TW200911922A - Resin composition, and film-forming material comprising the same - Google Patents

Abstract

Disclosed is a resin composition comprising: a component (A) which is a resin having an acid anhydride group and/or a carboxyl group; a component (B) which is an epoxy resin; and a component (C) which is a filler comprising hydrotalcite. The component (A) preferably has a polycarbonate skeleton, more preferably has a constituent unit represented by the general formula (1). (1) wherein multiple R's independently represent an alkylene group having 1 to 18 carbon atoms; multiple X's independently represent an alkylene having 1 to 18 carbon atoms or an arylene group; and m and n independently represent an integer of 1 to 20. The resin composition can be used suitably in screen printing, has reduced adhesion to a polyimide film which is a cured coating film, and enables to reduce the occurrence of black blister in an electrode upon applying current under high-temperature and high-humidity conditions. Also disclosed is a film-forming material comprising the resin composition.

Description

The resin composition such as the film forming material, the spin coater, and the like, and the resin composition of the resin, which is excellent in thickness, high imide resin, polyfluorene, and moisture resistance, are greatly warped and hardened, and a resin is proposed. Amine resin (Ref. 3). Resins such as such resins or organic chelating agents, or chelating agents and surface treating agents, etc. 200911922 IX. Field of the Invention [Technical Fields of the Invention] The present invention relates to a resin composition and the inclusion thereof, especially regarding the application to the net A thixotropy film-forming material containing a thixotropy in a coating machine or a cloth coating method. [Prior Art] In recent years, in the field of electronic components, a resin which is a material for heat-resistant and electrical property film formation has been used in place of an epoxy resin in place of a small-sized polyimide resin or a polyamide resin. However, when these thinner substrates are used, the substrate after curing has a problem that the film lacks flexibility and the flexibility is deteriorated. Therefore, in order to improve the warpage property, the flexibility of the flexibility, and the low elastic modulus of the polyimide, for example, Patent Document 1, Patent Document 2, and the patent document improve the printability and workability, and inorganic The chelating agent is dispersed in the resin solution. Further, in order to improve the adhesion between the substrate and the resin, additives of various crosslinking agents are used. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. However, on the surface of the copper wiring side of the flexible wiring board to which the copper wiring is applied on one side of the polyimide film, the above-mentioned film forming material is screen-printed, and then the flexible person is wound, and the flexibility is obtained. There is a problem in that a cured film composed of a film forming material is attached to the side surface of the wiring board on which the copper wiring is not applied. Conventionally, a spacer layer has been conventionally provided between the polyimide film and the cured film. Further, in the case where the wiring board in which the film forming material is formed into a hardened film by the film forming material is energized under high temperature and high humidity, there is a concern that the electrode has a black bulge and the electrical characteristics are lowered. The present invention has been made in view of the above-described conventional disadvantages, and an object of the present invention is to provide a resin composition in which the adhesion between the cured film and the polyimide film is reduced, and the black bulge of the electrode is reduced when the electrode is energized under high temperature and high humidity. And a film forming material containing the resin composition. [Means for Solving the Problems] In order to solve the above problems, the resin composition of the present invention is characterized by comprising (A) a component: a resin having an acid anhydride group and/or a carboxyl group, and (B) a component: an epoxy resin' and (C) ) Ingredients: A hydrazine containing hydrotalcite. In the resin composition having the above composition, the component (A) preferably has a polycarbonate skeleton. Further, the above component (A) preferably contains a structural unit represented by the following formula (1): 200911922 [Chemical 1] 0 0 0

II II II X-N-C-0-(R-0-C-0)^R-0-C-N- Η Η

(In the formula (1), a plurality of R each independently represent an alkylene group having 1 to 18 carbon atoms, and a plurality of X each independently represent an alkylene group or an extended aryl group having 1 to 18 carbon atoms, and 111 and 11 each independently represent 1 An integer of ~20). Further, the component (A) is preferably an isocyanate residue of at least one resin selected from the group consisting of a polyimine resin having a polycarbonate skeleton, a polyamidoximine resin, and a polyamide resin, and an acid anhydride group. A resin obtained by reacting a trivalent or higher polycarbonate or a derivative thereof. Further, in the resin composition having the above-mentioned composition, the content of the component (C) is preferably from 10 to 50% by mass based on 100 parts by weight of the component (A), and the hydrotalcite content in the component (C) is higher. Good is 1〇~50% by mass. Further, the resin composition of the present invention is suitably used as a protective film for a flexible printed circuit board substrate in which a copper box is laminated on a polyimide substrate. The film forming material of the present invention is characterized by comprising the above-described resin composition of the present invention. [Effect of the Invention] The resin composition of the present invention can reduce the adhesion of the film after hardening to the poly-yttrium film, and can reduce the black bulging of the electrode when the electrode is energized under high temperature and high humidity, and thus can be applied to the flexible wiring. The electronic parts such as boards are used to achieve the effect of obtaining electronic parts with high reliability. -8-200911922 [Embodiment] The resin composition of the present invention includes the component (A): a resin having an acid anhydride group and/or a carboxyl group, and (B) a component: an epoxy resin, and a component (C): A hydrazine containing hydrotalcite is an essential component. The necessary ingredients are explained in detail below. [(A) component: resin having an acid anhydride group and/or a carboxyl group] "Resin having an acid anhydride group and/or a carboxyl group" as an example of an epoxy resin or a phenol having a butadiene structure or a oxime structure Resin, acrylic resin, polyurethane, polybutadiene, hydrogenated polybutadiene, polyester, polycarbonate, polyether, poly maple, polytetrafluoroethylene resin, polyfluorene oxide, melamine resin, polyfluorene An acid anhydride group and/or a carboxyl group are introduced into a main chain and/or a side chain of a resin such as an amine, a polyamidimide or a polyimine. These may be used singly or in combination of two or more. Further, a resin having an acid anhydride group and/or a carboxyl group and a resin having no acid anhydride group and/or carboxyl group may be used. The method of introducing the above carboxyl group is an epoxy resin having a butadiene structure or a xenon structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a hydrogenated polybutadiene, a polyester, and a poly In the synthesis of carbonate, polyether, polyfluorene, polytetrafluoroethylene, polyfluorene oxide, melamine resin, polyamine, polyamidimide, polyimine resin, etc., free radical polymerization can be used. Obtained by polycondensation or ionic polymerization of a compound having a carboxyl group. Further, the method of introducing the above acid anhydride group can be derived from an epoxy resin having a butadiene structure or a xenon structure, a phenol resin, an acrylic resin, a polyaminomethyl-9-200911922 acid ester, a polybutadiene, and a hydrogenation polymerization. Epoxy residues of butadiene, polyester, polycarbonate, polyether, polyfluorene, polytetrafluoroethylene, polyfluorene oxide, melamine resin, polyamide, polyamidimide, polyimine resin, etc. The group, the isocyanate residue, the hydroxyl residue, the carboxyl group and the like are obtained by reacting with a compound represented by the following formula (2) and/or formula (3). [化2] 0

II W——Z1 c

II (2 ) 0 (In the formula (2), Ζ1 represents an organic group, and w represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group). [化3]

