JP5115321B2 - Resin composition and film-forming material containing the same - Google Patents

Description

  The present invention relates to a resin composition and a film-forming material containing the same, and more particularly to a resin composition having thixotropy suitable for a coating method such as a screen printer, a dispenser, a spin coater, and a film-forming material containing the same.

  In recent years, in the field of electronic components, polyimide resin, polyamide imide resin, and polyamide resin are used as resins excellent in heat resistance, electrical characteristics, and moisture resistance in response to miniaturization, thinning, and high speed, instead of epoxy resin. in use. These resins have a rigid resin structure, and when used as a thin film substrate, the cured substrate is greatly warped, and the cured film lacks flexibility and has poor flexibility.

  Therefore, in order to improve the low warpage and flexibility, a polyamideimide resin (Patent Document 1, Patent Document 2, and Patent Document 3) in which the resin is made flexible and modified to have a low elastic modulus has been proposed. In these resins, in order to improve printability and workability, inorganic fillers, organic fillers, and the like are dispersed in the resin solution. In addition, additives such as various coupling agents and surface treatment agents are used to improve the adhesion between the substrate and the resin or between the filler and the resin.

JP 62-106960 A Japanese Patent Laid-Open No. 8-12763 JP-A-7-196798

  However, there is a concern that the film forming materials described in Patent Documents 1 to 3 are one of the causes for lowering electrical characteristics when energized at high temperature and high humidity.

  In addition, when winding the film-cured material after screen printing, the opposite surface of the flexible wiring board (polyimide film coated with copper wiring) to which copper wiring is not applied and the film-forming material stick. There is a problem, and it is the actual situation that spacers are conventionally provided between the polyimide film and the coating material.

  The above problem can be improved by accelerating curing by, for example, bonding an acid anhydride to a resin having an isocyanate terminal, but storage stability is deteriorated, and a problem due to thickening occurs during screen printing.

  Further, the film-forming materials described in Patent Documents 1 to 3 are concerned that they may be a cause of lowering electrical characteristics when energized under high temperature and high humidity.

  The resin composition of the present invention can obtain stable electrical characteristics under high temperature and high humidity, has good storage stability, and can reduce stickiness with a cured polyimide film. This resin composition can be suitably used for electronic components such as flexible wiring boards, and has the effect of obtaining highly reliable electronic components.

The present invention contains (A) a resin having at least one acid anhydride group and / or carboxyl group, (B) an inorganic filler containing hydrotalcite and silica, and (C) an epoxy resin, and (B) The content of the inorganic filler containing hydrotalcite and silica is 50 to 100% by weight with respect to 100 parts by weight of the resin (A), and the content of hydrotalcite in the inorganic filler is 20 to 50 mass. Further, the present invention relates to a thermosetting resin composition having a silica content of 10 to 30% by mass .
In the present invention, (A) the resin having at least one acid anhydride group and / or carboxyl group is represented by the following general formula (I):
(In the formula, each R is independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) It is related with the said thermosetting resin composition which is a thermosetting resin containing the polyurethane structure shown by these .
In the present invention, the component (A) is selected from an imide bond, an amide imide bond, and an amide resin obtained by reacting an isocyanate residue with a trivalent or higher polycarboxylic acid having an acid anhydride group or a derivative thereof. It is related with the said thermosetting resin composition which is resin which has at least 1 sort of coupling | bonding .
Moreover, this invention relates to the said thermosetting resin composition in which the said (B) component further contains barium sulfate .
Moreover, this invention relates to the said thermosetting resin composition which is an object for the protective films of the flexible printed circuit board which laminated | stacked copper foil on the polyimide base material.

  The resin composition of the present invention can obtain stable electrical characteristics under high temperature and high humidity, has good storage stability, and can reduce stickiness with a cured polyimide film. This resin composition can be suitably used for electronic components such as flexible wiring boards, and has the effect of obtaining highly reliable electronic components.

Hereinafter, an embodiment of a resin composition and a film forming material according to the present invention will be described in detail. Note that the present invention is not limited to the embodiment.
The resin composition of the present invention contains (A) a resin having at least one acid anhydride group, (B) an epoxy resin, and (C) an inorganic filler containing silica as essential components.

[(A) component: resin having at least one acid anhydride group]
As the resin having at least one acid anhydride group as the component (A), epoxy resin having a butadiene structure or silicone structure, phenol resin, acrylic resin, polyurethane, polybutadiene, water-added polybutadiene, polyester, polycarbonate, polyether, polysulfone , Polytetrafluororesins, polysilicones, melamine resins, polyamides, polyamideimides, polyimides, and other resins having acid anhydride groups introduced into the main chain and / or side chains. These can be used alone or in combination of two or more. Further, a resin having an acid anhydride group and a resin not having an acid anhydride can be used in combination.
As a method for introducing an acid anhydride group, epoxy resin having a butadiene structure or silicone structure, phenol resin, acrylic resin, polyurethane, polybutadiene, hydrogenated polybutadiene, polyester, polycarbonate, polyether, polysulfone, polytetrafluororesin, poly Obtained by reacting the following general formula (I) and / or general formula (II) with epoxy residue, isocyanate residue, hydroxyl group residue, carboxyl group, etc. derived from silicone, melamine resin, polyamide, polyamideimide, polyimide resin Can do.

