for fabricating a polymer thick film resistor composition according to claim 20, wherein 1336086 is to be replaced on the fourth day of next year, and the epoxy resin system further comprises at least a bisphenol A type epoxy resin and a cyclic fat. Family epoxy tree. Fat, naphthalene ring epoxy resin, bisphenyl epoxy resin or phenol, rattan epoxy resin. 26. The method of fabricating a polymer thick film resistor composition according to claim 20, wherein the epoxy resin system comprises 30 to 80% by weight of the total solids. 27. The method of fabricating a polymer thick film resistor composition according to claim 20, wherein the conductive powder system is selected from the group consisting of silver powder, carbon black, and graphite. 28. The method according to claim 20, wherein the conductive powder system has carbon black and an average particle diameter of 1 〇 to 1 〇〇 nm. 29. The method of fabricating a polymer thick film resistor composition according to claim 28, wherein the conductive powder further comprises a silver flake, and the average particle diameter thereof is in the range of (7). 30. The method according to claim 29, wherein the silver sheet comprises 0 to 60% by weight of the total solids, and the carbon black comprises 5 to 2% by weight of the total solid. The method for producing a polymer thick film resistor composition according to claim 20, wherein the polymer dispersant accounts for 5 to 5% by weight of the total solids.