TW200835733A - Resin composition and coating-film-forming material comprising the same - Google Patents

Abstract

Disclosed is a resin composition showing excellent reliability even under high-temperature/constant-humidity conditions. Also disclosed is a material for forming a coating film, which comprises the resin composition. The resin composition comprises a resin, an inorganic microparticle and a triazinethiol derivative. The triazinethiol derivative is preferably a compound represented by the general formula (1). Wherein R1 represents -SH or -N(R2R3); and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent. The triazinethiol derivative is preferably used in an amount ranging from 0.1 to 5.0 wt% relative to the total solid content of the resin composition.

Description

200835733 IX. Description of the Invention [Technical Field] The present invention relates to a resin composition suitable for a coating method such as a screen printing machine, a jet foaming machine, a spin coater, and the like, and a film forming material containing the resin composition. . [Prior Art] In the field of φ electronic parts, polyetherimide resin, polyamidimide resin, and polyamide resin are used instead of epoxy resin, and heat resistance and electrical properties are reduced in size, thickness, and speed. And a resin excellent in moisture resistance. Since these resins have a rigid resin structure, when the film is formed on the surface of the substrate, the substrate after the film is cured is warped, and the formed cured film lacks flexibility and causes problems of poor bendability. In order to improve the low warpage of the base material formed by the cured film and the flexibility of the cured film, it is proposed to modify the resin to become a flexible and low-elasticity polyamidoximine resin (eg, φ patent document) 1. Patent Document 2, Patent Document 3). A ruthenium filling for improving heat resistance and moisture resistance can be added to these resins. In recent years, miniaturization, thinning, and high-speed electronic equipment include FPC (Flexible Printed Circuit) and TAB (Tape Automated Bonding). The semiconductor wafer and the circuit board are connected by a tape-like film. Technology such as mounting technology) and COF (Chip On F i 1 m; driver IC mounted on a film-shaped printed wiring board). According to such techniques, the wiring pitch of the flexible wiring board is further refined, and the wiring thickness is also thinned. -5-200835733 In the prior art, in order to maintain the insulation reliability of the wiring closet, the insulating thermosetting resin paste is applied and cured on the wiring, and an insulating protective film is formed. In the case of the fiber pitch wiring which is made up of 4 0 // m pitch, even if the thermosetting resin paste of the prior art is used, an insulating protective film is formed, and the insulating protective film is made to have a high temperature and humidity resistance. The performance is still insufficient. When the voltage is applied to the wiring under high temperature and high humidity conditions, the insulation between the wirings is lowered, and the problem of long-term insulation reliability cannot be maintained. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei 08-012763 (Patent Document 3) In view of the above problems of the prior art, the object of the invention is to provide a resin composition which has good insulation reliability under high temperature and humidity conditions, and a film forming material containing the same. In order to solve the problem, the resin composition of the present invention is characterized by containing a resin (A), inorganic fine particles (B), and a triazine thiol derivative (c). Further, the triazine thiol derivative (C) It is preferably a compound represented by the following general formula (1). -6 - 200835733

(1) (wherein R1 represents -SH and -N(R2R3), and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group which may have a substituent). Further, the content of the triazine thiol-based derivative (C) is preferably from 0.1% by weight to 5% by weight based on the total solid amount of the resin component. Further, the resin (A) of the resin composition of the present invention is preferably a polycarbonate skeleton. Further, the resin (A) of the resin composition of the present invention is preferably a urethane structure represented by the following general formula (2). [Chemical 2] 0 0 0 -[x-IJJC-0+ R-〇-〇-〇七R-OCN士(2) φ Η Η " (In the formula, multiple R systems are independently carbon number 1~ The extensor of 18, the X-valent divalent organic group, and the m and η systems are each independently an integer of 1 to 20). Further, as the resin, it is selected from the group consisting of a polyimine resin, a polyamide amine imide resin, a polyamide resin, a modified polyimide resin, and a modified polyamidimide resin. And modified polyamido resin is suitable for grouping. Further, the resin composition of the present invention preferably contains a solvent (D). Further, the resin composition of the present invention preferably contains an epoxy resin. Further, the resin composition of the present invention is a film forming tree for a flexible wiring board. Further, the film forming material of the present invention is characterized by containing the fat composition of the present invention. The resin composition and the film forming material of the present invention are excellent in printability, workability, and insulation reliability, and can form a film property having high temperature resistance and surface wettability, and are applicable to electronic component film materials, Electrolyte for liquid sealing material, varnish for enameled wire, varnish for electric insulation, varnish for laminate, varnish for friction material, interlayer insulating film for printed circuit board, surface protective film, solder resist film, conductive member, etc. Various films are formed in the part. It is especially suitable for the protective film of flexible wiring boards for use. [Embodiment] [Best Mode for Carrying Out the Invention] (Resin (A)) • To improve the heat resistance, properties, moisture resistance, solvent resistance, and chemical resistance of the cured film formed by the resin composition, for example, The resin main chain is incorporated as an example of a component which can improve heat resistance, and is used as a resin (A) such as an ethyl amide resin, a polyimine resin, a polyamide amide resin, or an amine resin or a resin having such a skeleton. Suitable. Among them, a resin having a polyester skeleton and a urethane bond is preferable in that it is flexible and low in elasticity. Further, from the viewpoint of high heat resistance, it is more preferable to use a resin containing an imide bond. In the present invention, the "polycarbon" can be used as the component (A).