(In formula (I), Z ¹ represents an organic group, and W represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group.)

(In formula (II), Z ² represents the following organic group. W represents a hydroxyl group, an isocyanate group, a carboxyl group, an epoxy group, or a glycidyl group.)

  In addition, the (A) resin of the present invention is preferably flexible and has a low elastic modulus so as to mainly correspond to a flexible substrate. (A) In order to make the resin flexible and have a low elastic modulus, it is possible to introduce a component capable of improving flexibility into the main chain of the resin. For example, a polybutadiene skeleton, a silicone resin skeleton and / or a polycarbonate A resin having a skeleton is preferred.

  In order to improve heat resistance, electrical properties, moisture resistance, solvent resistance and chemical resistance, it is possible to introduce a component capable of improving heat resistance into the main chain of the resin. For example, polyimide, polyamide Preference is given to imides or polyamides or resins having these skeletons. Among them, a resin having a polycarbonate skeleton and an imide skeleton is preferable from the viewpoint of flexibility, low elastic modulus, and high heat resistance.

  In the present invention, the resin containing a polycarbonate skeleton that can be used as the component (A) is usually a 1,6-hexanediol-based polycarbonate diol, a compound having a carboxyl group at the terminal, a compound having an acid anhydride, and It can be obtained by reacting with a compound having an isocyanate group at the terminal.

  In the present invention, the resin containing an imide bond that can be used as the component (A) usually contains (a) a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and an acid anhydride group. It can be obtained by reacting one or more compounds selected from tetravalent polycarboxylic acids having (b) an isocyanate compound or an amine compound.

The trivalent polycarboxylic acid having an acid anhydride group as the component (a) and a derivative thereof are not particularly limited, and examples thereof include formulas (III) and (IV):

(In the formulas (III) and (IV), R ′ represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y ¹ represents —CH ₂ —, —CO—, —SO ₂ —, or -O-)
The compound shown by these can be used.

Trimellitic anhydride is particularly preferable from the viewpoint of heat resistance and cost. Although the tetravalent polycarboxylic acid having an acid anhydride group is not particularly limited, for example, the formula (V):

(In the formula, Y ² represents a group represented by the formula (V):

Can be used. These can be used alone or in combination of two or more.

  In addition to these, as necessary, an aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc.) Aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used in combination. In this case, an amide bond is also formed in the molecular chain.

The isocyanate compound as the component (b) is, for example, the formula (VII):

(In the formula, a plurality of R's are each independently an alkylene group having 1 to 18 carbon atoms, and m and n are each independently an integer of 1 to 20).
Can be used (hereinafter referred to as (b-1) compound).

The compound represented by the formula (VII) is represented by the formula (VIII):

(In the formula, R is independently an alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 20).
Carbonate diols represented by formula (IX):
OCN-X-NCO (IX)
(Wherein X is a divalent organic group)
It can be obtained by reacting a diisocyanate represented by the following formula.

  X of the diisocyanates of the formula (IX) is, for example, an arylene group such as an alkylene group having 1 to 20 carbon atoms or an unsubstituted or phenylene group substituted with a lower alkyl group having 1 to 5 carbon atoms such as a methyl group. Is mentioned. The number of carbon atoms of the alkylene group is more preferably 1-18. A group having two aromatic rings such as a diphenylmethane-4,4'-diyl group and a diphenylsulfone-4,4'-diyl group is also preferable.

  Examples of the carbonate diols represented by the above formula (VIII) include α, ω-poly (hexamethylene carbonate) diol, α, ω-poly (3-methyl-pentamethylene carbonate) diol, and the like. Examples of such products include trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, and 220HL manufactured by Daicel Chemical Industries. These can be used alone or in combination of two or more.

  Examples of the diisocyanates represented by the above formula (IX) 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'-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; diphenyl Diphenyl ether-4,4'-diisocyanate; benzophenone-4,4'-diisocyanate; diphenylsulfone-4,4'-diisocyanate; tolylene-2,4-diisocyanate; tolylene-2,6 -Diisocyanate; m-xylylene diisocyanate; p-xylylene diisocyanate; naphthalene-2,6-diisocyanate; 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate. In these diisocyanates, it is preferable to use an aromatic polyisocyanate in which X in the formula (IX) has an aromatic ring. These can be used alone or in combination of two or more.

  Further, as the diisocyanate represented by the formula (IX), within the scope of the object of the present invention, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, Aliphatic or alicyclic isocyanates such as transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, or trifunctional or higher polyisocyanates can be used. As the diisocyanate represented by the formula (IX), a diisocyanate stabilized with a blocking agent necessary for avoiding aging may be used. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

  The mixing ratio of the carbonate diols represented by the above formula (VI) and the diisocyanates represented by the formula (IX) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 1.01 or more. It is preferable to do.

  The reaction between the carbonate diols represented by the above formula (VIII) and the diisocyanates represented by the formula (IX) can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C, more preferably 80 to 180 ° C. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like. For example, it can be 2 to 5 hours on a flask scale of 1 to 5 L (liter).