(In the formula (3), "Z represents an organic group, and w represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group). By introducing an acid anhydride group and/or a mercapto group at the terminal and/or the side chain of the resin, the reactivity with the epoxy resin of the component (B) described later becomes high, so that the adhesion to the spacer layer and the solder resist can be improved. Synergy. Further, the resin of the component (A) of the present invention is preferably inconvenient and low in modulus in order to correspond to the main flexible substrate. The resin for making the component is flexible and has a low modulus of elasticity. For example, a component capable of improving flexibility can be introduced on the main bond of the tree, which is preferably a polybutadiene skeleton. 'Oxygen resin skeleton and / or polycarbonate skeleton. Further, in order to improve heat resistance, electrical properties, moisture resistance, solvent resistance, and chemical resistance of the cured film, for example, a component capable of improving heat resistance is introduced into the main chain of the resin, and these components are preferably, for example, polyfluorene. Imine, polyamidamine or polyamine or such a skeleton. Among them, a polycarbonate skeleton and a ruthenium imide skeleton are preferable from the viewpoints of flexibility, low elastic modulus, and high heat resistance. In the present invention, the "resin having an acid anhydride group and/or a carboxyl group" as the component (A) is usually a compound having a carboxyl group, such as a 1,6-hexanediol-based polycarbonate diol, and an acid anhydride. It is obtained by reacting a compound and/or a compound having an isocyanate group. Further, in the present invention, the "resin having an acid anhydride group and/or a residue" as the component (A) may be, for example, a component selected from the group consisting of (a) component: a trivalent polycarboxylic acid having an acid field group, and a derivative thereof. And one or more compounds having a tetravalent polybasic acid having an acid anhydride group are obtained by reacting the component (b): an isocyanate compound or an amine compound. The "trivalent polyvalent residual acid having an acid anhydride group and the derivative thereof" of the component (a) is not particularly limited, and for example, a compound represented by the following formulas (4) and (5) can be used:

-11 - 0 200911922 [Chemical 5] FTOOC- (5) (In the formulas (4) and (5), R' represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y1 represents -CH2-, -CO -, -S02-, or -0-). The "trivalent polycarboxylic acid having an acid anhydride group" of the above component (a) is preferably a pyromellitic anhydride from the viewpoints of heat resistance and cost. As for the other "tetravalent polybasic acid having an acid anhydride group", there is no special formula such as OHC', which can be used to make J0.' 6 '. I limit o = c. 'Y2 acid carboxylic acid four

bMO

In the bMO formula, the number of bases selected by white is 2 Y is the number of bases. -12- 200911922

). These groups may be used singly or in combination of two or more. Further, in addition to these, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or the like) may be used as an acid component. Aromatic dicarboxylic acid (isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxygen-13-200911922 bisdibenzoic acid, etc.). In this case, a guanamine bond is also formed in the molecular chain. As the isocyanate compound to be used as the component (b), a diisocyanate represented by the following formula (8) (hereinafter also referred to as a compound (b-1)) can be used:

0 II

0 II 0 0CN-[x-NC-04R-0-C-0-^R-0CN^X-NC0 η Η Π

(In the formula (8), a plurality of R groups each independently represent a carbon number of a stretch alkyl group 'X is a divalent organic group, and m and η are each independently an integer of 1 to 2 Å). The compound (b_丨) represented by the above formula (8) is a carbonate diol represented by the following formula (9): [Chemical 9] r π ί

H0--R-0-C"0 --R-OH v- m (9 ) (In the formula (9), a plurality of R are each independently a carbon number of the alkyl group, and m is an integer of 2 It is obtained by reacting with a diisocyanate represented by the following formula (1〇): OCN—X—NCO (1〇) (wherein X is a divalent organic group) ^ is represented by X in the above formula (10) The divalent organic group is exemplified by, for example, an alkylene group having 1 to 20 carbon atoms or an extended aryl group such as a phenyl group which is unsubstituted or substituted with a low carbon group having a carbon number of 1 to 5 such as a methyl group. The carbon number of the above alkyl group is more preferably 18. Further preferably, it is a group having two aromatic rings such as diphenylmethyl _4,4,-diyl, bis-14-200911922 phenylfluorene-4,4'-diyl. The carbonate diol represented by the above formula (9) can be exemplified by, for example, α,ω-poly(hexamethylene carbonate) diol, α,ω-poly(3-methyl-pentamethylene carbonate). The diol or the like is exemplified by the trade name "PLACCEL CD-205, 205PL, 205HL, 210, 210PL > 210HL, 220, 220PL, 220HL" manufactured by Diacell Chemical Co., Ltd., and the like. These may be used singly or in combination of two or more. Further, the diisocyanate represented by the above formula (10) can be exemplified by, for example, diphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'-, 4, 3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate; 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; diphenylmethane ― 3,4′-diisocyanate; diphenyl ether _4,4,-diisocyanate; benzophenone-4,4′-diisodecanoate; diphenylboron-4,4,diisocyanate ; toluene-2,4_ diisine lys; toluene 2,6-diisocyanate; m-xylene diisocyanate; p-xylene diisocyanate; naphthalene 2,6-diisocyanate; 4,4 , _ [2,2_bis(4,phenoxyphenyl)propane] diisocyanate, and the like. Among these diisammonic acid vinegars, it is preferred to use the X-type aromatic sulfonate of the formula (8). These may be used singly or in combination of two or more kinds of diisocyanates represented by 〇X^ (10). In the range of -15-200911922 of the present invention, hexamethylene diisocyanate, 2,2,4-tri can be used. Methylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trans cyclohexane-1,4-diisocyanate, hydrogen-m-xylene diisocyanate, leaving An aliphatic or alicyclic isocyanate such as an amino acid diisocyanate or a trifunctional or higher polyisocyanate. The diisocyanate represented by the above formula (10) may be stabilized with a necessary blocking agent in order to avoid a change with time. The blocking agent is an alcohol, a phenol, a hydrazine or the like, but is not particularly limited. The ratio of the number of hydroxyl groups to the number of isocyanate groups is the ratio of the number of hydroxyl groups to the number of isocyanate groups, and the ratio of the number of hydroxyl groups to the number of isocyanate groups is from the ratio of the number of hydroxyl groups to the number of isocyanate groups. It is better. The reaction of the carbonate diol represented by the above formula (9) with the diisocyanate represented by the above formula (10) can be carried out in the absence of a solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 2 ° C, more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the size of the batch, the reaction conditions employed, and the like. For example, it may be 2 to 5 hours in a flask scale of 1 to 5 L (liter), and the number average molecular weight of the compound (b-1) (isocyanate compound) thus obtained is preferably 500 to 10,000, and is 1,000. ~9,500 is better, with 1,50 0~9,000 as the best. When the number average molecular weight is less than 500, the warpage property tends to be deteriorated. When the amount exceeds 1 Torr, the reactivity of the isocyanate compound is lowered, and it is difficult to resinize the polyimide. Further, the number average molecular weight in the present specification is measured by gel permeation chromatography (GPC) and converted using a calibration line 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 (Μη) Μ„ = Σ ( NjMj ) /Ni^ZXjMj (X, = molecular mole fraction of molecular weight Mi ζΝι /ΣΚ) b) Weight average molecular weight MW = I ( N,Mj2) /ΣΝ1Μί = ΣΨ1Μί (Wi = molecular weight fraction of molecular weight Mi ^ΝίΜ, /ΣΝίΜί) c) Molecular weight distribution (dispersion) Dispersion = MW / Mn As the isocyanate compound of the above component (b), a compound other than the compound (b-1) (hereinafter referred to as the compound (b-2)) can be used. The compound (b-2) is an isocyanate other than the compound (b-oxime). The compound is not particularly limited, and examples thereof include a diisocyanate represented by the above formula (9), a trivalent or higher polyisocyanate, etc. These may be used singly or in combination of two or more. Compound (b-2) The preferred range of the number average molecular weight of the isocyanate compound is the same as that of the above compound (b-1). Especially in terms of heat resistance, it is preferred to use the compound (b-1) and the compound (b-2). And, separately, using the combination In the case of (b-1) and the compound (b-2), it is preferred to use the compound (b-1) from the viewpoints of improvement in flexibility and warpage of the protective film for a flexible wiring board. As the compound (b - 2 ), an aromatic polyisocyanate is preferably used in an amount of from 50 to 100% by weight based on the total amount, and heat resistance, solubility, mechanical properties, mechanical properties, and the like are considered. The equilibrium is preferably 4,4,-diphenylmethane diisocyanate. When compound (b-Ι) and compound (b-2) are used, compound (b-1)/compound (1>-2) The equivalent is preferably 〇.1/〇.9 to 0.9/0.1, more preferably 0.2/0.8 to 0.8/0.2, and most preferably 0.3/0.7 to 0.7/0.3. If the equivalent ratio is within the range, At the same time, good film properties such as low warpage, adhesion, and good heat resistance are obtained. The amine compound in the above component (b) can be exemplified by converting an isocyanate group in the isocyanate compound of the above component (b) into an amine. a compound of a group. The conversion of an isocyanate group to an amine group can be carried out by a conventional method. The preferred range of the number average molecular weight of the amine compound is The compound (b-oxime) is the same. The blending ratio of the "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 (a) component The ratio of the total number of carboxyl groups and acid anhydride groups to the total number of isocyanate groups in the component (b) is preferably from 0.6 to 1.4, more preferably from 0.7 to 1.3, and most preferably from 0.8 to 1.2. If the ratio is less than 0.6 or exceeds 1.4, the molecular weight of the resin containing the polyimine bond tends to be difficult to increase. In addition, when the compound represented by the above formula (2) is used as the component (a) and the compound (b-1) is used as the component (b), a polyamidamine having a repeating unit represented by the following formula (11) can be obtained. Imine resin: 【化1 0】

