JP5239335B2 - 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. It is used. 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, some of the additives such as the above-mentioned various coupling agents and surface treatment agents ooze out on the surface of the film and the periphery of the film during the curing, and the resin coating is applied to the circuit board during the subsequent bonding process of the circuit with a resin or the like. There was a problem that it peeled off from and had an adverse effect. Therefore, there has been a demand for a resin composition and a film-forming material containing the same that improve the adhesion between the base material and the resin and the printing workability without causing the resin film to peel from the circuit board.

  This invention is made | formed in view of the above, Comprising: It aims at obtaining the resin composition which improved the adhesiveness of a base material and resin, and the film forming material containing the same.

  The resin composition according to the present invention is a resin composition containing (A) a resin and (B) an inorganic filler and / or an organic filler, and the number average molecular weight of the (A) resin is 22,000-50, 000.

  In the resin composition of the present invention, (B) inorganic filler and / or organic filler are dispersed in a resin solution containing a solvent in which two or more (A) resins having different number average molecular weights are mixed. It is characterized by.

  In the resin composition of the present invention, the (A) resin has a polycarbonate skeleton.

  Moreover, in the resin composition of this invention, the said (A) resin has an imide bond, It is characterized by the above-mentioned.

  In the resin composition of the present invention, the resin (A) is at least one selected from the group consisting of a polyimide resin having a polycarbonate skeleton, a polyamideimide resin, a polyamide resin, and derivatives thereof. It is characterized by.

  Moreover, in the resin composition of this invention, content of the said (B) inorganic filler and / or organic filler is 1-350 weight part with respect to 100 weight part of said (A) resin. Features.

  Moreover, in the resin composition of this invention, the said (B) inorganic filler and / or organic filler contain barium sulfate, It is characterized by the above-mentioned.

  In the resin composition of the present invention, the (B) inorganic filler and / or organic filler further contains silica and talc.

  The resin composition of the present invention is further characterized by containing an epoxy resin as a curing agent.

  Moreover, in the film forming material of this invention, the said resin composition is included.

  The resin composition and film-forming material of the present invention contain (A) a resin having a number average molecular weight of 22,000 to 50,000, and (B) an inorganic filler and / or an organic filler, and are therefore suitable for screen printing. It does not cause peeling at the film edge after tin plating. Further, the resin composition and the film-forming material of the present invention have thixotropic properties in addition to the above-mentioned excellent characteristics, an overcoat material for electronic parts, a liquid sealing material, an varnish for varnish electrical insulation for enamel wires, Laminate varnish, friction material varnish, interlayer insulation film in the printed circuit board field, surface protective film, solder resist film, adhesive layer, etc., and can be suitably used for electronic components such as semiconductor elements, flexible wiring boards, There is an effect that a highly reliable electronic component can be obtained.

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 and (B) an inorganic filler and / or an organic filler as essential components.

[(A) component: resin]
As the resin of component (A), epoxy resin having a butadiene structure or silicone structure, phenol resin, acrylic resin, polyurethane, polybutadiene, water-added polybutadiene, polyester, polycarbonate, polyether, polysulfone, polytetrafluororesin, polysilicone, Examples include melamine resin, polyamide, polyamideimide, and polyimide. These can be used alone or in combination of two or more.

  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 (I) and (II):

（式（Ｉ）及び（ＩＩ）中、Ｒ′は、水素、炭素数１〜１０のアルキル基又はフェニル基を示し、Ｙ¹は、−ＣＨ₂−、−ＣＯ−、−ＳＯ₂−、又は−Ｏ−である）
で示される化合物を使用することができる。

(In the formulas (I) and (II), 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.

（式中、Ｙ²は、式（ＩＶ）で示される基：

である）で示されるテトラカルボン酸二無水物を使用することができる。これらは、単独で又は２種類以上を組み合わせて使用することができる。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 (III):

Wherein Y ² is a group represented by the formula (IV):

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.