  The number average molecular weight of the isocyanate compound of the compound (b-1) thus obtained is preferably 500 to 10,000, more preferably 1,000 to 9,500, and 1,500 to Particularly preferred is 9,000. When the number average molecular weight is less than 500, the warping property tends to be deteriorated. When the number average molecular weight exceeds 10,000, the reactivity of the isocyanate compound is lowered, and it tends to be difficult to obtain a polyimide resin.

In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Moreover, the number average molecular weight and dispersion degree of this invention are defined as follows.
a) Number average molecular weight (M _n )
M _n = Σ (N _i M _i ) / N _i = ΣX _i M _i
(X _i = Mole fraction of molecules with molecular weight M _i = N _i / ΣN _i )
b) Weight average molecular weight M _w = Σ (N _i M _i ² ) / ΣN _i M _i = ΣW _i M _i
(W _i = weight fraction of molecules of molecular weight M _i = N _i M _i / ΣN _i M _i )
c) Molecular weight distribution (dispersity)
Dispersity = M _w / M _n

  As the isocyanate compound of component (b), a compound other than compound (b-1) (hereinafter referred to as compound (b-2)) can also be used. The compound (b-2) is not particularly limited as long as it is an isocyanate compound other than the compound (b-1), and examples thereof include diisocyanates represented by the formula (IX), trivalent or higher polyisocyanates, and the like. . These can be used alone or in combination of two or more. A preferred range of the number average molecular weight of the isocyanate compound of the compound (b-2) is the same as that of the compound (b-1).

  In particular, from the viewpoint of heat resistance, it is preferable to use the compound (b-1) and the compound (b-2) in combination. In addition, when using a compound (b-1) and a compound (b-2) each independently, a compound (b-1) is used from points, such as a softness | flexibility as a protective film for flexible wiring boards, and curvature property. It is preferable to do.

  As compound (b-2), 50 to 100% by weight of the total amount is preferably aromatic polyisocyanate, and considering the balance of heat resistance, solubility, mechanical properties, cost, etc., 4, 4 '-Diphenylmethane diisocyanate is particularly preferred.

  When the compound (b-1) and the compound (b-2) are used in combination, the equivalent ratio of compound (b-1) / compound (b-2) is 0.1 / 0.9 to 0.9 / 0.1. Is preferable, 0.2 / 0.8 to 0.8 / 0.2 is more preferable, and 0.3 / 0.7 to 0.7 / 0.3 is particularly preferable. When the equivalence ratio is within this range, film properties such as good warpage, adhesion and good heat resistance can be obtained.

  Among the components (b), examples of the amine compound include compounds obtained by converting the isocyanate group in the isocyanate compound of the component (b) to an amino group. Conversion of the isocyanato group to an amino group can be performed by a known method. The preferred range of the number average molecular weight of the amine compound is the same as that of the above compound (b-1).

  The blending ratio of the trivalent polycarboxylic acid or derivative thereof having an acid anhydride group of the component (a) and / or the tetravalent polycarboxylic acid having acid anhydride group is the isocyanate group in the component (b). Preferably, the ratio of the total number of carboxyl groups and acid anhydride groups in component (a) to the total number of is 0.6 to 1.4, preferably 0.7 to 1.3. It is more preferable that the ratio is 0.8 to 1.2. When this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the resin containing polyimide bonds.

When the compound represented by formula (I) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (X):

(Wherein R, X, m and n are as defined above)
The polyamideimide resin which has a repeating unit shown by can be obtained.

When the compound represented by the formula (IV) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (XI):

(Wherein R, X, m, n and Y ¹ are as defined above)
The polyamideimide resin which has a repeating unit shown by can be obtained.

When the compound represented by the formula (V) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (XII):

(Wherein R, X, m, n and Y ² are as defined above)
The polyimide resin which has a repeating unit shown by can be obtained.

  In the present invention, (a) a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and a tetravalent having an acid anhydride group in the process for producing a resin containing an imide bond used as the component (A). The reaction between one or more compounds selected from polycarboxylic acids and (b) an isocyanate compound or an amine compound is carried out by using a carbon dioxide gas generated free in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent. It can be carried out by heat condensation while removing 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, triethylene glycol diethyl ether; sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, Sulfolane; ester solvents such as γ-butyrolactone, cellosolve acetate; ketone solvents such as cyclohexanone, methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene, xylene, etc., which may be used alone or in combination of two or more. Can be used in combination.

  It is preferable to select and use a solvent that dissolves the resulting resin. After the synthesis, it is preferable to use a suitable paste solvent as it is. Γ-Butyrolactone is the most preferable because it is highly volatile, can impart low-temperature curability, and reacts efficiently in a homogeneous system. It is preferable that the usage-amount of a solvent shall be 0.8 to 5.0 times (weight ratio) of resin containing the imide bond to produce | generate. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.

  The reaction temperature is preferably 80 to 210 ° C, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C., the reaction time becomes too long, and if it exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.

  If necessary, the reaction may be performed 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, cobalt, or a metalloid compound.