ο ο ο 〇P fr II II II , II η -{X-NC-O-fR-OCO^-R-OCN^XNC N— Η Η Η 1 -18- 200911922 (in equation (11), plural R Each is independently an alkylene group having a carbon number of 1 to 18, and X is a divalent organic group 'm and η are each independently an integer of 1 to 20). Further, when the compound represented by the above formula (5) is used as the component (a) and the compound (b-1) is used as the component (b), a polyamine having a repeating unit represented by the following formula (12) can be obtained.醯 imine resin: 【化1 1】

12)

〇 〇〇〇 r II it II ^ II

-fX-N C-0-(-R_0-C-0-^R_0 CN^-XNC Η Η Η (In the formula (12), a plurality of R are each independently an alkylene group having a carbon number of 1 to 18, and X is The divalent organic group, m and η are each independently an integer of from 1 to 20, and γΐ is -CH2-, -CO-, -so2- or -0-). Further, a compound represented by the above formula (6) is used as ( When the component (a) is used as the component (b), a polyimine resin having a repeating unit represented by the following formula (1 3 ) can be obtained:

[1 1 I

0 0

0 〇 〇 C C -{X-NC-0-(-R-0-C-0^; R-0CN-^X-N Y2 NJ_

Η H C C

II II (In the formula (13), the plurality of R are each independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, m and η are each independently an integer of 1 to 20, and Y2 is selected from the above The formula (7) represents the basis of a plurality of bases). In the production method of the "resin having an acid anhydride group and/or -19-200911922 or a carboxyl group" used in the present invention, the component (a) is selected from a trivalent polycarboxylic acid having an acid anhydride group. And a derivative thereof and one or more compounds of a tetravalent polycarboxylic acid having an acid anhydride group, and the component (b): an isocyanate compound or an amine compound are reacted in an organic solvent, preferably in the presence of a non-nitrogen-containing polar solvent. It is carried out by heating and condensing under the removal of freely generated carbonic acid gas from the reaction system. Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; a sulfur-containing solvent such as methyl sulfoxide, diethyl boron, dimethyl hydrazine or cyclobutyl ketone; an ester solvent such as γ-butyrolactone or fibrin acetate; cyclohexanone, methyl ethyl ketone, etc. A ketone solvent; an aromatic hydrocarbon solvent such as toluene or xylene. These may be used alone or in combination of two or more. It is preferred to use a solvent which dissolves the resin generated in the above solvent. After the synthesis, it is preferred to use a solvent suitable as a paste. In order to carry out the reaction with high volatility, low-temperature curability, and efficient and uniform, it is also preferable to use γ-butyrolactone. Further, the solvent is preferably used in an amount of from 0.8 to 5.0 times by weight (by weight) based on the resin containing the produced quinone bond. If it is less than 8 times, the viscosity at the time of the synthesis is too high, and it is difficult to synthesize because it cannot be stirred. If it exceeds 5 · 〇, the reaction rate tends to decrease. The reaction temperature is preferably from 80 °C to 210 °C, preferably from 1 Torr to 190 °C, and from 120 ° to 180 °C. (:The best. If the temperature is less than 80 °C, the reaction time is too long. If it exceeds 210 °C, the reaction will be easy to cause gelation. The reaction time can be made according to the batch size and the reaction conditions. -20- 200911922 Also, 'Reaction can be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, tin, zinc, titanium, cobalt or a metal or a semimetal compound, as required. The polyamine resin, the polyamidimide resin, and the polyimine resin are those having an isocyanate residue, and the above isocyanate residue can be obtained by the above formula (2) and/or the above formula (3) By reacting the compound to obtain a resin having an acid anhydride group, the reactivity with the epoxy resin of the component (B) described later can be improved, and the adhesion to the polyimide substrate can be lowered. 2) and/or the compound of the above formula (3), a blocking agent such as an alcohol, an indoleamine or an anthracene may be used in combination to the extent that the effects of the present invention are not impaired. / or the compound of the above formula (3) is preferably represented by the following formula (14) The tetracarboxylic dianhydride (pyromellitic anhydride).

The amount of the above pyromellitic anhydride added is in the range of 1 Torr to 20% based on the total amount of the isocyanate. If the amount is more than 20%, it is difficult to control the viscosity and the workability is lowered. Further, when it is less than 1%, it tends to adhere to the polyimide film after hardening. Further, in the present invention, other components of the resin having an acid anhydride group and/or a carboxyl group which can be used as the component (A) can be, for example, a mixture of the general formula (9), the general formula (10) and the following general formula (15). It is obtained by the reaction under the same conditions as in the synthesis of the above (b-1) - 21 - 200911922. The resin thus obtained is a carboxyl group-containing urethane resin having a repetitive structure represented by the following formula (16), which can improve the reactivity with the epoxy resin of the component (B) described later and reduce Adhesion of the amine substrate. When the urethane resin having a carboxyl group obtained as described above has an isocyanate residue, the formula (2), the formula (3), an alcohol, an indoleamine, an anthracene or the like may be used as described above. The isocyanate residue is reacted. The compound represented by the formula (15) is exemplified by, for example, dimethylolpropionic acid, dimethylolbutanoic acid or the like. [1 1] R1