The tree has a moisture-preserving impregnation domain, etc., a semi-COF, a special conductive group, a polyfluorene carbonate, a phthalate ester--8-200835733 skeleton resin, usually a 1,6-hexanediol-based polycarbonate. The diol is obtained by reacting a terminal with a compound having a carboxyl group, a compound having an acid anhydride, and/or reacting a terminal with a compound having an isocyanate group.

Further, in the present invention, the "resin containing a fluorene bond" which is used as the component (A) is usually a component (a): one or more selected from the group consisting of trivalent polycarboxylic acids having an acid anhydride group and derivatives thereof And a compound of the tetravalent polycarboxylic acid having an acid anhydride group, which is obtained by reacting the component (b): an isocyanate compound or an amine compound with each other. The "trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof" used as the component (a) is not particularly limited, and generally, the following formula (3) and formula (4) can be used.

(3)

FTOOC

(4) (In the formulas (3) and (4), R' represents hydrogen, carbon number! ~; 〇 alkyl or phenyl, Y1 represents -CH2-, -CO-, -S02-, or - 〇- ) the compound shown. As the "trivalent polycarboxylic acid having an acid anhydride group" used in the component (a), it is particularly preferable from the viewpoints of heat resistance, cost, and the like, and trimellitic anhydride -9 - 200835733. As the component (a), "the 4-valent polyresoric acid having an acid anhydride group is limited to one. c=o special / \ 2 \ γ / is also I o = c < , c = o , ο 者 ο If the formula is as follows, the formula can be used to describe the white form. 2 Υ 中-10-200835733

The tetracarboxylic dianhydride shown in one of the majority of the bases shown. These may be used singly or in combination of two or more. -11 - 200835733 In addition, if necessary, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, arachidic acid, suberic acid, azelaic acid, sebacic acid) may be used as an acid component. , lauric acid, dimer acid, etc.), aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, hydroxydibenzoic acid, etc.). At this time, a guanamine bond is also formed in the molecular chain. As the isocyanate compound used in the component (b), for example, the following formula (7) can be used:

0 0 0 OCN 彳X-NC-0+R-0-C-0 cut-〇01n+X-NGO (7) Η Η (In equation (7), multiple R series indicate independent carbon numbers 1~ "Alkyl group of 18, X is a divalent organic group, and !!1 and n are each an integer of 1 to 2 of each of the independent integers") "a compound having a polycarbonate skeleton and a urethane bond" . The "compound having a polycarbonate skeleton and a urethane bond" represented by the above formula (7) is represented by the following formula (8): [Chemical 8] Γ ^ Ί HO-R-0-C - ΌΗ (8), Jrc\ (in the formula (8), R represents a alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 2 0), and a carbonate diol represented by the following formula (9) ): OCN-X-NCO (9) (wherein X is a divalent organic group) is obtained by reacting diisocyanates represented by each other. The divalent organic compound represented by X in the above formula (9) is, for example, an alkylene group having a carbon number of -12 to 200835733 1 to 20 or a lower alkyl group having an unsubstituted or substituted carbon number of 1 to 5 by a methyl group or the like. Substituting an extended aryl group such as a phenyl group. It is more preferred that the alkyl group has a carbon number of from 1 to 18. Further, it may be an example of a group having an aromatic ring such as two diphenylmethane_4,4'-diyl groups, hydrogenated one group of a 4-methyl group, a 4,4,-diyl group or a diphenylsulfonyl group. Examples of the carbonate diol represented by the above formula (8) include, for example, αω _ poly(hexamethylene carbonate) diol and α, ω-poly(3-methyl-pentamethylene carbonate) diol. For example, the product name "PLACCEL CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220HL" manufactured by D ice 11 Chemical Co., Ltd. is used. These may be used alone or in combination of two or more. Further, examples of the diisocyanate represented by the above formula (9) include diphenylmethane-2,4, diisocyanate; 3,2'-, 3,3'-, 4, 2, 4, 3 , -, 5, 2, -, 5, 3, -, 6, 2, -, or 6,3'-dimethyldiphenylmethane 2,4,-cyanate; 3,2,-, 3,3,4,2,4,3'-,5,2'-,5,3'-, 6,2,-, or 6,3,-diethyldiphenylmethane-2, 4'-diisocyanate; 3,2'-, 3,3,·, 4,2,-, 4,3,·, 5,2,-, 5,3,-, 6,2'-, or 6 , 3'-dimethoxydiphenylmethane-2,4,-diisocyanate; diphenylmethane_4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate; diphenyl Diphenylmethane diisocyanate compounds such as methane-3,4'-diisocyanate and such hydrides; diphenyl ether-4,4'-diisocyanate; benzophenone-4,4'-diisocyanate diphenyl Sulfo-4,4'-diisocyanate; toluene-2,4-diisocyanate, toluene 2,6-diisocyanate; m-xylene diisocyanate; P-xylene diisocyanate; naphthalene- 2,6-diisocyanate; 4,4'-[2,2 bis(4- -13- 20083 5733 base 8 benzene C based oxygen, benzene