  The number average molecular weight of the resin thus obtained is 22,000 to 50,000, more preferably 24,000 to 45,000, and particularly preferably 26,000 to 40,000. Preferably, the degree of dispersion at that time is preferably 1.5 to 3.5, and more preferably 2.0 to 3.0. When the number average molecular weight is less than 22,000, sticking to the polyimide film tends to occur, and when the number average molecular weight exceeds 50,000, the viscosity of the resin increases, and the inorganic filler and / or the organic filler. There is a tendency that workability such as screen printing and workability such as screen printing tend to deteriorate, which is not preferable.

  In the case of the resin containing the imide bond, various epoxy resins can be added in addition to the component (A) in order to improve thermosetting. Examples of the epoxy resin as the curing agent include bisphenol A type epoxy resin (trade name Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) and bisphenol F type epoxy resin (trade name YDF- manufactured by Tohto Kasei Co., Ltd.). 170, etc.), phenol novolac type epoxy resin (Oilized Shell Epoxy Co., Ltd. trade name Epicoat 152, 154; Nippon Kayaku Co., Ltd. trade name EPPN-201; Dow Chemical Co., Ltd. trade name DEN-438 Etc.), o-cresol novolac type epoxy resins (trade names EOCN-125S, 103S, 104S, etc., manufactured by Nippon Kayaku Co., Ltd.), polyfunctional epoxy resins (trade names, Epon 1031S, manufactured by Yuka Shell Epoxy Co., Ltd.)・ Product name Araldite 0163 manufactured by Specialty Chemicals Co., Ltd .; Product manufactured by Nagase Kasei Co., Ltd. Denacol EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, etc., amine type epoxy resin (oilification shell epoxy (stock) ) Product name Epicoat 604; Toto Kasei Co., Ltd. product name YH434; Mitsubishi Gas Chemical Co., Ltd. product names TETRAD-X and TERRAD-C; Nippon Kayaku Co., Ltd. product name GAN; Sumitomo Chemical brand name ELM-120, etc.), heterocyclic-containing epoxy resins (Ciba Specialty Chemicals brand name Araldite PT810, etc.), alicyclic epoxy resins (UCL ERL4234, 4299) , 4221, 4206, etc.), and these can be used alone or in combination of two or more. Among these epoxy resins, amine-type epoxy resins having 3 or more epoxy groups in one molecule are particularly preferable in terms of improving solvent resistance, chemical resistance, and moisture resistance.

  These epoxy resins may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 20% by weight with respect to the total amount of the resin containing an imide bond as the component (A). Examples of such an epoxy compound include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromocresyl glycidyl ether. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.

  The amount of these epoxy resins used is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and even more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the resin containing an imide bond as the component (A). Part. When the compounding amount of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance and moisture resistance tend to decrease, and when it exceeds 50 parts by weight, the heat resistance and viscosity stability tend to decrease. is there.

  As an addition method of the epoxy resin, the epoxy resin to be added may be added after being dissolved in the same organic solvent as the component (A) that dissolves the resin containing an imide bond, or added directly. May be.

[(B) component: inorganic filler]
The inorganic filler used as the component (B) in the present invention contains hydrotalcite and silica. Moreover, inorganic fillers and / or organic fillers other than hydrotalcite and silica can be added to such an extent that the effects of the present invention are not impaired.

Examples of inorganic fillers other than hydrotalcite and silica include alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N _4). ), Barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (2MgO.2Al ₂ O ₃ / 5SiO ₂ ), talc (3MgO.4SiO _2. H ₂ O), aluminum titanate (TiO ₂ —Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ —ZrO ₂ ), barium silicate (Ba O.8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic Bentonite, carbon (C), hydrotalcite (Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O) and the like can be used, and one or more of these can also be used.

  Among these, it is preferable to contain barium sulfate from the viewpoint of improving the screen printability and electrical characteristics.

  As the organic filler, fine particles of a heat resistant resin having an amide bond, an imide bond, an ester bond or an ether bond are preferable. As such a heat-resistant resin, polyimide resin or a precursor thereof, polyamideimide resin or a precursor thereof, or fine particles of polyamide resin are preferably used from the viewpoint of heat resistance and mechanical properties.

The heat resistant resin as the organic filler can be produced as follows.
First, a polyimide resin can be obtained by reacting (a) an aromatic tetracarboxylic dianhydride and (b) an aromatic diamine compound.

  (A) As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-bis Phenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3 , 4-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-di Carboxyphenyl Ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′- Benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic 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-terolachlornaphthalene-1, 4,5,8-tetracar Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3 , 4-Dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2,2-bis (3,4-di Carboxyphenyl) 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 (trimellitate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexa Methylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitate anhydrous) ), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- ( Dodecamemethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. May be used.

  In the above (a) aromatic tetracarboxylic dianhydride, a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride is added according to the purpose, and 50 mol% of the aromatic tetracarboxylic dianhydride is added. It can be used within a range not exceeding. Examples of such tetracarboxylic dianhydrides include ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic Acid dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-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, bis {exobicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride Thing} sulfone, bishi Rho- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like.

  Next, as the (b) aromatic diamine compound, 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 sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl Ketone, 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 (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3- Bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4 ′-[1 , 4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] Examples thereof include sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-aminophenoxy) phenyl] sulfone. These may be used in combination.