HOH, CC-CH, OH 1 I 2 COOH , (in the formula (15), R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms) [Chemical Formula 1 5] Ο Ο Ο Ί Ο II II II II XNC-0 -(-R-〇-C-〇-)-R-〇-CN- -XNC-0-HC-C-CH-0-C- Ν I m II 2 ι 2 Η

ο II I Η I Η

COOH (16) (In the formula (16), the plurality of R are each independently an alkylene group having 1 to 18 carbon atoms. R1 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and X is a divalent organic group, m and η is independently an integer from 1 to 20). The number average molecular weight of the resin thus obtained is preferably from 15,000 to 50, more preferably from 20,000 to 45,000, and most preferably from 25,000 to 40,000, and the dispersion at this time is preferably from 1.5 to 3 to 5, and from 2 to 3.0. better. If the number average molecular weight is less than 15,000, the hardened film is liable to be attached to the polyimide film. -22-200911922 The tendency is 'If the average molecular weight exceeds 50,000, the viscosity of the resin becomes high' and the inorganic chelating agent And the compatibility of the organic chelating agent and the tendency to reduce the workability such as screen printing are not preferable. (Component (B): Epoxy resin) Various epoxy resins can be added to the resin composition of the present invention to improve thermosetting properties. The epoxy resin as the curing agent is exemplified by, for example, a bisphenol a-type epoxy resin (trade name "EPICOTE 82 8" manufactured by the oil-coated clamshell epoxy resin), and a bisphenol F-type epoxy resin (Dongdu Huacheng (share) "The product name "YDF-170", etc.), the novolac type epoxy resin (the product name "EPICOTE 152, 154" made by the oily clamshell epoxy (share); the product name of the Nippon Chemical Co., Ltd." EPPN-201"; trade name "DEN-43 8" manufactured by Dow Chemical Co., Ltd.), o-cresol varnish type epoxy resin (trade name "EOCN-125S, 103S, 104S" manufactured by Nippon Kayaku Co., Ltd. Etc.), multi-functional epoxy resin (trade name "Ep〇nl031S" made by oily clamshell epoxy (shares); trade name "ARALDITE 〇1 63" made by steam batter chemicals (shares); Nagase chemical conversion (shares) The product name "DENACOL EX-6 1 1 , EX-6 1 4, EX-6 1 4B, EX-622, EX-5 1 2, EX-521, EX-421, EX-411, EX-321" "Equivalent Epoxy Resin" (EPICOTE 604, manufactured by Oyster Chemical Co., Ltd.): The product name "YH43 4" manufactured by Tohto Kasei Co., Ltd.; Mitsubishi Gas The trade name "TETRAD-X" and "TERRAD-C" of the chemical (share) system; the trade name "GAN" of the Japanese chemical company (share): the product name "ELM-120" by Sumitomo Chemical Co., Ltd., etc. Epoxy resin containing a heterocyclic ring (trade name "ARALDITE PT810" manufactured by 234-200911922 Chemicals Co., Ltd.), and alicyclic epoxy resin ("ERL4234, 4299, 4221, 4206" manufactured by UCC Corporation ", etc.), these may be used alone or in combination of two or more. Among these epoxy resins, an amine type epoxy resin containing three or more epoxy groups per molecule is preferable from the viewpoint of improving solvent resistance, chemical resistance, and moisture resistance. These epoxy resins also contain an epoxy compound containing one epoxy group per molecule. The epoxy compound is preferably used in an amount of from 〇 to 20% by weight based on the total amount of the "melamine bond-containing resin" of the component (A). These epoxy compounds are n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromoglyceryl glycidyl ether and the like. Further, an alicyclic epoxy compound such as a 3,4-epoxycyclohexyl group or a methyl (3,4·epoxycyclohexanyl) carboxylate can be used. The amount of the epoxy resin used is preferably from 1 to 50 parts by weight, more preferably from 2 to 45 parts by weight, per 100 parts by weight of the "resin having an acid anhydride group and/or a carboxyl group" used as the component (A). 'It is better for 3 to 40 parts by weight. When the amount of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance, and moisture resistance of the resin composition tend to decrease. When it exceeds 50 parts by weight, heat resistance and viscosity stability are improved. Reduce the tendency. The method of adding the epoxy resin may be carried out by dissolving the added epoxy resin in an organic solvent having the same organic solvent as the "resin having an acid anhydride group and/or a carboxyl group" used as the component (A), and then adding 'additional' Can be added directly. -24- 200911922 [(C) component: hydrazine containing hydrotalcite] The hydrazine used as the component (C) in the present invention. The component (C) used in the resin composition of the present invention is a chelating agent as an essential component. The content of the chelating agent is preferably from 100 to 200 parts by weight, based on 100 parts by weight of the component (A), and from 30 to 200 parts by weight, and from 50 to 100 parts by weight, less than the above, the resin composition The paste coefficient of the material is low, and the draw of the paste increases the film thickness of the resin composition after printing, which tends to be thinned, and the hard characteristics tend to deteriorate. Further, when the component (C) is contained, the viscosity and the thixotropic coefficient of the resin composition paste become high, and the transfer property to the substrate is lowered and the porosity in the printed film tends to be lowered. (Particle size of component (c)) The component (C) used in the resin composition of the present invention preferably has an average particle diameter of 5 Å or less and a maximum particle diameter of the particle size. When the average particle diameter exceeds 5 〇 μηι, it is difficult to obtain a resin composition paste having a coefficient of 1.1 or more, and if it is the most ΙΟΟμη, there is a coating film appearance and adhesion of the resin composition. The average particle diameter of the component (C) is more preferably 3 〇μηη or less ΙΟμηα or less, and is preferably 1 μm or less. Further, the maximum particle diameter is preferably 8 〇 μΐη or less, and more preferably 6 〇 μπι is preferably 40 μηι or less. Containing hydrotalcite is preferred to contain water slippery relative to the above. The (c) viscosity and the thixotropic material flow out of the film are larger than the above, so the paste and pinhole increase: the thixotropy is less than 1 〇 0 μ m, and then the thixotropy & particle size exceeds the tendency of insufficient More preferably, it is below c), and most -25-200911922 (hydrotalcite) Hydrotalcite is a rehydrated oxide represented by the following general formula (17). M1g.xM2x(0H)i6C03 * nH20 (17) (In the formula (17), Μ1 represents Mg2+, Fe2+, Zn2+, Ca2+, Li2+, Ni2+, Co2+, Cu2+, and M2 represents Al3+, Fe3+, Mn3+. x represents 2~5 An integer, n is a positive integer). Among these, magnesium and aluminum compounds represented by the following chemical composition formula are preferred, and are commercially available from HT-P (trade name, manufactured by Seiko Chemical Co., Ltd.).