The cyanide ester isocyanate, polycyanate, isoxiang, diaryl, etc. The fragrant esters such as the family have the same acid as the cyanide. These may be used alone or in combination of two or more. Further, in the case of the diisocyanate represented by the above formula (9), hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, or the like may be used within the scope of the object of the present invention. An aliphatic or alicyclic isocyanate such as 4,4'-dicyclohexylmethane diisocyanate, trans cyclohexane-1,4-diisocyanate, hydrogenated m-xylene diisocyanate, lysine diisocyanate, or A trifunctional or higher polyisocyanate. The diisocyanate represented by the above formula (9) may be stabilized by using a necessary blocking agent in order to avoid a change in the elapsed time. The blocking agent is not particularly limited, and examples thereof include alcohol, phenol, hydrazine and the like. The ratio of the ratio of the number of hydroxyl groups to the number of isocyanate groups of the carbonate diol represented by the above formula (8) and the diisocyanate represented by the above formula (9) is preferably an isocyanate group/hydroxy group = 1.01 or more. The reaction of the carbonate diol represented by the above formula (8) with the diisocyanate represented by the formula (9) can be carried out in the absence of a solvent or an organic solvent. The reaction temperature is preferably 60 to 200 ° C, and more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the program group, the reaction conditions employed, and the like. For example, in the flask size of 1~5L (liter), it can be set for 2~5 hours. The number of the compound (b-1) (isocyanate compound) thus obtained is preferably from 50 to 10,000, more preferably from 1,000 to 9,500, and particularly preferably from 1,500 to 9,000. If the number average molecular weight is less than 500, the warpage property is deteriorated, and if it exceeds 1 Torr, the reactivity of the isocyanate-14-200835733 compound is lowered, resulting in difficulty in resinization of the polyimine. Further, in the present specification, the number average molecular weight is measured by gel permeation chromatography (GPC), and converted to 値 using a calibration curve of standard polystyrene. Further, the number average molecular weight and the degree of dispersion of the present invention are defined as follows. a) number average molecular weight (Mn) Μη = Σ (NiMi ) / Ni = Σ XiMi (Xi = molecular weight of the molecule of the molar fraction = Ν " ΣΝϊ) b) weight average molecular weight MW = Z (NiMi2) / ENiMi = EWiMi (Wi = weight fraction of molecular weight Mi = ΝίΜί / Σ NiMi) c) Molecular weight distribution (dispersion) Dispersion = MW / Mn As the isocyanate compound of the component (b), a compound (b- The compound other than Ι) (hereinafter referred to as the compound (b-2)). The compound (b-2) is not particularly limited as long as it is an isocyanate compound other than the compound (b-oxime), and examples thereof include diisocyanates represented by the formula (9) and polyisocyanates having a trivalent or higher value. These may be used alone or in combination of two or more. The number average molecular weight range of the isocyanate compound of the desired compound (b-2) is the same as that of the compound (b-oxime), particularly from the viewpoint of heat resistance, and the compound (b-1) and the compound (b-2) are used in combination. Suitable. In addition, when the compound (b-oxime) and the compound (b_2) are used alone, 'the flexibility of the protective film for a flexible wiring board, the improvement of the curvature of the -15-15 - 200835733, etc., and the use of the compound ( b - 1 ) is preferred. As the compound (b-2), the total amount of 5 〇 to 〇〇 〇〇 〇〇 为 is preferably aromatic polyisocyanate, and the balance of heat resistance, solubility, mechanical properties, cost surface, etc., especially 4 4,-diphenylmethane diisocyanate is preferred. When compound (b-1) and compound (b_2) are used, the equivalent ratio of compound (b-Ι) / compound (b-2) is 01/0·9~〇·9/〇·ι More preferably, it is 0.2/0.8~0.8/0.2; especially 〇.3/〇.7~0.7/0.3 is the best. When the equivalent ratio is within this range, film properties excellent in warpage, adhesion, heat resistance, and the like can be effectively obtained. As the amine compound in the component (b), for example, a compound in which the isocyanate group in the (b) component isocyanate compound is changed to an amine group is exemplified. The conversion of the amino group of the isocyanate group can be carried out by a known method. The desired average number of molecular weights of the amine compound is the same as that of the above compound (b - ). φ Further, the compounding ratio of the "a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and/or a tetravalent polycarboxylic acid having an acid anhydride group" of the component (a) is the total number of isocyanate groups in the component (b) (a) The ratio of the total number of carboxyl groups to the acid anhydride groups in the component is preferably 〇·6~1 · 4 , preferably 〇. 7~1 · 3, particularly preferably 0.8 to 1.2. If the ratio is less than 〇6 or exceeds 1/4, it will be difficult to increase the molecular weight of the resin containing the polyimine bond. Further, when the compound represented by the formula (3) of the component (a) and the compound (b-1) of the component (b) are used, the following formula (1 〇 ) can be obtained: -16- (10) 200835733

0 0 0 0

r 11 II II , II

- {X-NC-0 十 R-0-C-0^; R-OCN 士 XNC Η Η Η (In the formula (10), a plurality of R systems are independently alkylene groups having a carbon number of 1 to 18, X A polyamidoquinone imine resin which is a repeating unit represented by a divalent organic group and m and η are each independently represented by an integer of 1 to 20).