  For the (b) aromatic diamine compound, a diamine compound other than the aromatic diamine compound can be used in a range not exceeding 50 mol% of the aromatic diamine compound depending on the purpose. Examples of such diamine compounds include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino. Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethylpolysiloxane and the like. The (a) aromatic tetracarboxylic dianhydride and the (b) aromatic diamine compound are preferably reacted in an approximately equimolar amount from the viewpoint of film characteristics.

  The reaction between (a) aromatic tetracarboxylic dianhydride and (b) aromatic diamine compound is carried out in an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2. -Nitrogen-containing compounds such as imidazolidinone; sulfur compounds such as sulfolane and dimethyl sulfoxide; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, etc. Lactones; dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) E) ethers such as ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, Alcohols such as tetraethylene glycol monomethyl (or monoethyl) ether; phenols such as phenol, cresol, xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate; toluene, xylene, diethylbenzene, cyclohexane, etc. Hydrocarbons: Halogenated charcoal such as trichloroethane, tetotachloroethane, monochlorobenzene Hydrogen fluorides and the like are used. These organic solvents are used alone or in combination. In consideration of solubility, low hygroscopicity, low temperature curability, environmental safety, etc., it is preferable to use lactones, ethers, ketones and the like.

  The reaction temperature is 80 ° C or lower, preferably 0 to 50 ° C. As the reaction proceeds, the reaction solution gradually thickens. In this case, polyamic acid which is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, and this is also included in the polyimide resin precursor.

  The polyimide resin is obtained by dehydrating and ring-closing the reactant (polyamide acid). Dehydration ring closure can be performed by a method of heat treatment at 120 ° C. to 250 ° C. (thermal imidization) or a method of using a dehydrating agent (chemical imidization). In the case of the heat treatment at 120 ° C. to 250 ° C., it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water may be removed azeotropically using benzene, toluene, xylene or the like.

  In the method of performing dehydration and ring closure using a dehydrating agent, it is preferable to use an acid anhydride such as acetic anhydride, propionic anhydride or benzoic acid, a carbodiimide compound such as dicyclohexylcarbodiimide, or the like as the dehydrating agent. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, or aminopyridineimidazole may be used. The dehydrating agent or the dehydrating catalyst is preferably used in an amount of 1 to 8 moles per mole of aromatic tetracarboxylic dianhydride.

  Polyamideimide resin or precursor thereof is trimellitic anhydride or trimellitic anhydride derivative (trimellitic anhydride derivative) instead of aromatic tetracarboxylic dianhydride in the production of polyimide resin or precursor thereof. And the like, and trivalent tricarboxylic acid anhydrides or derivatives thereof. Moreover, it can also manufacture using the diisocyanate compound corresponding to the diamine compound in which residues other than an amino group replace with an aromatic diamine compound and another diamine compound. Diisocyanate compounds that can be used include those obtained by reacting the aromatic diamine compound or other diamine compounds with phosgene or thionyl chloride.

  Polyamide resins are produced by reacting aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, derivatives of these dichlorides, acid anhydrides, etc. with the above-mentioned aromatic diamine compounds or other diamine compounds. be able to.

  Examples of the heat resistant resin having an ester bond include a polyester resin, and examples of the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, derivatives of these dichlorides, acid anhydrides, and the like. Some are obtained by reacting aromatic diol compounds such as 1,4-dihydroxybenzene, bisphenol F, bisphenol A, and 4,4′-dihydroxybiphenyl.

  As the polyamideimide resin, a polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, those described above are used. The molar ratio of isophthalic acid dihydrazide in the aromatic diamine compound is preferably 1 to 100 mol%. If it is less than 1 mol%, the solubility in the modified polyamideimide resin tends to decrease, and if the content of isophthalic acid dihydrazide is large, the moisture resistance of the layer formed by the paste of the present invention tends to decrease. 80 mol% is more preferable, and 20-70 mol% is used especially preferably. This polyamide-imide resin can be obtained in the same manner as the synthesis of the polyimide resin, with respect to the compounding ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, the synthesis method, and the like.

  The polyamideimide resin obtained by reacting trimellitic anhydride and, if necessary, dicarboxylic acid and polyisocyanate is likely to become insoluble in organic solvents when heated, and organic fine particles made of this polyamideimide resin should be used. You can also. About the manufacturing method of this polyamideimide resin, it can manufacture similarly to the manufacturing method of an above described polyamideimide resin.

  Examples of the fine particle forming method include a non-aqueous dispersion polymerization method (Japanese Patent Publication No. 60-48531, Japanese Patent Laid-Open No. 59-230018), and a precipitation polymerization method (Japanese Patent Laid-Open No. 59-108030, Japanese Patent Laid-Open No. 60). No. -22425), a method of mechanically pulverizing powder modified from a resin solution, a method of finely pulverizing a resin solution while adding the resin solution to a poor catalyst, a method of obtaining fine particles by drying a spray solution of a resin solution, a detergent Alternatively, there is a method in which a resin having a temperature dependency of solubility in a solvent in a resin solution is formed into fine particles.