（式中、複数個のＲは、それぞれ独立に炭素数１〜１８のアルキレン基であり、ｍ及びｎは、それぞれ独立に１〜２０の整数である）
で示されるジイソシアネート類を用いることができる（以下、（ｂ−１）化合物とする）。The isocyanate compound as the component (b) is, for example, the formula (V):

(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).

（式中、Ｒは、独立に炭素数１〜１８のアルキレン基であり、ｍは、１〜２０の整数である）
で示されるカーボネートジオール類と、式（ＶＩＩ）：
ＯＣＮ−Ｘ−ＮＣＯ （ＶＩＩ）
（式中、Ｘは、二価の有機基である）
で示されるジイソシアネート類を反応させることにより得られる。The compound represented by the above formula (V) is represented by the formula (VI):

(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 (VII):
OCN-X-NCO (VII)
(Wherein X is a divalent organic group)
It can be obtained by reacting a diisocyanate represented by the following formula.

  X in the diisocyanate of the formula (VII) is, for example, an arylene group such as a C1-C20 alkylene group or a phenylene group which is unsubstituted or 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 diphenylmethane-4,4′-diyl group and diphenylsulfone-4,4′-diyl group is also preferable.

  Examples of the carbonate diols represented by the above formula (VI) 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 (VII) 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 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 (VII) has an aromatic ring. These can be used alone or in combination of two or more.

  Further, as the diisocyanates represented by the formula (VII), 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 (VII), 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 blending ratio of the carbonate diols represented by the formula (VI) and the diisocyanates represented by the formula (VII) 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 of the carbonate diols represented by the above formula (VI) and the diisocyanates represented by the formula (VII) 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 (VII) and trivalent or higher polyisocyanates. . 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.

（式中、Ｒ、Ｘ、ｍ、ｎは上記で定義したとおりである）
で示される繰り返し単位を有するポリアミドイミド樹脂を得ることができる。In the case where the compound represented by the formula (I) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (VIII):

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

（式中、Ｒ、Ｘ、ｍ、ｎ、Ｙ¹は上記で定義したとおりである）
で示される繰り返し単位を有するポリアミドイミド樹脂を得ることができる。When the compound represented by the formula (II) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (IX):

(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.

（式中、Ｒ、Ｘ、ｍ、ｎ、Ｙ²は上記で定義したとおりである）
で示される繰り返し単位を有するポリイミド樹脂を得ることができる。When the compound represented by formula (III) 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, 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. In addition, after the synthesis is completed, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams, and oximes. In addition, it is preferable to use a thermosetting resin as (A) component.

  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, the film properties after tin plating tend to be deteriorated. When the number average molecular weight exceeds 50,000, it is difficult to dissolve in a non-nitrogen-containing polar solvent. Easy to insolubilize. In addition, workability tends to be inferior.

  The resin (A) used in the resin composition of the present invention is preferably a mixture of two or more resins having different molecular weights if the number average molecular weight measured by the GPC method is within the above range, from the viewpoint of easy synthesis. . The difference in molecular weight is preferably a difference in number average molecular weight of 5,000 or more. If the difference in number average molecular weight is less than 5,000, the adhesion effect tends to be difficult to obtain.

  Of the resins having different number average molecular weights, the minimum molecular weight is preferably 20,000 or more in terms of number average molecular weight. If the number average molecular weight is less than 20,000, the moisture resistance and heat resistance tend to decrease, which is not preferable. On the other hand, among resins having different number average molecular weights, the maximum molecular weight is preferably less than 50,000 in number average molecular weight. When the number average molecular weight exceeds 50,000, the viscosity of the resin is increased, and the workability such as mixing of the inorganic filler and / or organic filler and screen printing is not preferable.

  The mixing ratio when mixing two or more resins having different number average molecular weights used in the present invention can be mixed without particular limitation as long as the number average molecular weight measured by the GPC method is within the above range. Further, the concentration of the resin solution can be selected without limitation.

  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 Corporation);・ 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 fine particles and / or organic fine particles]
The inorganic fine particles and / or organic fine particles used as the component (B) in the present invention are those that form a paste by dispersing in the thermosetting resin or thermosetting resin solution of the component (A). There is no particular limitation.