In the formula (11), a plurality of R systems are each independently a carbon number of 1 to 18, and a fluorene-based divalent organic group, and m and η are each independently 1 to 2 0' Υ-CH2·, -CO-, -S〇2-, or -0-) is not a repeating mono-polyamidimide resin. Further, when the compound represented by the formula (5) of the component (a) and the compound b (b) are used, the following formula (12) can be obtained:

0 1 one NIH one0- Νo=c/\v=oo=c/\\/c=o onNH ο R- 2) Alkyl (in the formula (12), a plurality of R systems are independently carbon numbers 1 to 18 X, the divalent organic group, m and η are each independently 1~2〇-17-200835733 integer, Y2 is selected from the basis of the majority of the base represented by the formula (6) Unit of polyimide resin. The resin (A) of the component (A) is particularly preferred from the viewpoint of flexibility and low modulus of elasticity, and a polyurethane structure represented by the following general formula (2). [Chemical 2] 0 0 0 r II II II Ί /Λ, -j*X-NC-〇-f R-〇-C~〇-)^R~OCN*·- (2) Η Η " (where, Each of the plurality of R groups is independently an organic group having a carbon number of 1 to 18, and the m and η are each independently an integer of 1 to 20. In the present invention, the (Α) component is used. (a) component in the production method of "resin containing quinone bond": one or more compounds selected from trivalent polycarboxylic acids having an acid anhydride group and derivatives thereof, and tetravalent polycarboxylic acids having an acid anhydride group And the component (b): the isocyanate compound or the amine compound is reacted with each other in an organic solvent, preferably in the presence of a non-nitrogen-containing polar solvent, and the freely produced carbonic acid gas is removed from the reaction system while being heated and condensed. It. The non-nitrogen-containing polar solvent is, for example, an ether-based solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether; a sulfur-containing solvent such as ethyl hydrazine, dimethyl hydrazine or cyclopentane; an ester-based solvent such as r-butyrolactone or cellosolve acetate; a ketone-based solvent such as cyclohexanone or methyl ethyl ketone; toluene, xylene, etc. The aromatic hydrocarbon-based solvent may be used singly or in combination of two or more. It is preferred to use a solvent which dissolves the resin formed in the solvent. After -18-200835733, it is suitable for use as a solvent for resin paste. R-butyrolactone is preferred because it can impart high volatility and low-temperature hardenability, and is carried out under the uniformity of good efficiency. Further, the amount of the solvent to be used is preferably from 0.8 to 5.0 times (weight ratio) of the resin to be produced. When it is less than 0.8 times, the viscosity at the time of synthesis is too high, and it is impossible to stir and it is not easy to synthesize, and if it exceeds 5.0 times, there is a tendency to lower the reaction rate. 反应 φ The reaction temperature is preferably 80 to 210 ° C, and more preferably 100. ~190 ° C, especially 120 ~ 180 ° C is the best. When the temperature is less than 80 ° C, the reaction time will be too long, and the reaction time will exceed 2 1 (TC will produce a three-dimensional reaction, which is prone to gelation. The reaction time can be appropriately selected by the program group size and the reaction conditions used. Further, if necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium or cobalt, or a semi-metal compound. The isocyanate group at the resin terminal may be blocked by a blocking agent such as an alcohol, an indoleamine, an anthracene, a carboxylic acid or an acid anhydride, and it is preferred to use a thermosetting resin as the component (A). Preferably, the average molecular weight is from 15,000 to 50,000, more preferably from 20,000 to 45,000, particularly preferably from 25,000 to 40,000, and the dispersion is preferably from 1.5 to 3,5, more preferably 2.0 to 2. 3.0. When the number average molecular weight is less than 1,500, the film property after tinning is lowered, and if the number average molecular weight exceeds 50,000, it will be insoluble in the non-nitrogen-containing polar solvent, which may cause insolubilization in the synthesis. Poor workability. -19- 2 00835733 The resin of the component (A) used in the resin composition of the present invention may be a number average molecular weight measured by the GPC method, or may be a mixture of two or more resins having different molecular weights. In the mean, the minimum molecular weight is preferably 15,000 or more in terms of number average molecular weight. When the number average molecular weight is less than 1,5,0 0 〇, the moisture resistance and heat resistance are lowered, which is not desirable. Conversely, the number average molecular weight is different. In the resin, the maximum molecular weight is less than 50 in terms of number average molecular weight, which is preferable. When the number average molecular weight exceeds 50,00 Å, the viscosity of the resin becomes high, and the mixing of the inorganic mash and/or the organic mash is lowered. The workability such as screen printing is not preferable. The mixing ratio when two or more different number average molecular weight resins are mixed in the present invention is not particularly limited as long as the number average molecular weight measured by the GPC method is within the range. The concentration of the resin solution is not particularly limited. The content of the resin composition of the resin (A) in the resin composition of the invention is the resin composition of the inorganic fine particles (B) of the present invention. The total solid content is preferably from 50 to 9 9 parts by weight, preferably from 60 to 98 parts by weight, more preferably from 70 to 95 parts by weight. When the resin (A) content is less than 50 parts by weight In the case of the above, the heat resistance and the reliability are lowered. When the amount exceeds 99 parts by weight, the curability is lowered. (Inorganic particles (B)) The inorganic fine particles (B) to be added to the resin composition of the present invention are dispersed in the above resin (A). In the solution, the paste can be formed, and is not particularly limited to -20-200835733. The inorganic fine particles can be used, for example, cerium oxide (Si〇2), aluminum oxide (Al2〇3), titanium dioxide (Ti02), oxidized giant ( Ta205), oxidation pin (Zr02), tantalum nitride (Si3N4), barium titanate (BaO · Ti02), barium carbonate (BaC03), lead titanate (Pb0*Ti02), lead zirconate titanate (PZT), titanium Lead bismuth chromate (PLZT), gallium oxide (Ga203), spinel (MgO · Al2〇3), mullite (3Al2〇3 · 2Si02), kedile (2MgO·2Al2〇3/5Si〇) 2), talc (3MgO·4Si02·H20), aluminum titanate (Ti02-Al203), chromium oxide containing antimony trioxide (Y2〇3-Zr02), barium strontium silicate (BaO · 8Si02 ), boron nitride (BN), calcium carbonate (CaC03), calcium sulfate (CaS04), zinc oxide (ZnO), magnesium titanate (MgO · Ti02), barium sulfate (BaS04), organic bentonite, carbon (C), Hydrotalcite and the like. These may be used alone or in combination of two or more. From the viewpoint of suppressing the outflow of the paste after printing, it is preferable to use ceria, and from the viewpoint of the insulation reliability of the cured film, barium sulfate is preferred. The inorganic particles (B) to be blended in the resin composition of the present invention are preferably those having an average particle diameter of 50 Å / m or less and a maximum particle diameter of 1 〇〇 # m or less. When the average particle diameter exceeds 50/m, the thixotropy coefficient described later will not easily obtain a paste of 1:1 or more. On the contrary, when the maximum particle diameter exceeds 1 #m, the appearance and adhesion of the coating film of the resin composition will be insufficient. The preferred average particle size is 30 μm or less, and more preferably 1 〇# m or less, particularly preferably 1 # m or less, and the most desirable maximum particle size is 8 〇μm or less. 6 0 // m or less, especially 4 0 # m or less is the best. The content of the inorganic particles used as the component (B) is preferably from 10 to 200 parts by weight, more preferably from 20 to 180 parts by weight, based on 100 parts of the total amount of (2008) of 200835733 parts (A). 150 parts by weight is most preferred, and most preferably 50 to 120 parts by weight. When the content of the component (B) is less than 1 part by weight, the viscosity and the thixotropic coefficient of the paste are lowered, the drawing phenomenon of the paste is increased, and the paste after printing is discharged, and the film thickness is also thinned, and the film is coated after tin plating. Both the end state and the electrical characteristics are poor. Further, if the content of the component (B) exceeds 200 parts by weight, the viscosity and the thixotropic coefficient of the paste are increased, which not only reduces the reproducibility to the paste substrate, but also increases the voids and perforations in the printed film. The method of dispersing the inorganic particles (B) in the resin solution is usually applied to a method in which kneading, kneading, mixing, or the like in the coating material field is sufficiently carried out, and the dispersion method is not particularly limited. (Triazine thiol-based derivative (C)) The triazine thiol-based derivative (C) to be incorporated in the resin composition of the present invention is not particularly limited, and a compound represented by the following general formula (1) is generally used. Suitable. [1 2] R1