  As the inorganic fine particles and / or organic fine particles in the present invention, those having an average particle size of 50 μm or less and a maximum particle size of 100 μm or less are preferably used. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropic coefficient of 1.1 or more, which will be described later, and when the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient. The average particle size is more preferably 30 μm or less, further preferably 10 μm or less, particularly preferably 1 μm or less, and the maximum particle size is more preferably 80 μm or less, still more preferably 60 μm or less, particularly preferably 40 μm or less.

[Resin composition]
The resin composition of the present invention can be produced by dissolving the resin as component (A) in an organic solvent to obtain a resin solution and dispersing the inorganic fine particles and / or organic fine particles as the component (B).

  In the resin composition of the present invention, the content of inorganic fine particles and / or organic fine particles used as the component (B) is preferably 1 to 250 parts by weight with respect to 100 parts by weight of the component (A), preferably 30 to 200. It is more preferable to set it as a weight part, and it is especially preferable to set it as 50-100 weight part. When the content of the component (B) is less than this, the viscosity and thixotropy coefficient of the paste are lowered, the stringing of the paste is increased, the flow of the paste after printing is increased, and the film thickness tends to be reduced. Yes, electrical characteristics tend to be inferior. Moreover, when there is more content of (B) component, the viscosity of a paste and a thixotropy coefficient become high, and there exists a tendency for the void and pinhole in a printing film to increase while the transferability to the base material of a paste falls. is there.

  As the organic solvent for dissolving the resin of component (A), an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; a sulfur-containing solvent; For example, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; ester solvents such as γ-butyrolactone, cellosolve acetate; ketone solvents such as cyclohexanone, methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene, xylene, etc. These may be used alone or in combination of two or more. Since the solubility varies depending on the resin to be produced, a solvent capable of dissolving the resin is selected and used.

  As a method of dispersing inorganic and / or organic fine particles in a thermosetting resin solution, roll kneading, mixer mixing, etc., which are usually performed in the paint field, are applied and sufficient dispersion is performed. good.

  In the resin composition of the present invention, surfactants such as antifoaming agents and leveling agents, colorants such as dyes and pigments, heat, Stabilizers, antioxidants, flame retardants, and lubricants can also be added.

  The resin composition of the present invention has a viscosity at 25 ° C. of 20 Pa · s to 80 Pa · s, particularly preferably 30 to 50 Pa · s, at 25 ° C. Moreover, it is preferable that a thixotropy coefficient is 1.1 or more. When the viscosity is less than 20 Pa · s, the flow of the paste after printing tends to increase and the film thickness tends to be reduced, and when the viscosity exceeds 80 Pa · s, the transferability of the paste to the substrate decreases. There is a tendency for voids and pinholes in the printed film to increase. When the thixotropy coefficient is less than 1.1, the stringing of the paste increases, the flow of the paste after printing increases, and the film thickness also tends to be reduced.

  Here, the viscosity of the resin composition is expressed as a viscosity at a rotation speed of 10 rpm measured with a sample amount of 0.2 ml or 0.5 ml using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U type). Also, the thixotropy coefficient (TI value) of the paste was applied only to the paste at the rotation speeds of 1 rpm and 10 rpm measured with a sample amount of 0.2 ml or 0.5 ml using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model RE80U). Viscosity is expressed as the ratio η1 / η10 of η1 and η10.

  The present invention can also be suitably used for a flexible wiring board in which the above resin composition is screen-printed on a wiring pattern of a flexible wiring board and then thermally cured to form a cured film to form a protective film. In particular, it is suitable for use as a protective film on the surface of a flexible wiring board in which all of the wiring pattern portion is plated. The conditions for thermosetting are preferably 80 ° C. to 130 ° C., particularly preferably 90 ° C. to 120 ° C., from the viewpoint of preventing the diffusion of the plating layer and obtaining warpage and flexibility suitable as a protective film. It is not limited to this range, For example, it can also be made to harden | cure in the range of 50-200 degreeC, especially 50-140 degreeC. In addition, the heating time is 60 to 150 minutes, preferably 80 to 120 minutes from the viewpoint of preventing the plating layer from being diffused and obtaining warpage and flexibility suitable as a protective film, but is limited to this range. However, it can be cured in the range of 1 to 1,000 minutes, for example, 5 to 300 minutes, especially 10 to 150 minutes.

[Film-forming material]
The resin composition of the present invention contains the above-described resin composition, and is suitably used for coating methods such as screen printing, dispenser, and spin coating as film forming materials for various electric products and electronic parts. In particular, it is suitably used for screen printing.

  The resin composition according to the present invention is suitably used, for example, as an overcoat material for electronic components in the field of semiconductor elements, printed circuit boards, etc., a liquid sealing material, an interlayer insulating film, a surface protective film, a solder resist layer, an adhesive layer, etc. . It can also be used for sheet varnishes, varnishes for MCL laminates, varnishes for friction materials, etc. in combination with a base material such as enameled wire varnish, impregnating varnish for electrical insulation, cast varnish, mica, glass cloth. In addition, since the resin coating is not peeled off from the circuit board or the like, the adhesion between the base material and the resin and the printing workability are excellent, so that a highly reliable electronic component can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these.