Mg6Al2(0H)16C03 · 4H20 The hydrotalcite added as a hydrazine component in the resin composition of the present invention has an action as an antacid, and has a resin composition capable of alleviating a resin containing an acid anhydride group and/or a carboxyl group. The effect of thickening. Further, the hydrotalcite dissociates the carbonic acid group to produce carbonate ions (co?) which have a function of replacing the chloride ions (cr) and/or sulfate ions (so) contained in the resin composition. If chloride ions (cr) and/or sulfate ions (sor) are present in the cured film, the insulating reliability is adversely affected, and the insulating reliability can be improved by the replacement with the above carbonate ions. However, too much blending will result in poor print appearance and is therefore not good. Further, by blending the hydrotalcite in the resin composition of the present invention, the black ridge of the electrode after the electrification of the wiring board protected by the hardened film of the resin composition of the present invention can be alleviated. In addition, the hydrotalcite can obtain good flammability effects from -26 to 200911922. The content of the hydrotalcite is preferably 1 to 50 parts by weight with respect to 100 parts of the component (A), more preferably 5 to 40 parts by weight, and most preferably 11 parts by weight. When the content of the hydrotalcite is less than 1 part by weight, the effect of reducing the viscosity of the tree sap is insufficient, and when the electrode black ridge is inclined to 50 parts by weight or more, the printed appearance of the resin composition does not tend to be affected. Further, the content of the hydrotalcite in the component (C) is preferably 10% by mass, and is 10 to 30% by mass. /. Better' and 1 5~2 5 is the best. If the hydrotalcite content in the component (C) is less than 10%, the viscosity-reducing effect of the fat composition is insufficient. If it exceeds 50%, the adverse effect of the printed appearance of the resin composition is poor. In the component (C) used in the present invention, an inorganic chelating agent and/or an organic hydrazine agent may be used in addition to the hydrotalcite. First, the machine is filled with sputum. The hydrotalcite is one of the above inorganic chelating agents, but other inorganic ceraming agents other than the inorganic cerium can be used, for example, cerium oxide (Si〇2), Al2〇3), titanium oxide (Ti02), cerium oxide (Ta205), Zr02) , tantalum nitride (Si3N4), barium titanate (BaO. Ti02 钡 (B a C ◦ 3 ), lead titanate (pb 〇 · T i Ο 2 ), titanium dichromate), bismuth titanate titanate ( PLZT), gallium oxide (Ga203) (MgO · Al2〇3), mullite (3Al203.2SiO2), 2MgO · 2Al203/5Si〇2), talc (3MgO · 4Si02. Alginate (Ti02-Al203), containing The oxidation amount of cerium oxide is in the range of ～~30 weight composition, and if it is good quality % to 50% by mass: %, then tree: %, there is a chelating agent, indicating that there is no such Hydrotalcite alumina (oxidized pin ( ), carbonic acid i lead (PZT, spinel cordierite (H2〇), f (Y 2 ο 3 -27- 200911922