(wherein R1 represents -SH and -N(R2R3). R2 and R3 represent each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group having a substituent) ° 2, 4, 6 - Examples of the compound represented by the above general formula (1): -22- 200835733 Trihydrothio-S-triazine, 2-dibutylamine-4,6-dihydrothio-ss嗓, 2-aniline Examples of benzyl-4,6-dihydrothio-S-triazine and the like. The products of these compounds are "disnetF" (trade name - with amyl-s-triazine) and "disnetDB" manufactured by Sankyo Chemical Co., Ltd. (trade name: 2 _ dibutylamine · 4 dichlorothio group) -s-diazine), "disnet AF" (trade name: 2-aniline, 4 6 monohydrothio-s-triazine), and the like. The triazine thiol-based derivative may be used singly or in various cases in an amount of 0.1 part by weight based on the amount of the resin solid portion of the (B) inorganic fine particles from which the resin composition is removed. /. 〜5% by weight is preferably '0.5% by weight to 3% by weight. If it is less than 0% by weight, the effect is less likely to occur, and if it is more than 5% by weight, the printability and workability are lowered. ((D) component: solvent) In the resin composition of the present invention, various solvents can be used as the (D) component. The solvent is, for example, an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol, diethyl ether or triethylene glycol diethyl ether which is not a nitrogen-containing polar solvent; dimethyl sulfoxide, one acetylene, one a sulfur-containing solvent such as Feng's ring-shaped Dingfeng; an ester solvent such as butyrolactone, 2-(2-η-butoxyethoxy)ethyl acetate or cellosolve acetate; cyclohexanone and methyl ethyl ketone For example, a ketone-based solvent; an aromatic hydrocarbon-based solvent such as toluene or xylene; and a monoterpene-based solvent such as limonene may be used alone or in combination of two or more. Among the above solvents, the use of r-butyrolactone is more advantageous for printing. (Other resin component) -23- 200835733 In the resin composition of the present invention, in order to improve thermosetting property, various epoxy resins may be optionally added as the component (E). As the epoxy resin of the curing agent, for example, a bismuth A-type epoxy resin (trade name "epikote 828" manufactured by the oil-based shllepoxy (share), etc.), and a bisphenol F-type epoxy resin (made by Toho Chemical Co., Ltd.) Product name "YDF-170", etc., phenolic epoxy resin for phenol paint (product name "epikotel52, 154" made by oiled shellepoxy (share); product name "EPPN-201" made by Nippon Chemical Co., Ltd. Dawchemical company's trade name "DEN-438", etc., phenol-based epoxy resin for bismuth-cresol paint (trade name "EOCN-125S, 103S, 104S" by Nippon Chemical Co., Ltd.), multi-functional Epoxy resin (trade name "Eponl031S" made by oily shellepoxy (share); chiba · specia 11 y · chemca 1 s (share) product name "Araldit0 163"; product name of Changchun Huacheng (share) system" Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-42 1, EX-411, EX-3 2 1", etc.), amine type epoxy resin (oil The trade name "epikote604" made by the company Shellepoxy (share); the business of Dongdu Huacheng (share) system "YH434"; trade name "TETRAD-X" and "TERRAD-C" manufactured by Mitsubishi Gas Chemical Co., Ltd.; trade name "GAN" manufactured by Nippon Chemical Co., Ltd.: the name of the product of Sumitomo Chemical Co., Ltd. "ELM-120", etc., including a heterocyclic epoxy resin (trade name "Araldit PT810" manufactured by Chiba Specialty Chemicals Co., Ltd.), and an alicyclic epoxy resin ("ERL4234, 42 99" manufactured by UCC Corporation , 422 1,42 06", etc.), etc., may be used singly or in combination of two or more. Among these epoxy resins, one of the epoxy groups of three -24-200835733 or more is contained in one molecule. The amine type epoxy resin is particularly preferable in terms of improvement in solvent resistance, chemical resistance, and moisture resistance. These epoxy resins may contain an epoxy compound having only one epoxy group in one molecule. The oxygen compound is preferably used in the range of 〇 20 to 20% by weight based on the total amount of the "resin" used as the component (A). Examples of the epoxy compound include n-butyl glycidyl ether and phenyl glycidol. Ether, dibromophenyl glycidyl ether, dibromocresol glycidyl ether, etc. Further, an alicyclic epoxy compound such as 3,4-epoxycyclohexyl or methyl (3,4-epoxycyclohexane)carboxylate may be used. The "resin" used as the component (A) is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, still more preferably 3 to 40 parts by weight. When the content of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance, and moisture resistance are lowered, and when it exceeds 50 parts by weight, heat resistance and viscosity stability are lowered. As a method of adding the epoxy resin, the "resin" containing the epoxy resin as the component (A) may be dissolved in an organic solvent similar to the dissolved organic solvent, and may be added as it is, or may be added as it is. (Other Additives) As the defoaming agent or correcting agent to be added to the resin composition of the present invention, "KS-602A", "KS-603", "KS-608", and "FA-600" can be applied (above, Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd.; product name), "BYK-A506", "BYK-A525", "BYK-A5 3 0", "BYK-A5 00", "BYK-A501", "BYK-A515", "BYK -A555 -25-200835733", "Byketol-OK" (above, bigchemi, Japan company, product name), "ARUFON UP-1 000" (made by East Asia Synthetic Co., Ltd.: trade name), etc. kind. The antifoaming agent, the correcting agent and the like may be used singly, and in some cases, several kinds may be used. For the solid content of the resin composition, the content is preferably 0.05% by weight to 1% by weight, more preferably 0.05% by weight. %~0.5% by weight. When the content is 0.05% by weight or less, the defoaming agent and film formability are lowered. On the other hand, if it exceeds 1% by weight or more, the defoaming property is improved and the shape retention is lowered. The resin composition of the present invention is suitably used as a material for forming various films. In the resin composition, a coloring agent such as an epoxy resin, a phenol resin, a dye or a pigment, a heat stabilizer, an antioxidant, and a flame retardant may be added to improve the workability at the time of coating and the film properties before and after the film formation. , lubricants, etc. (Film Forming Material) The resin composition of the present invention is suitably used for a resin composition for forming a film or a film forming material. As a film forming material, it can be used for a varnish for a sheet such as a protective film material for an electronic component, a liquid sealing material, a varnish for an enameled wire, a varnish for electrical insulation, a varnish for casting, a mica, or a glass sandpaper. 