Synthesis example 1
[Synthesis of polymer resin]
In a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer, 61.72 g of γ-butyrolactone, Plaxel CD-220 (manufactured by Daicel Chemical Industries, Ltd., 1,6- Hexanediol-based polycarbonate diol trade name) 74.64 g (0.37 mol), 4,4′-diphenylmethane diisocyanate 125.14 g (0.46 mol) toluene diisocyanate 58.4 g (0.34 mol), 150 The temperature was raised to ° C. The reaction was carried out at 150 ° C. for 4 hours.

  Next, 88.4 g (0.46 mol) of trimellitic anhydride was charged and reacted at 70 ° C. for 3 hours. Subsequently, 6.76 g (0.027 mol) of 4,4′-diphenylmethane diisocyanate was added again and 0.0034 g (0.00002 mol) of toluene diisocyanate was reacted at 120 ° C. for 1 hour and at 180 ° C. for 3 hours. After the reaction, 341.6 g of γ-butyrolactone was charged and cooled, 9.5 g (0.11 mol) of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and reacted at 120 ° C. for 3 hours. A resin having an average molecular weight of 38,000 was obtained. The number average molecular weight can be adjusted by collecting a small amount of the reaction solution for each reaction time and observing the rate of change in viscosity using a Gardner bubble viscometer. The obtained resin was diluted with γ-butyrolactone to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 50% by weight.

(Synthesis Example 2)
In a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer, 61.72 g of γ-butyrolactone, 1,6-hexanediol-based polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd.) , 74.64 g (0.37 mol) of trade name “Placcel CD-220”, 125.14 g (0.46 mol) of 4,4′-diphenylmethane diisocyanate, 58.4 g (0.34 mol) of toluene diisocyanate, The temperature was raised to 150 ° C. and reacted at 150 ° C. for 4 hours.

  Next, 88.4 g (0.46 mol) of trimellitic anhydride was added to the reaction product and reacted at 70 ° C. for 3 hours. Subsequently, 6.76 g (0.027 mol) of 4,4′-diphenylmethane diisocyanate and 0.0034 g (0.00002 mol) of toluene diisocyanate were charged again and reacted at 120 ° C. for 1 hour and at 180 ° C. for 3 hours. After the reaction, 341.6 g of γ-butyrolactone was charged and cooled, and 0.02 g (0.0001 mol) of pyromellitic anhydride was further charged and reacted at 120 ° C. for 3 hours to give a resin having a number average molecular weight of 38,000 (polycarbonate) Modified polyamideimide resin: (A) component of the present invention) was obtained. The number average molecular weight can be adjusted by collecting a small amount of the reaction solution for each reaction time and observing the rate of change in viscosity using a Gardner bubble viscometer. The obtained resin was diluted with γ-butyrolactone to obtain a polycarbonate-modified polyamideimide resin solution having a nonvolatile content of 50% by weight.

Example 1
The polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 38,000 obtained in Synthesis Example 1 is mixed, and 1 part by weight of the solvent treatment liquid is added to 100 parts by weight of the resin component. Kasei Kogyo Co., Ltd. product name: Disparon 230) was stirred at 0.1 parts by weight at 20 ° C. for 30 minutes. Furthermore, 70 parts by weight of barium sulfate (trade name: B-31 manufactured by Sakai Chemical Industry Co., Ltd.), 20 parts by weight of hydrotalcite (trade name: HT-P manufactured by Sakai Chemical Co., Ltd.), silica (manufactured by Nippon Aerosil Co., Ltd.) Product name: R-974) 10 parts by weight previously dispersed in a bead mill is blended. If necessary, a solvent such as γ-butyrolactone is added and stirred at 20 ° C. for 1 hour. Further, an amine type epoxy resin (Toto) 10 parts by weight of Kasei Co., Ltd. product name: YH-434L) was added and stirred at 20 ° C. for 1 hour to obtain a polycarbonate-modified polyamideimide resin composition.

Example 2
Except that hydrotalcite was changed to 30 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Example 3
Except that hydrotalcite was changed to 50 parts by weight in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Example 4
Except for using 20 parts by weight of silica in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Example 5
Except for using 30 parts by weight of silica in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Comparative Example 1
Except that hydrotalcite was not blended in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Comparative Example 2
Except that silica was not blended in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Comparative Example 3
Except that talc (trade name: ST-200 manufactured by Nippon Talc Co., Ltd.) was used instead of silica in Example 1, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

Comparative Example 4
The polycarbonate-modified polyamide-imide resin solution having a number average molecular weight of 38,000 obtained in Synthesis Example 2 is mixed, and 1 part by weight of the solvent treatment liquid is added to 100 parts by weight of the resin, and the antifoaming agent (A) (Enomoto Kasei Kogyo Co., Ltd. product name: Disparon 230) was stirred at 0.1 parts by weight at 20 ° C. for 30 minutes. Furthermore, 70 parts by weight of barium sulfate (trade name: B-31, manufactured by Sakai Chemical Industry Co., Ltd.) and 20 parts by weight of hydrotalcite (trade name: HT-P, manufactured by Sakai Chemical Co., Ltd.) were previously dispersed in a bead mill. Add, if necessary, a solvent such as γ-butyrolactone and stir at 20 ° C. for 1 hour, and add 10 parts by weight of an amine-type epoxy resin (trade name: YH-434L, manufactured by Tohto Kasei Co., Ltd.). The mixture was stirred at 0 ° C. for 1 hour to obtain a polycarbonate-modified polyamideimide resin composition.
The adhesion properties of the polycarbonate-modified polyamideimide resin composition and the polyamideimide resin composition obtained in the above Examples and Comparative Examples to the polyimide film were measured by the following methods, and the results are shown in Table 1.

