WO2006098409A1

WO2006098409A1 - Resin composition and coating film forming material

Info

Publication number: WO2006098409A1
Application number: PCT/JP2006/305270
Authority: WO
Inventors: Katsuhiro Onose; Tomohiro Hirata; Susumu Kaneko
Original assignee: Hitachi Chemical Company, Ltd.
Priority date: 2005-03-17
Filing date: 2006-03-16
Publication date: 2006-09-21
Also published as: JPWO2006098409A1; TWI325438B; CN101128543B; TW200641051A; KR100880500B1; CN101128543A; JP5239335B2; KR20070087036A

Abstract

A resin composition that is suitable for use in screen printing, achieving improvement to peeling at resin coating film edges after tin plating; and a coating film forming material containing the same. There is provided a resin composition comprising a resin (A) and an inorganic and/or organic filler (B), wherein the resin (A) has a number average molecular weight of 22,000 to 50,000. The inorganic filler and/or organic filler (B) may be dispersed in a solvent-containing solution of mixture of two or more resins (A) with different number average molecular weights. Further, there is provided a coating film forming material comprising the resin composition.

Description

Specification

Resin composition and film-forming material containing the same

Technical field

[0001] The present invention relates to a resin composition and a film-forming material comprising the same, and in particular, a resin composition having thixotropic properties suitable for coating methods such as a screen printer, a dispenser, a spin coater, and a film-form comprising the same. Regarding materials.

Background art

[0002] In recent years, in the field of electronic components, polyimide resin, polyamide instead of epoxy resin is used as a resin excellent in heat resistance, electrical characteristics, and moisture resistance in response to downsizing, thinning, and high speed. Imido resin and polyamide resin are used. These resins have a problem that when the resin structure is rigid and used as a thin film substrate, the substrate after curing is greatly warped, the cured film lacks flexibility and has poor flexibility.

[0003] Therefore, in order to improve low warpage and flexibility, polyamide imide resin (Patent Document 1, Patent Document 2, and Patent Document 3) in which the resin is made flexible and has a low elastic modulus is modified. Proposed. In these resins, inorganic fillers, organic fillers, etc. are dispersed in the resin solution in order to improve printability and workability. In addition, additives such as various coupling agents and surface treatment agents are used to improve the adhesion between the base material, the resin and the filler and the resin.

[0004] Patent Document 1: Japanese Patent Laid-Open No. 62-106960

Patent Document 2: JP-A-8-12763

Patent Document 3: Japanese Patent Laid-Open No. 7-196798

Disclosure of the invention

Problems to be solved by the invention

[0005] However, some of the additives such as coupling agents and surface treatment agents ooze out on the surface of the film and the periphery of the film during curing, and then the circuit is bonded with grease. Occasionally, the resin coating has a problem in that the circuit board force is also peeled off. Therefore, the adhesion between the base material and the resin and the printing work without the resin film being peeled off from the circuit board cover. There has been a demand for a resin composition with improved properties and a film-forming material containing the composition.

[0006] The present invention has been made in view of the above, and an object of the present invention is to obtain a resin composition having improved adhesion between a substrate and the resin and a film-forming material containing the composition. .

Means for solving the problem

[0007] A resin composition according to the present invention is a resin composition comprising (A) a resin, (B) an inorganic filler and Z or an organic filler, the (A) the number average of the resin Molecular weight 22,000-50, 0

It is characterized by being 00.

[0008] In addition, in the rosin composition of the present invention, the number average molecular weight is different. (A) In a rosin solution containing a solvent in which two or more rosins are mixed, (B) an inorganic filler and Z or an organic filler Is characterized by being dispersed.

[0009] In addition, the resin composition of the present invention is characterized in that the resin (A) has a polycarbonate skeleton.

[0010] Further, in the resin composition of the present invention, the (A) resin has an imide bond.

[0011] In the resin composition of the present invention, the (A) resin is 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 at least one selected.

[0012] Further, in the resin composition of the present invention, the content of the (B) inorganic filler and Z or organic filler is 1 to 350 with respect to 100 parts by weight of the (A) resin. It is characterized by its weight part.

[0013] Further, in the resin composition of the present invention, the (B) inorganic filler and Z or organic filler contain barium sulfate.