'MCL laminate varnish, friction material varnish, interlayer insulating film, surface protection film, solder resist layer, 4 layers, etc. in the field of printed circuit boards. Further, the resin composition for forming a film or the film forming material can be used for an electronic component such as a semiconductor element, and can be particularly suitably used for the protection of a flexible wiring board of a c〇F application in which a wiring pattern portion is formed by a tin plating treatment. membrane. -26- 200835733 When the resin composition of the present invention is used for a flexible wiring board protective film for a C 0 F wiring pattern, the heating temperature condition of the heat curing is prevented by the diffusion of the tin plating layer. The viewpoint of appropriate warpage and flexibility of the film is preferably 80 to 130 ° C, and particularly preferably 90 to 120 ° C. Further, the heating time of the thermosetting is prevented from being diffused by the tin-plated chips, and it is preferable to obtain appropriate warpage and flexibility as a protective film, and it is preferably from 60 minutes to 150 minutes, particularly from 80 minutes to 120 minutes. good. In the film forming material of the present invention, the resin composition of the present invention or the resin composition of the present invention may be added with other components as necessary. The film-forming material of the resin-containing composition of the present invention is preferably one having a moderate wettability. The wettability is defined by the contact angle of the liquid sealing material with respect to the cured coating film of the film forming material of the present invention, and the contact angle with the liquid sealing material dropped onto the hard coating film is 35. Below the corner is appropriate. When the contact angle with the liquid sealing material is greater than 35. At the corners, the wet diffusion of the liquid sealing material will be insufficient. For example, when used for coating of a semiconductor, the periphery of the 1C connecting portion cannot be sufficiently covered. The contact angle with the sealing material can be measured by contact with an angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.). [Examples] Hereinafter, the present invention will be described in more detail by way of examples. The following examples are presented to illustrate examples of the invention, and the invention is not limited in any way. (Example 1) -27- 200835733 In a four-necked flask equipped with a 5 L vessel of a cooling tube, a nitrogen gas tube, and a thermometer equipped with a stirrer and a water separator, 1000.0 g (0.50 m) of 1,6- was placed. Hexanediol-based polycarbonate diol (manufactured by Daicell Chemical Co., Ltd., trade name "PLACCEL CD-220") and 250.27 g (1.00 mol) of 4,4'-diphenylmethane diisocyanate and 833.51 g R-butyrolactone, heated to 140 °C. The reaction was carried out at 140 ° C for 5 hours to obtain a diisocyanate. Next, 28 8.20 g (1.50 mol) of trimellitic anhydride and 125.14 g (0.50 mol) of 4,4'-diphenylmethyl diisocyanate and 1361.14 g of r were added to the reaction liquid (diisocyanate). - Butyrolactone, after raising the temperature to 160 ° C, the reaction was carried out for 6 hours to obtain a resin having a number average molecular weight of 18,000 (resin (a)). The obtained resin was diluted with r-butyrolactone to obtain a resin solution having a viscosity of 160 Pa·s and a nonvolatile content of 52% by weight. 10 parts by weight of an amine type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "YH-434", an epoxy equivalent of about 120, and an epoxy group of 4 / molecule) were added to 100 parts by weight of the resin portion of the resin solution. And 7_butyrolactone, a resin solution having a viscosity of 100 Pa·s and a nonvolatile content of 52% by weight. 61.7 g of cerium oxide particles as inorganic particles (B) were added to a resin solution of 23 73 g (resin solid content of 1 23 4 g) (manufactured by Aerozil Co., Ltd., trade name "Aerozil 380", average The particle size of 0.2 / m or less and 185.3 g of barium sulfate particles (product name "B - 30, average particle size 0 · 3 μ m" manufactured by Seiko Chemical Industry Co., Ltd.) are first coarsely kneaded. Then, the resin composition is dispersed and kneaded three times by a high-speed three-roller to form a resin composition for dispersing uniform oxidized fine particles. -28-200835733 Adding 丨·234^ to the obtained resin composition as three "Disnet DB" (trade name "Sankyo Chemicals Co., Ltd.") of the sulfin-thiol derivative (c) was stirred for 3 minutes from a revolving stirrer to obtain a resin composition of the present invention. (Example 2) The resin composition of the present invention was obtained in the same manner as in Example 1 except that the content of "DisnetDB" (triazine thiol derivative (C)) of Example 1 was 12.34 g. Things. (Example 3) The resin composition of the present invention was obtained in the same manner as in the Example except that the content of "DisnetDB" (triazine thiol derivative (C)) of Example 1 was changed to 6 1 · 7 g. . # (Example 4) Adding "DisnetF" (trade name of Sankyo Chemicals Co., Ltd.) of I234g in place of "0丨51^08" of triazine thiol derivative (C). 'With Example 1 The resin composition of the present invention was obtained by the same operation. (Example 5) A resin composition was obtained in the same manner as in the shell example 1 except that the content of "DisnetF" in the shell example 4 was made to be 12.34 g. -29-200835733 (Example 6) A resin composition was obtained in the same manner as in Example 1 except that the content of "DisnetF" of Example 4 was changed to 61.7 g. (Example 7) When 12.34 g of DisnetF of Example 4 was added, a resin composition was obtained in the same manner as in Example 1 except that 3.8 g of DisnetDB was added. (Example 8) When 12.34 g of DisnetF of Example 4 was added, I9.7 g was added.