Examples of the inorganic fine particles include silica (SiO ₂ ), 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 (PLZT) 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 (BaO · 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 ) And the like, and one or more of these can also be used.

  Among these, it is preferable to contain barium sulfate from the viewpoint that the state of the film end after tin plating can be improved. Moreover, it is preferable that barium sulfate, a talc, and a silica are included from a viewpoint which can make an electrical property favorable.

  The organic fine particles are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond. 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 fine particles 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) Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 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, 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 -Dicarboxyfe E) 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-tetra Rubonic 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- (Hexamethylene) bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate) Water), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12 -(Dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride) and the like. You may mix and use.

  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-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, bis [4- (4-aminophenoxy) phenyl] sulfone, and the like.

  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 from 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. There are those 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 350 parts by weight with respect to 100 parts by weight of the component (A), and is preferably 30 to 300 parts. More preferably, it is more preferably 50 to 280 parts by weight, and most preferably 100 to 250 parts by weight. 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. There is a tendency that the state and electrical characteristics of the coating end after tin plating are 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 preferably has a viscosity with a rotary viscometer of 0.5 Pa · s to 500 Pa · s at 25 ° C. and a thixotropic coefficient of 1.1 or more. If the viscosity is less than 0.5 Pa · s, the flow of the paste after printing tends to increase and the film thickness tends to be reduced. If the viscosity exceeds 500 Pa · s, the transferability of the paste to the substrate decreases. At the same time, voids and pinholes in the printed film tend 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. The viscosity is more preferably 1 to 250, and particularly preferably 10 to 100. Further, the thixotropic coefficient is more preferably 1.2 or more, and particularly preferably 1.4 or more.

  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.

  Furthermore, it is preferable that the 5% thermal weight loss temperature of the resin composition of the present invention as a cured film is 250 ° C. or higher. If the 5% thermal weight loss temperature is less than 250 ° C., the cured film may be deformed and decomposed due to heat applied at the time of connection with a rigid wiring board, IC chip, electronic component or LCD panel. The 5% weight loss temperature is the same as the generation of a cured film for measurement of tensile modulus and the like, that is, 80 to 130 ° C., and the time for forming a protective film on the surface of a normal flexible wiring board. It heats within the range, forms a cured film with a film thickness of about 30 μm, and takes a value measured by the TG-DTA method in an air atmosphere at a heating rate of 10 ° C./min.

  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 hardened 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.

[Coating 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.

Example 1
(Synthesis of polymer resin)
Plaxel CD-220 (manufactured by Daicel Chemical Industries, Ltd., 1,6-hexanediol-based polycarbonate diol) is added to a 3 liter four-necked flask equipped with a stirrer, a condenser with an oil separator, a nitrogen inlet tube and a thermometer. Name) 2000.0 g (100 mol), 292.0 g (2.00 mol) of adipic acid and 114.6 g of xylene were charged, and the temperature was raised to 200 ° C. while removing by-product condensed water. The mixture was reacted at 200 ° C. for 2 hours to obtain dicarboxylic acid A having an acid value of 49.7 KOH mg / g.

  Subsequently, 150.0 g (0.60 mol) of 4,4′-diphenylmethane diisocyanate and 69.12 g of trimellitic anhydride (into a 2 liter four-necked flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer ( 0.36 mol) and 541.44 g (0.24 mol) of dicarboxylic acid A obtained in the above synthesis and 760.56 g of γ-butyrolactone were heated to 160 ° C. and reacted for 8 hours to obtain a number average molecular weight of 38, 000 resins were 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 40% by weight.

[Synthesis of low molecular weight resin]
A low molecular resin having a number average molecular weight of 29,000 and a nonvolatile content of 40% by weight was obtained in the same manner as the synthesis of the polymer resin except that the temperature was raised to 160 ° C. and the reaction was performed for 7 hours.