[0014] In addition, the resin composition of the present invention is characterized in that the (B) inorganic filler and Z or organic filler further contain silica and talc.

[0015] Further, the resin composition of the present invention is characterized by further containing an epoxy resin as a curing agent.

[0016] Further, the film forming material of the present invention is characterized in that it contains the above-mentioned rosin composition. The invention's effect

[0017] The resin composition and film-forming material of the present invention include (A) a resin having a number average molecular weight of 2 000 to 50,000, and (B) an inorganic filler and Z or an organic filler. It can be suitably used for screen printing, and does not cause peeling at the edge of the coating after being tinned. The resin composition and film-forming material of the present invention have thixotropy in addition to the above-described excellent characteristics, and include an overcoat material for electronic parts, a liquid sealant, and an impregnation for varnish electrical insulation for enamel wires. Suitable for electronic parts such as varnish, varnish for laminated board, varnish for friction material, interlayer insulation film, surface protective film, solder resist film, adhesive layer in printed circuit board field, etc., semiconductor element, flexible wiring board, etc. It can be used, has high reliability, and has an effect when an electronic component is obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] 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) resin and (B) inorganic filler and Z or organic filler as essential components.

[0019] (component (A): rosin]

As the resin (A), epoxy resin having a butadiene structure or silicone structure, phenol resin, acrylic resin, polyurethane, polybutadiene, water-added polybutadiene, polyester, polycarbonate, polyether, polysulfone, polytetrafluoride. Examples thereof include resins, polysilicones, melamine resins, polyamides, polyamideimides, and polyimides. These can be used alone or in combination of two or more.

[0020] 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 a flexible and low elastic modulus, it is possible to introduce a component capable of improving the flexibility into the main chain of the resin, for example, a polybutadiene skeleton, a silicone resin skeleton. And Z or a resin having a polycarbonate skeleton is preferred.

[0021] In order to improve heat resistance, electrical properties, moisture resistance, solvent resistance, and chemical resistance, the introduction of a component capable of improving heat resistance into the main chain of the resin includes, for example, , Polly Preferred are imides, polyamideimides, polyamides or cocoons having these skeletons. Among these, a resin having a polycarbonate skeleton and an imide skeleton is preferred from the viewpoint of flexibility, low elastic modulus, and high heat resistance.

[0022] In the present invention, the resin containing a polycarbonate skeleton that can be used as the component (A) is usually a 1,6-hexanediol polycarbonate diol, etc., a compound having a forceloxyl group at the terminal, an acid It can be obtained by reacting with a compound having an anhydride and a compound having an isocyanate group at the terminal or Z.

[0023] In addition, in the present invention, the resin containing an imide bond that can be used as the component (A) is usually (a) a trivalent polycarboxylic acid having an acid anhydride group and a derivative thereof, and an acid. It can be obtained by reacting one or more compounds selected from tetravalent polycarboxylic acids having an anhydride group with (b) an isocyanate compound or an amine compound.

[0024] The trivalent polycarboxylic acid having an acid anhydride group as the component (a) and its derivative are not particularly limited. For example, the compounds represented by formulas (I) and (ii):

[Chemical 1]

[0025] [Chemical 2]

(In the formulas (I) and (Π), represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and Y ¹ is CH 2 CO—SO— or 1 O—)

twenty two

The compound shown by these can be used.

[0026] Trimellitic anhydride power is particularly preferred from the standpoint of heat resistance and cost. Has an acid anhydride group The tetravalent polycarboxylic acid is not particularly limited. For example, the formula (ΠΙ): [Chemical Formula 3]

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

[Chemical 4]

(IV) can be used. These can be used alone or in combination of two or more.

In addition to these, as the acid component, aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid, Anilic acid, dimer acid, etc.) and 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.

[0028] The isocyanate compound of component (b) is, for example, the formula (V):

[Chemical 5]

(Wherein 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).