In the same manner as in Example 1, except for DisnetDB, a resin composition was obtained. (Comparative Example 1) A resin composition was obtained in the same manner as in Example 1 except that "DisnetDB" (triazine thiol derivative (C)) of Example 1 was not used. # The properties of the respective resin compositions obtained in the above examples and comparative examples were measured by the following methods. The results are shown in (Table 1) and (Table 2). (1) The resin composition is obtained on a copper foil of 3 5 /zm, and the resin composition is obtained by a printing machine (manufactured by Newlong Co., Ltd., trade name "LZ-045") and a mesh screen (150 mesh of the company murakami) Paving), printing at a printing speed of 100 mm/sec at a 10 mm angle, drying in an air atmosphere at 90 ° C for 3 minutes, and then heating and hardening at 120 ° C for 60 minutes to form a resin film. Resin film, in the universal projector (nikon stock -30- 200835733 company made a magnification of 50 times), observe the surface state, the surface is not uneven, the evaluation is 〇, the surface of the bump is evaluated as x ° (2) insulation reliability In the copper wiring pattern of the test L/S=15 μm/15 //m, the film thickness after printing on the sputter substrate of the copper wiring is hardened to obtain a resin composition, and the film thickness is 1 〇//m, Heat hardened at 120 ° C for 60 minutes. The obtained resin film was placed in an atmosphere of a temperature of 120 ° C and a humidity of 85%, and a voltage of DC 60 V was continuously applied to evaluate the retention of the insulation resistance after 1 〇 〇 hours. 1 绝缘 绝缘 After the insulation resistance is 107Ω or more, it is rated as 〇, and if it is less than 1〇7, it is rated as X. (3) Wetting property (contact angle) of the sealing material The resin composition obtained by coating the rough surface of the electrolytic copper foil having a thickness of 35/zm or the thickness of 5 Å/m of the 醯5 amine thin fe, 9 Dry under the armpit for 15 minutes - after the second m signal, 12 (heated at TC for 00 minutes, obtained from the hardened coating film X r ^ 20~3 0 / zm of each resin composition), dropped into i〇 / zl The epoxy-based sealing material (manufactured by 曰I into a process (k part), trade name "CEL-C-5020"), 壬π ρπ 4-·^ and measured by a contact angle measuring device (manufacturing interface science) With hardened coating film; furnace: net heart e fee tentacles. In addition, the interface between the sealing material and the cured coating film was observed using a universal projector (magnifications of nik〇n Co., Ltd., 5 0 &, (b)). The baseline of observation is as follows. 〇·The boundary between the material and the cured film X ^Elevation of the sealing material and the cured film-31 - 200835733 [Table 1] Item Example 1 Example 2 Example 3 Example 4 Example 5 Triazine thiol Derivative content (%) DisnetDB 0.1 1 5 - - DisnetF • • • 0.1 1 Printability 〇〇〇〇〇 Insulation reliability 〇〇〇〇〇 Sealing material contact angle (.) 30 30 28 30 30 Wetting 〇〇 〇〇〇 [Table 2] Item Example 6 Example 7 Example 8 Comparative Example 1 Content of triazine thiol derivative (%) DisnetDB • 0.3 1.6 • DisnetF 5 1 1 — Printability 〇〇〇〇 insulation reliability 〇〇〇X Sealing material contact angle (.) 28 30 30 34 Wetting 〇〇〇〇