  20% of the obtained polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 29,000 and 80% of the polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 38,000 were mixed, and the resin content was 100 parts by weight. Then, 1 part by weight of the solvent treatment liquid and 0.3 part by weight of silicone-based antifoaming agent (A) (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) were blended and stirred at 20 ° C. for 10 minutes. Furthermore, 30 parts by weight of barium sulfate (trade name: B-30, manufactured by Sakai Chemical Industry Co., Ltd.) was blended, and a solvent such as γ-butyrolactone was added as necessary, followed by stirring at 50 ° C. for 1 hour. Add 20 parts by weight of -1004 (trade name, bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), stir at 20 ° C. for 1 hour, and then add a silicone antifoam (B) (Shin-Etsu Chemical Co., Ltd.) Product name: KS-603) 0.2 parts by weight was blended and stirred at 20 ° C. for 30 minutes to obtain a polycarbonate-modified polyamideimide resin composition.

<Measurement of number average molecular weight and weight average molecular weight of resin>
It was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The measurement conditions for GPC are shown below.
(GPC conditions)
Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Detector: Hitachi L-4000 UV [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-S300MDT-5 (two in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: DMF / THF = 1/1 + phosphoric acid (0.06M) + lithium bromide (0.06M)

Example 2
The polycarbonate-modified polyamideimide resin was prepared in the same manner as in Example 1 except that the polycarbonate-modified polyamideimide resin having number average molecular weights of 25,000 and 32,000 was prepared by adjusting the reaction time. An imide resin composition was obtained.

Example 3
A polycarbonate-modified polyamideimide resin composition was prepared in the same manner as in Example 1 except that the polycarbonate-modified polyamideimide resin having a number average molecular weight of 23,000 and 29,000 was used. Got.

Example 4
Except that the polycarbonate-modified polyamideimide resin having the number average molecular weights of 36,000 and 42,000 was prepared by adjusting the reaction time in Example 1, the same procedure as in Example 1 was performed, and the polycarbonate-modified polyamideimide resin was prepared. An imide resin composition was obtained.

Example 5
20% of the polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 29,000 obtained in Example 1 and 80% of the polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 38,000 are mixed, and the resin content is 100 weight. 1 part by weight of the solvent treatment liquid and 0.3 part by weight of the silicone-based antifoaming agent (A) (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 minutes at 20 ° C. did. Furthermore, 100 parts by weight of barium sulfate (trade name: B-30, manufactured by Sakai Chemical Industry Co., Ltd.), 20 parts by weight of talc (trade name: Microace P-3, manufactured by Nippon Talc Co., Ltd.) and silica (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by weight of a product name: AEROSIL 380) is added, if necessary, a solvent such as γ-butyrolactone is added and stirred at 50 ° C. for 1 hour, and further an amine type epoxy resin (manufactured by Tohto Kasei Co., Ltd., product name: YH-). 434 L) was added, and the mixture was stirred at 20 ° C. for 1 hour. Further, 0.2 part by weight of silicone-based antifoaming agent (B) (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended, The mixture was stirred for 30 minutes at a temperature to obtain a polycarbonate-modified polyamideimide resin composition.

Example 6
The polycarbonate modified polyamideimide was prepared in the same manner as in Example 1 except that a resin having a number average molecular weight of 32,000 in the polycarbonate modified polyamideimide resin in Example 1 was prepared by adjusting the reaction time and used alone. A resin composition was obtained.

Comparative Example 1
The polycarbonate-modified polyamideimide was prepared in the same manner as in Example 1 except that the polycarbonate-modified polyamideimide resin having number average molecular weights of 15,000 and 23,000 was prepared by adjusting the reaction time. A resin composition was obtained.

  The characteristics of the polycarbonate-modified polyamideimide resin composition and the polyamideimide resin composition obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2.