Zr02), barium strontium silicate (Ba0.8Si02), boron nitride (bn) 'calcium carbonate (CaC03), calcium sulfate (CaS04), zinc oxide (ZnO), magnesium titanate (Mg0.Ti02), barium sulfate (BaS 〇 4), organic bentonite, carbon (C), and the like. One or more of these may be used. Among these inorganic chelating agents, in particular, from the viewpoint of good electrical properties (insulation reliability, etc.), it is preferred to use barium sulfate or talc. Further, it is preferable to use barium sulfate from the viewpoint of printability and workability. On the other hand, the organic chelating agent is preferably a fine particle having a heat resistant resin having a guanamine bond, an oxime bond, an ester bond or an ether bond. From the viewpoint of heat resistance and mechanical properties, the heat resistant resin is preferably a polyimine resin or a precursor thereof, a polyamidoximine resin or a precursor thereof, or a fine particle of a polyamide resin. The heat resistant resin used as the above organic chelating agent can be produced as follows. First, the (C) aromatic tetracarboxylic dianhydride and (d) aromatic diamine compound can be reacted to obtain one of the above heat resistant resins, and the poly(imine) resin 〇(C) aromatic tetracarboxylic dianhydride is exemplified. For example, pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-bisphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, ι , ι_bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, double (3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether di-28- 200911922 anhydride, benzene- 1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylate Acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylate Acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylate Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl) Phenyl decane dianhydride, bis(3,4-dicarboxyphenyl)diphenyl phthalane dianhydride, 1,4-bis(3,4-dicarboxyphenyldimethyl decyl) phthalic anhydride, 1 ,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis{4-(3,4-dicarboxyphenoxy)phenyl}hexafluoropropane dianhydride, 2, 2-bis{4-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1, 4-bis(2-hydroxyhexafluoroisopropyl) benzene bis(trimellitic anhydride), :1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,2 -(Extended ethyl) bis(trimellitic anhydride), 1,3-(trimethylene) bis(trimellitic anhydride), 1,4-(tetramethylene) bis (bias) Tricarboxylic anhydride), 1,5-(pentamethylene)bis(trimellitic anhydride), 1,6-(hexamethylene)bis(trimellitic anhydride), 1,7-(heptamethylene) Bis(trimellitic anhydride), 1,8-(octamethylene)bis(trimellitic anhydride), 1,9-(nonamethylene)bis(trimellitic anhydride), 1,10-(ten Methylene) bis(trimellitic anhydride), 1,12-(dodecyl)bis(trimellitic anhydride), 1,16-(hexamethylene-29-200911922) bis(phenylene) Tricarboxylic anhydride), 118-(octamethylidene)bis (trimellitic anhydride), etc., may also be used in combination. The above (c) aromatic tetracarboxylic dianhydride may be a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride in an amount not exceeding 50 mol% of the aromatic tetracarboxylic dianhydride depending on the purpose. The tetracarboxylic dianhydrides are exemplified by, for example, ethyltetracarboxylic dianhydride 1, 1,2,3,4-butanetetracarboxylic dianhydride, piperidine _ 2.3.5.6-tetracarboxylic dianhydride, thiophene- 2,3,4,5-tetracarboxylic dianhydride, decalin-1,4,5,8·tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6, 7-hexahydronaphthalene - 1.2.5.6- tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, double {exo(6乂〇)-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride}, Bicyclo-(2,2,2)-octane (7)-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl 3-cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, and the like. Next, the above (d) aromatic diamine compound is exemplified by, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3 '-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 3,4,-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4 '_Diaminodiphenylmethane, 3,3,diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3,-diaminodiphenyl Maple, 3,4'-diaminodiphenyl maple, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl sulfide, 3,3'-diamine Diphenyl ketone, 3,4,-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2- Bis(3,4'-diaminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis-30- 200911922 (3-aminophenyl)hexafluoropropane , 2,2-bis(3,4,-diaminophenyl)hexa-propyl, 2,2-bis(4-aminophenyl)hexafluoropropanone, hydrazine, 3_bis (3-amine Phenyl, phenyl, 1,4-bis(4-aminophenyl)benzene, phenyl bis(indole-methylethylidene)] Amine ' 3,4,_[1,4_phenylene bis(indenyl)ethylidene)]diphenylamine, 4,4'-[1,4-phenylphenylbis(methylethylidene)] Diphenylamine, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(3-aminophenoxy)benzyl]/, fluoropropylin 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, double [4 - (3-Aminophenoxy)phenyl]sulfate, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]anthracene, Bis[4-(4-aminophenoxy)phenyl], etc., may also be used in combination with the above (d) aromatic diamine compound, depending on the purpose, not exceeding 50 of the aromatic diamine compound. A diamine compound other than the aromatic diamine compound is used in the range of % by mole. Such diamine compounds are exemplified by, for example, 1,2 _-aminoethyl acetoin, 1,3 -aminopropyl propylene, 1,4 -diaminobutyl butyl, 1,5-diaminopentane, 1, 6-Diaminohexane, 1,7-diaminoheptane, hydrazine, 8 · diaminooctane, 1,9-diamino broth, 1,1 〇-diamino decane, i , u-diaminoundecane, U3-bis(3-aminopropyl)tetramethyldioxane', 3_bis(3-aminopropyl)tetramethylpolyoxane, and the like. The above (c) aromatic tetra-residual dianhydride and the above (d) aromatic diamine compound are preferably in a molar reaction from the viewpoint of the film properties of the resin composition. (C) Aromatic S 矣 tetraresidic acid di dry and (d) aromatic diamine compound -31 - 200911922 The reaction is carried out in an organic solvent. The organic solvent in this case is, for example, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6- Nitrogen-containing compounds such as tetrahydro-2(11^)-furanone, 1,3-dimethyl-2-imidazophenone; sulfur compounds such as cyclobutyl, monomethyl arsenate; γ-butyrolactone , γ-valerolactone, γ-caprolactone, heptanolactone, α·ethionyl γ-butyrolactone, ε·caprolactone and other lactones; dioxane, hydrazine, 2-dimethoxy Ethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, four An ether such as ethylene glycol dimethyl (or diethyl, dipropyl or dibutyl) ether; a ketone such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or acetophenone; Alcohol, octanol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or Alcohols such as monoethyl ether; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl Su acetate esters; toluene, xylene, diethylbenzene, hydrocarbons such as cyclohexane; trichloroethane, tetrachloroethane, halogenated hydrocarbons such as monochlorobenzene and the like. These organic solvents may be used singly or in combination. In view of solubility, low hygroscopicity, low-temperature hardenability, environmental safety, and the like, it is preferred to use lactones, ethers, ketones, and the like. The reaction temperature is preferably 80 ° C or lower, preferably 0 to 50 ° C. The viscosity of the reaction solution increases slowly during the reaction. In this case, poly-proline which is a precursor of a polyimide resin is produced. The polyamic acid may also be partially imidized by the oxime. These are also included in the precursor of the polyimide. The above polyimine resin is obtained by subjecting the above reactant (polyglycine) to dehydration ring closure. The dehydration ring closure can be carried out by a method of heat treatment at -120 ° C ~ 2 5 -32 - 200911922 (thermal imidization) or by a method using a dehydrating agent (chemical hydrazide). For the heat treatment at 12 CTC to 25 ° C, it is preferred to carry out the water produced by the dehydration reaction while being excluded from the system. At this time, water may be azeotropically removed using benzene, toluene, xylene or the like. The dehydration ring closure method using a dehydrating agent is preferably a dehydrating agent such as an acid anhydride such as acetic anhydride, propionic anhydride or benzoic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide. In this case, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine or aminopyridazole may also be used as the case may be. The dehydrating agent or dehydrating catalyst is preferably used in an amount of from 1 to 8 mol per mol of the aromatic tetracarboxylic dianhydride. The polyamidoximine resin or precursor may be used in the manufacture of the above polyimine resin or a precursor thereof, using trimellitic anhydride or a trimellitic anhydride derivative (a gasification of a meta-benzoic acid liver, etc.) of a divalent three-residual acid liver. Or a derivative thereof is produced in place of an aromatic tetracarboxylic dianhydride. Further, in place of the aromatic diamine compound and other diamine compounds, a residue other than the amine group may be produced by using a diisocyanate compound corresponding to the diamine compound instead. The diisocyanate compound which can be used is obtained by reacting the above aromatic diamine compound or other diamine compound with carbon ruthenium chloride or sulfinium chloride. The polyamine resin may be an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, a derivative such as a dichloride or an acid anhydride, and the above aromatic diamine compound or the like. The heat resistant resin having the above ester bond by reacting an amine compound is exemplified by, for example, a polyester resin, and the polyester resin is an aromatic dicarboxylic acid such as the above terephthalic acid, isophthalic acid or phthalic acid-33-200911922. A derivative such as an acid, such a dichloride or an acid anhydride is obtained by reacting an aromatic diol compound such as hydrazine, 4-dihydroxybenzene, bisphenol F, bisphenol A or 4,4'-dihydroxybiphenyl. Further, as the polyamidoximine resin, a polyamidoximine resin obtained by reacting an aromatic tetra-resin dianhydride with an aromatic diamine compound containing diterpenoid isophthalate as an essential component is preferably used. The above may also be used for the aromatic tetracarboxylic dianhydride and the aromatic diamine compound. The molar ratio of the aromatic diamine compound of dioxonium isophthalate is preferably from 1 to 100 mol%. If it is less than 1 mol%, there is a tendency that the solubility resistance of the modified polyamidoximine resin is lowered, and if the content of diterpene isophthalate is large, the resin composition of the present invention The turbidity tends to lower the moisture resistance of the formed layer, so that 10 to 80 moles are used. /〇 Better, take 2 0~7 0 Mo %% best. The polyamidoximine resin is a compounding ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine compound, and can be obtained by using an organic solvent, a synthesis method, or the like, as in the synthesis of the above polyimine resin. The polyamidoquinone imine resin obtained by reacting trimellitic anhydride and, if necessary, a dicarboxylic acid with a polyisocyanate, may be an organic fine particle composed of the polyamidoximine resin which is insoluble by heating in an organic solvent. The method for producing the polyamidoximine resin can be produced in the same manner as the above-described method for producing a polyamidamine resin. In the method of using the (C) component: the chelating agent, the method of dispersing the above-mentioned resin is, for example, a non-aqueous dispersion polymerization method (for example, refer to Japanese Patent Publication No. Sho 60-23 00 1 pp. And a precipitation polymerization method (for example, a method of mechanically pulverizing a powder modified from a resin solution); a resin solution; a method of adding microparticles under high shear in a weak solvent; a method of drying a spray solution of a resin solution to obtain fine particles; and precipitating a resin having solubility dependence on a solvent in a detergent or a resin solution and The method of microparticles. As described above, the component (C) used in the present invention: a chelating agent (inorganic fine particles containing hydrotalcite and/or organic fine particles) is preferably one having an average particle diameter of 50 μm or less and a maximum particle diameter of 1 〇〇μηι or less. Path. When the average particle size exceeds 50 μm, it is difficult to obtain a paste having a thixotropic coefficient of 1. i or more, which is described later. When the maximum particle diameter exceeds ΙΟΟμηι, the appearance and adhesion of the coating film of the resin composition tend to be insufficient. The average particle diameter is more preferably 3 0 μηα or less, and still more preferably ΙΟμηι or less and preferably 1 μηη or less. The maximum particle diameter is preferably 80 μm or less, more preferably 60 μm or less, and most preferably 40 μm or less. [Resin composition] The resin composition of the present invention can dissolve the resin of the (Α) component in an organic solvent to form a resin solution, and disperse the "hydrotalcite-containing inorganic fine particles and/or organic fine particles" of the component (C) therein. Then, it is produced by adding an epoxy resin of a mixed (Β) component. In the resin composition of the present invention, the content of the "hydrotalcite-containing inorganic fine particles and/or organic fine particles" used as the component (C) is as described above, and is preferably 250 based on 100 parts by weight of the component (A). The parts by weight are more preferably 30 to 200 parts by weight and most preferably 50 to 1 part by weight. When the content of the component (c) of -35-200911922 is less than the above, the viscosity and the thixotropic coefficient of the resin composition paste are decreased, and the threading of the paste is increased to cause the outflow of the paste to become large after printing, and The tendency of the film thickness of the resin composition to be thinned and the tendency of electrical characteristics to deteriorate. When the content of the component (C) is more than the above, the viscosity and the thixotropic coefficient of the resin composition paste become high, so that the transfer property of the paste to the substrate is lowered and the pores and pinholes in the printed film are increased. tendency. The organic solvent in which the resin of the component (A) is dissolved is as described above, and is a non-nitrogen-containing polar solvent, and is diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl glycol. An ether solvent such as an ether or a triethylene glycol diethyl ether; a sulfur-containing solvent such as dimethyl sulfoxide, diethyl hydrazine, dimethyl hydrazine or hydrazine; γ-butyrolactone and fibrin acetate An ester solvent; a ketone solvent such as cyclohexanone or methyl ethyl ketone; an aromatic hydrocarbon solvent such as toluene or xylene; and the like. These solvents may be used singly or in combination of two or more. Since the solubility differs depending on the resin produced, a solvent which can dissolve the resin is selected. Dispersion in a solution of a thermosetting resin (component (A)) (C) Component: a method of dispersing inorganic and/or organic fine particles containing hydrotalcite, and it is possible to suitably use a roll kneading, a kneading machine, or the like which is usually carried out in the field of coating materials. 'It is preferably a method of sufficiently performing dispersion. In order to improve the handleability at the time of coating and the film characteristics before and after the film formation, the resin composition of the present invention may be added with a surfactant such as an antifoaming agent or a flow agent, a coloring agent such as a dye or a pigment, or a thermal stabilizer. Antioxidants, flame retardants, lubricants. The viscosity of the resin composition of the present invention measured by a rotary viscometer is preferably 20 Pa.s to 8 Å pa.s at 25 ° C, particularly preferably 30-50 pa.s -36 to 200911922. Further, the thixotropic coefficient is preferably 1.1 or more. If the viscosity is less than 20 Pa · s ', the flow of the paste becomes large after printing and the film thickness tends to be thinned. If the viscosity exceeds 80 pa · s, the transfer property of the paste to the substrate is lowered and there is The tendency of the pores and pinholes in the printed film to increase. Further, if the thixotropic coefficient is less than 1 · 1 ', the draw of the paste is increased and the flow of the paste after printing is increased, and the film thickness tends to be thin. Here, the viscosity of the resin composition is expressed by using an E-type viscosity agent (manufactured by Toki Sangyo Co., Ltd., RE80U type), and the viscosity of the rotation number i〇rpnl is measured at a sample amount of 0.2 ml or 0.5 ml. The thixotropy coefficient (TI値) of the paste was measured using an E-type viscosity agent (manufactured by Toki Sangyo Co., Ltd., RE80U type), and the apparent viscosity of the paste of the rotation number of 1 rpm and 10 rpm was measured under the sample amount of ml2 ml or OJrnl. And expressed by the ratio η 1 /η 1 0 of ηΐ and η1〇. Further, the resin composition of the present invention is printed on a flexible wiring board by a screen printing pattern and then cured by heat to form a cured film, which is preferably used as a protective film on a flexible wiring board. It is especially suitable for protective film applications where the wiring pattern portion is tinned on the surface of a flexible wiring board. The thermosetting condition is preferably from 80 ° C to 130 ° C, particularly preferably from 90 ° C to 120 °, in order to prevent diffusion of the tin-plated layer and obtain appropriate low warpage and flexibility as a protective film. C, but is not limited to the above range, for example, 50 ° C to 200 ° C, wherein it can be hardened in the range of 50 ° C to 140 ° C. Further, the heating time prevents the tin-plated layer from diffusing and obtains a viewpoint of appropriate low warpage and flexibility as a protective film, and is preferably 60 to 150 minutes, more preferably 80 to 120 minutes, but is not limited thereto. The above range may be 1 to 1, 〇〇〇 minutes, for example, 5 to 3 00 minutes, and in -37 to 200911922, it may be hardened for 10 to 15 minutes. [Film forming material] The film forming material of the present invention contains the above resin group as a coating method for a film forming material plate printing, a cloth applicator, a spin coater or the like of various electric products and electronic parts. Printed on the screen. The film forming material according to the present invention can be suitably used as an overcoat material for an electronic component such as an element or a printed circuit board, an interlayer insulating film, a surface protective film, a solder resist layer, and a varnish for electric enamel and electricity. A varnish for a MCL laminate, a varnish for a friction material, or the like, which is combined with a varnish for insulation and a substrate such as mica or glass cloth. Further, since the film is difficult to be peeled off from the circuit board or the like, and the substrate and the resin are excellent in printing workability, electric power with high reliability can be obtained. [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, but the invention is limited. (Synthesis Example 1: Synthesis of Polymer Resin) In a 3 liter four-necked flask equipped with a mixer, an oil separator, a cooling tube, and a thermometer, a feed of 61.72 g of 74.72 g (0.37 mol) of 1,6 g was fed. The hexanediol-based polycarbohydrate is suitable for use in a mesh, and is particularly suitable for, for example, a semiconductor, a liquid encapsulating layer, or the like. A varnish for immersion varnish, varnish for injection, and a sub-component for adhesion between resins. Not subject to such nitrogen, γ · butyl vinegar, I ester diol ( -38- 200911922