Printability The printing speed of the polycarbonate-modified polyamideimide resin composition obtained on a 35 μm copper foil is increased by a printing machine (trade name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.). A 30 mm square was printed at 100 mm / sec, and leveling properties immediately after printing and stringing of the resin composition were visually observed. The case where the leveling is good and there is no threading is indicated by ◯, the case where the leveling is slightly bad and the threading is also indicated by Δ, and the case where the leveling and threading are remarkable is indicated by ×.
Printing appearance The obtained polycarbonate-modified polyamideimide resin composition is printed on a 35 μm copper foil by a printing machine (trade name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.). Print 30mm square at 100mm / sec,
The appearance after printing (foam marks, aggregates, etc.) was observed with a 100-power microscope. The case where there are no bubble marks and aggregates is indicated as ◯, the case where there is a slight amount as Δ, and the case where it is noticeable as X.

Electrical properties A printing machine (manufactured by Neurong Co., Ltd.) was applied to the obtained polycarbonate-modified polyamideimide resin composition so as to cover a copper electrode tin-plated in a comb shape with a line width of 15 μm and a space width of 15 μm. : LS-34GX) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.), printing at a printing speed of 100 mm / sec, heating and curing in an air atmosphere at 120 ° C. for 60 minutes, and a polyimide substrate comb with a polycarbonate-modified polyamideimide resin coating A mold electrode was obtained. The resulting polyimide base comb-coated electrode with a polycarbonate-modified polyamide-imide resin film was subjected to a continuous resistance measuring machine (trade name: Ion Migration Tester MIG-8600, manufactured by IMV Corporation) and unsaturated pressure cooker (trade name, manufactured by Hirayama Manufacturing Co., Ltd.). : HAST PC-422R8D), and holding of a resistance of 10 ⁸ Ω or more after energization is confirmed under conditions of a temperature of 120 ° C., a humidity of 85%, an applied voltage of 60 V, and an applied time of 100 hours. The evaluation is performed three times under the same conditions, and it is good if the resistance can be confirmed three times.

Adhesiveness A test piece obtained by curing a polycarbonate-modified polyamideimide resin composition after printing in an air environment at 120 ° C. for 60 minutes is sandwiched between reel-shaped polyimide films, wound up, and subjected to a load of 500 g, and 25 ° C. Leave for 48 hours. The load at which the test piece after leaving for a predetermined time is peeled off from the polyimide film is measured. The closer the load that peels from the film is to zero, the better.

Storage Stability Viscosity of the produced polycarbonate-modified polyamideimide resin composition is measured at 10 rpm with an E-type viscometer at a temperature of 25 ° C. After measurement, it was stored in a refrigerator at a set temperature of 7 ° C., and after 1 month, the viscosity was measured under the same conditions, and the viscosity increase rate from the time of preparation was calculated according to the following formula.
Thickening rate = viscosity after 1 month / viscosity at the time of preparation

From the above results, we found the following.
By blending hydrotalcite and silica in the resin composition, stable electrical properties can be obtained under high temperature and high humidity, and storage stability is good, and the adhesiveness with the cured polyimide film is reduced. it can. However, an excessive blending amount is not preferable because it causes problems in printing appearance such as defoaming property and deterioration of leveling property.

As described above, the resin composition and the film-forming material according to the present invention are suitably used for coating methods such as screen printing, dispenser, and spin coating as film-forming materials for various electric products and electronic parts. Moreover, since it is hard to stick with the polyimide film after hardening, there exists a possibility that it may be useful in terms of workability and cost, such as eliminating the spacer between a polyimide film and a cured film.

Claims (5)

(A) a resin having at least one acid anhydride group and / or carboxyl group, (B) an inorganic filler containing hydrotalcite and silica, and (C) an epoxy resin, and (B) the hydrotalcite and The content of inorganic filler containing silica is 50 to 100% by weight with respect to 100 parts by weight of the resin (A), and the content of hydrotalcite in the inorganic filler is 20 to 50% by weight, Furthermore, the thermosetting resin composition whose content rate of a silica is 10-30 mass% . (A) A resin having at least one acid anhydride group and / or carboxyl group is represented by the following general formula (I):
(In the formula, each R is independently an alkylene group having 1 to 18 carbon atoms, X is a divalent organic group, and m and n are each independently an integer of 1 to 20) The thermosetting resin composition according to claim 1, which is a thermosetting resin containing a polyurethane structure represented by:   The component (A) is at least one selected from an imide bond, an amide-imide bond, and an amide resin obtained by reacting an isocyanate residue with a trivalent or higher polycarboxylic acid having an acid anhydride group or a derivative thereof. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a resin having a bond. The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (B) further contains barium sulfate. The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition is for a protective film of a flexible printed board in which a copper foil is laminated on a polyimide base material.