Film end state after tin plating The obtained polycarbonate-modified polyamideimide resin composition is printed on a 35 μm copper foil with 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 a printing speed of 100 mm / sec, and heat-cured at 120 ° C. for 60 minutes in an air atmosphere to obtain a polycarbonate-modified polyamideimide resin film. The obtained polycarbonate-modified polyamide-imide resin film was immersed in a tin plating solution (trade name: LT-34 manufactured by Shipley Far East Co., Ltd.) at 70 ° C. for 3 minutes, and then immersed in ion-exchanged water at 80 ° C. for 10 minutes. After drying with a hot air circulating dryer for 30 minutes, the peeled state of the resin coating around the polycarbonate-modified polyamideimide resin coating on the copper foil was observed with a universal projector (Nikon Corporation magnification 50 ×). A resin film without peeling was marked with ◯, a film with slight peeling was marked with Δ, and a film with peeling was marked with 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 substrate comb-shaped electrode with a polycarbonate-modified polyamideimide resin coating was used as a continuous resistance measuring instrument (trade name: Ion Migration Tester, manufactured by IMV Corporation).
MIG-8600) and unsaturated pressure cooker (trade name: HAST PC-422R8D manufactured by Hirayama Mfg. Co., Ltd.) were used to measure resistance under conditions of a temperature of 110 ° C., a humidity of 85%, an applied voltage of 40 V, and an applied time of 100 hours. .

For the polycarbonate-modified polyamideimide resin compositions obtained in Examples 1 to 6 and Comparative Example 1, three samples were prepared and measured. 100 hours after the voltage application, the resistance value of all three samples was 1 × 10 ⁻⁶ Ω or more “A”, and the two samples were 1 × 10 ⁻⁶ Ω or more “B”, 1 A sample having a value of 1 × 10 ⁻⁶ Ω or higher was evaluated as “C”, and a sample in which all three samples were less than 1 × 10 ⁻⁶ Ω was evaluated as “D”.

Printing workability The obtained polycarbonate-modified polyamide-imide resin composition is printed on a 2 mm glass plate with a printing machine (product name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Co., Ltd.). A 100 mm square was printed at a speed of 100 mm / sec, and cured by heating at 120 ° C. for 60 minutes in an air atmosphere to obtain a polycarbonate-modified polyamideimide resin film. The obtained polycarbonate-modified polyamideimide resin coating was observed with a universal projector (Nikon Corporation magnification 20 ×), and the resin coating was observed for scraping and end chipping. A resin film having no chipping or chipping at the end was rated as ◯, and a resin film having chipping or chipping at the end was marked as x.

From the above results, we found the following.
In Examples 1 to 6, since a resin having a number average molecular weight of 22,000 to 50,000 is used, the printing workability is excellent without causing peeling at the film end after tin plating.

  Moreover, in Examples 1-5, the film edge part state after tin plating was favorable, and the electrical property was also generally favorable. The printing workability was good except in Example 4. On the other hand, in Comparative Example 1, scraping and chipping of the end portions were observed at the film end portions after tin plating.

  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. In addition, it is excellent in printing workability without causing peeling at the film edge after tin plating, overcoat material for electronic parts, liquid sealing material, varnish for enameled wire varnish for electrical insulation, varnish for laminate, It is useful for electronic parts such as varnishes for friction materials, interlayer insulation films in the field of printed circuit boards, surface protective films, solder resist films, adhesive layers, and semiconductor elements including these.

Claims (6)

A resin composition comprising (A) a resin and (B) an inorganic filler and / or an organic filler,
(A) the number average molecular weight of the resin Ri der 22,000～50,000,
The (A) resin is at least one selected from the group consisting of a polyimide resin having a polycarbonate skeleton, a polyamideimide resin, a polyamide resin, and derivatives thereof,
A resin solution containing a solvent having a number average molecular weight was mixed two or more different (A) resin, (B) a mineral filler and / or a resin composition in which the organic filler is characterized that you have dispersed.   2. The resin composition according to claim 1, wherein the content of the (B) inorganic filler and / or the organic filler is 1 to 350 parts by weight with respect to 100 parts by weight of the (A) resin.   The resin composition according to claim 1 or 2, wherein the (B) inorganic filler and / or organic filler contains barium sulfate.   The resin composition according to claim 3, wherein the (B) inorganic filler and / or organic filler further contains silica and talc.   Furthermore, an epoxy resin is included as a hardening | curing agent, The resin composition of any one of Claims 1-4 characterized by the above-mentioned.   A film-forming material comprising the resin composition according to any one of claims 1 to 5.