Diacell Chemical Industry Co., Ltd. 'trade name "PLACCEL CD-220"), 125.14g (〇.46 Moer) 4,4'-a base of an isocyanate and 58.4g (0.34 mole) The toluene diisocyanate was heated to 150. (:, and at 1 50. (: 4 hours of reaction. Next, 88_4 g (0.46 mol) of phthalic acid liver was fed into the above reaction, and reacted at 701 for 3 hours. Then fed again. 6·76g (0.027 mol) of 4,4,-diphenylmethane diisocyanate, 0.0034 § (0.00002 mol) of toluene diisocyanate was reacted at 120 ° C for 1 hour, and at 18 ° C The reaction was carried out for 3 hours. After the reaction, 3 4 1.6 g of butyl carbitol acetate was fed and cooled, and then 0.02 g (0-0001 mol) of pyromellitic anhydride was fed at 120 ° C. Resin for 3 hours' to obtain a resin having a number average molecular weight of 380 (polycarbonate-modified polyamidoximine resin: component (A) of the present invention). The number average molecular weight can be taken in a small amount per reaction time. The reaction solution was observed by a bubble type viscosity agent manufactured by Gardner, and the viscosity change rate was observed and adjusted. The obtained resin was diluted with butyl carbitol acetate to obtain a polycarbonate modified polyfluorene having a nonvolatile content of 50% by weight. Amine imine resin solution (Example 1) Polycarbonate having an average molecular weight of 38,000 obtained in the above (Synthesis Example 1) In the modified polyamidoximine resin solution, 1 part by weight of the solvent treatment liquid and 0.3 part by weight of the antifoaming agent (manufactured by BYK Chemie Co., Ltd., "product name" are prepared with respect to 10 parts by weight of the resin portion of the resin solution. BYK-051"), 〇_75 parts by weight of advection agent (BYK Chemie, s-39-200911922, product name "ΒΥΚ-3 54"), stirred at 20 ° C for 1 。 minutes. Then 'prepended with beads in advance The honing machine contains 66.5% by weight of barium sulfate (manufactured by Daimlersei Chemical Co., Ltd., trade name "B-31"), and I3.5 parts by weight of talc (trade name "ST-made by Japan Talc Co., Ltd." 2000) and 1 part by weight of hydrotalcite (product name "HT-P" manufactured by Seiko Chemical Co., Ltd.) (component (C) of the present invention), and a solvent such as γ-butyrolactone is added as needed, and The mixture was stirred at 50 ° C for 1 hour, and further, 10 parts by weight of an amine-type epoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "YH-434L") as a component of the present invention (B) was added, and at 20 °. The mixture was stirred for 1 hour at C to obtain a polycarbonate modified polyamidoximine resin composition. (Example 2) According to Example 1, except that the hydrotalcite was 20 parts by weight, the same operation as in Example 1 was carried out to obtain a polycarbonate-modified polyamidoximine resin composition. 3) According to Example 1, except that the hydrotalcite was changed to 30 parts by weight, the same operation as in Example 1 was carried out to obtain a polycarbonate-modified polyamidoximine resin composition. (Example 4) Example 1 The operation was carried out in exactly the same manner as in Example 1 except that the hydrotalcite was changed to 50 parts by weight to obtain a polycarbonate-modified polyamine-40-200911922 quinone imine resin composition. (Comparative Example 1) In the synthesis example 1, except that the resin to be blended is not a resin terminal isocyanate which is reacted with pyromellitic anhydride, but a ruthenium reactant (resin having no acid anhydride group and/or carboxyl group) is used. A polycarbonate-modified polyamidolimine resin composition was obtained by the same operation as in Example 1 (Comparative Example 2) According to Example 1, except that the hydrotalcite was not formulated, the same procedure as in Example 1 was carried out. In operation, a polycarbonate modified polyamidoximine resin composition is obtained. The various polycarbonate modified polyamidoximine resin compositions obtained in the above examples and comparative examples and the hardened coatings of the polyamidoximine resin compositions were tested for the polyimide film by the following method. The characteristics, printed appearance, and reduction of black bulge are shown in Table 1). (Storage stability) The viscosity of the polycarbonate-modified polyamidoimine resin composition produced was measured by a rotary viscometer, and the viscosity was measured in the same manner after 48 hours' calculation. The smaller the number, the better the storage stability. (Printed Appearance) -41 - 200911922 Printing speed 1 〇〇mm/sec by a printing machine (trade name "LS-34GX", manufactured by New Long Co., Ltd.) and screen (MURAKAMI Co., Ltd., 150 mesh) The obtained polycarbonate modified polyamidoximine resin composition was printed on a copper foil of 35 μm on a side length of 30 mm, and the appearance after printing was observed by an optical microscope at a magnification of 100 (bubble, condensation) Things, etc.). None of the defects such as bubbles and aggregates were found to be 〇. It was observed that one of the printed parts had defects such as bubbles and condensates, and was evaluated as △. It was observed that all the printed parts had blistering and condensate. The defect is evaluated as X. (The presence or absence of the black bulge of the electrode after energization) On a polyimide substrate, a tin-plated copper electrode coated with a comb shape with a line width of 15 μm and a width of 15 μm is used, and a printing machine (N ew L ο ng Co., Ltd.) is used. System, trade name: LS-34GX) and screen (MURAKAMI Co., Ltd., 150 mesh), polycarbonate modified polyamidoximine resin composition obtained by printing at a printing speed of lOOmm/sec, in air The film was heat-hardened at 120 ° C for 60 minutes in an atmosphere to obtain a polyimine substrate comb-shaped electrode coated with a hardened film of a polycarbonate-modified polyamidoximine resin. The obtained polyimide electrode coated with a polycarbonate-modified polyamidoximine resin hardened film was subjected to a continuous resistance measuring machine (manufactured by IMV Co., Ltd., trade name "Ion Migration Tester MIG" -8600") and the unsaturated type Cooker (trade name "HSAT PC-422R8D", manufactured by Hirayama Seisakusho Co., Ltd.), with a temperature of 120 ° C, a humidity of 85%, an applied voltage of 60 V, and an application time of 1 hour - 42 - Power was supplied under the conditions of 200911922, and the electrode was observed to have a black bulge after energization at a magnification of 1 Ο 0. Those without black ridges were evaluated as 〇, those with a few black ridges were evaluated as △, and those with a large number of black ridges were evaluated as X. (Adhesiveness) The polycarbonate-modified polyamidoximine resin composition after printing is cured in an air environment at 120 ° C for 60 minutes, and the test piece overlaps with the polyimide film and further with the copper plate. The adhesion of the test piece to the polyimide film was measured after heating at 90 to 120 t on a hot plate for 30 seconds under a load of 2 kg. It is evaluated by the temperature at which the attachment is initiated. The higher the temperature at which the attachment begins to occur, the better. (Table 1)