The above results are proved as follows. Examples 1 to 8 show that the voltage of DC 60V set in an atmosphere of 120 ° C and 85% humidity for 100 hours can maintain the insulation resistance. Therefore, it has been confirmed that the resin composition of the present invention and the resin film thereof exhibit stable insulation resistance for more than 100 hours under a high temperature and high humidity atmosphere of temperature 12 (TC, humidity 85%, voltage 60 V), and contact with the sealing material. The angle is also small, and the wettability is also improved. On the contrary, Comparative Example 1 reduces the insulation resistance at 50 hours. [Industrial Applicability] -32- 200835733

The resin composition for screen printing and the film-forming material of the present invention have _ _ different characteristics, and are suitable for protective materials for electronic parts, liquid sealing materials, varnishes for varnishes for electrical insulation, varnishes for laminates, friction varnishes, An electronic component such as an interlayer insulating film, a surface protective film, a solder resist, an adhesive layer, or the like, and a semiconductor element in the field of a printed circuit board. -33-

Claims (1)

200835733 X. Patent Application Range 1 · A resin composition characterized by containing resin (A) microparticles (B) and triazine thiol-based derivatives (c). 2. The resin composition of claim 1, wherein the thiol derivative (C) is a compound represented by the following general formula (1), [Chemical Formula 1] R1 (wherein R1 represents -SH and N(R2R3), and R2 and: independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or may have an aryl group). 3. The resin composition of claim 1, wherein the triazine thiol derivative (C) is from 0.1% by weight to 5% by weight based on the total solid content of the fat component. • 4 • The resin composition of the first application of the patent scope, wherein (A) is a polycarbonate matrix. 5) The resin composition of the first application of the patent scope, wherein (A) is a polyurethane containing the following general formula (2): 2 [Chemical 2] 0 0 0 r II II II Ί X-IJJC-0+ R-0-C-0 First R-OCN Gentry Η Π (In the formula, multiple R series are independently carbon-numbered 1~18 X-type divalent organic groups, melons and η series The resin is independently 1 to 20, and the inorganic triazine is the content of the tree. The resin is the resin, (2) alkyl, (a) 〇-34- 200835733 6 · as claimed in the patent scope A resin composition of the item 1, wherein the resin (A) is selected from the group consisting of a polyimine resin, a polyamide amine imide resin, a polyamide resin, a modified polyimine resin, and a modified polyamine. A group of bismuth imine resins and modified polyamido resins. 7 · A resin composition according to claim 1 of the patent scope, wherein hydrazine contains a solvent (D). 8 · As claimed in claim 1 The resin composition containing the epoxy resin (E). The resin composition of the first aspect of the invention is a resin composition for forming a film of a flexible wiring board. * 1 square - kind of film-forming material characterized by comprising patent range based resin composition, Paragraph 1. -35- 200835733 七明说单单单符表 is the representative table of the generation of the map table. • The representative map of this book, the table of the first and second refers to the CC without the eight, if the case has a chemical formula, please reveal the most Chemical formula showing the characteristics of the invention: none -4-