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Storage stability 1.41 1.21 1.18 1.15 1.01 1.50 Printing appearance 〇〇Δ X 〇〇 Electrode black bulge with or without Δ 〇〇〇〇X Attachment 120 ° C 120 ° C 120. . 120 ° C 90 ° C 120 ° C From the above results, the following can be confirmed. That is, from the comparison of Comparative Example 1 with other examples, it is understood that when the terminal isocyanate is modified with pyromellitic anhydride, the reaction with the amine type epoxy resin is promoted, and the adhesion to the polyimide film after hardening can be alleviated. Sex. Further, in Examples 2 to 4 and Comparative Example 2, when the amount of hydrotalcite was increased, the viscosity was reduced. Furthermore, by blending hydrotalcite, the black bulge of the electrode -43-200911922 after power-on can be reduced. Therefore, an excessive amount of blending will result in poor print appearance. [Industrial Applicability] As described above, the resin composition and the film forming material of the present invention can be used as a film forming material for various electrical products and electronic parts, and are suitable for screen printing, cloth coating, and spin coating. Etching method. Further, since the adhesion to the polyimide film after hardening is less likely to cause adhesion, workability such as a spacer layer between the polyimide film and the cured film can be eliminated, which is advantageous in terms of cost. -44-

Claims (1)

200911922 X. Patent Application No. 1. A resin composition comprising: (A) component: a resin having an acid anhydride group and/or a carboxyl group, (B) a component: an epoxy resin, and (C) component: containing water A talc filling agent. 2. The resin composition of claim 1, wherein the component (A) has a polycarbonate skeleton. 3. The resin composition of claim 1, wherein the structural unit component represented by (A) has the following general formula (Chemical Formula 1) 〇0 0 II , II II XNCO-(R-〇-C-0 R^-CN Η Η (In the formula (1), a plurality of R independently represent an alkylene group having 1 to 18 carbon atoms, and a plurality of X independently represent an alkylene group or a stretch of 1 to 18 carbon atoms. The aryl group, 111 and 11 each independently represent an integer of from 1 to 20). 4. The resin composition of claim 1, wherein the component (A) is selected from the group consisting of a polyimide resin having a polycarbonate skeleton. a resin obtained by reacting an isocyanate residue of at least one resin of a polyamidoximine resin or a polyamide resin with a trivalent or higher polycarbonate or a derivative thereof having an acid anhydride group. The resin composition of the present invention, wherein the content of the component (C) is 10 to 50 parts by weight based on 100 parts by weight of the component (a), and the hydrotalcite content in the component (c) is 1% by mass. ～50质量质量。 6_ The resin composition of any one of claims 1 to 5 is -45-200911922, which is used for A protective film for a flexible printed circuit board substrate on which a copper foil is laminated on a polyimide substrate. 7. A film forming material characterized by containing the resin composition according to any one of claims 1 to 5. -46 - 200911922 无明说单无简.. rhyme is the map of the map element on behalf of the map: the table pattern represents the book one or two fingers / IV seven eight, if the case has a chemical formula, please reveal the best display invention Chemical formula of the feature: none