[0029] The compound represented by the formula (V) is represented by the formula (VI):

[Chemical 6]

(Wherein 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 diisocyanates represented by

[0030] X in the diisocyanates of the formula (VII) is, for example, phenyl substituted with an alkylene group having 1 to 20 carbon atoms or a lower alkyl group having 1 to 5 carbon atoms such as unsubstituted or methyl group. And arylene groups such as a len group. The number of carbon atoms of the alkylene group is more preferably 1 to 18. Groups having two aromatic rings such as diphenylmethane 4, 4 '— diyl group and diphenyl sulfone 1, 4' — diyl group are also preferred.

[0031] Examples of the carbonate diols represented by the above formula (VI) include α, ω-poly ( Hexamethylene carbonate) diol, α, ω-poly (3-methyl-pentamethylene force-bonate) diol, etc. are listed on the market and are sold by Daicel Chemical Co., Ltd. 205 205PL, 205HL, 210 210PL, 210HL, 2 20 220PL 220HL, and the like. These can be used alone or in combination of two or more.

[0032] The diisocyanates represented by the above formula (VII) include, for example, diphenylmethane 1, 2, 4'-diisocyanate; 3, 2 '3, 3' 4, 2 '4, 3' 5, 2 ' — 5, 3 '6, 2' — or 6, 3 '— Dimethyldiphenylmethane 1, 4' — Diisocyanate; 3, 2 '3, 3' 4, 2 '4, 3' 5, 2 '5 , 3 '6, 2' — or 6, 3 '— Jetyl diphenylmethane 2, 4' — Diisocyanate; 3, 2 '3, 3' 4, 2 '4, 3' 5, 2 '5, 3' 6 , 2 '— or 6, 3' — Dimethyoxydiphenylmethane 2, 4 ′ — Diisocyanate; Diphenolmethane 4, 4 ′ Diisocyanate; Diphenylmethane 3, 3 ′ — Diisocyanate; Diphenylmethane 3, 4 ′ Isocyanate; Diphenylenoateolene 4 4 'Diisocyanate; Benzophenone 4, 4' Diisocyanate; Diphenylsulfone 4, 4 'Diisocyanate; Tolylene 2,4 Diisocyanate M-xylylene diisocyanate; p xylylene diisocyanate; naphthalene 2, 6 diisocyanate; 4, 4 '— [2, 2bis (4phenoxyphenol) propane] diisocyanate, etc. Can be mentioned. 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.

[0033] In addition, the diisocyanates represented by the formula (VII) include hexamethylene diisocyanate, 2, 2, 4 trimethylhexamethylene diisocyanate, isophorone dioxysilane within the scope of the object of the present invention. Fats such as isocyanate, 4,4'-dicyclohexylenemethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate Aliphatic or cycloaliphatic isocyanates, or trifunctional or higher polyisocyanates can be used. As the diisocyanates represented by the formula (VII), those stabilized with a blocking agent necessary for avoiding changes over time may be used. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

[0034] The blending ratio of the carbonate diol represented by the above formula (VI) and the diisocyanate 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 Z hydroxyl group = 1.01 or more. I prefer to be.

[0035] The reaction of the carbonate diol represented by the above formula (VI) and the diisocyanate 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 2-5 hours on a 1-5 L (liter) flask scale.

[0036] 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, more preferably S. 1,500-9,000 is particularly preferable. If the number average molecular weight is less than 500, the warping property tends to be poor. If the number average molecular weight exceeds 10,000, the reactivity of the isocyanate compound tends to be low, and it becomes difficult to make polyimide resin. is there.

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. The number average molecular weight and the degree of dispersion of the present invention are defined as follows.

a) Number average molecular weight (M)

M = ∑ (N M) / N = ΣΧΜ

(X = molar fraction of molecules with molecular weight M = N Z ∑ N)

b) Weight average molecular weight

M = ∑ (NM ² ) / ∑NM = ∑WM

(W = molecular weight fraction of molecular weight M = N M Z ∑ N M)

c) Molecular weight distribution (dispersity)

Dispersity = M / M

[0038] 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). For example, the compound (b-2) is represented by the formula (VII). Isocyanates, 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).

[0039] 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 the case where the compound (b-l) and the compound (b-2) are used alone, the compound (b--) is used from the viewpoint of flexibility, warpage, etc. as a protective film for a flexible wiring board. It is preferable to use 1).

[0040] The compound (b-2) has a balance of heat resistance, solubility, mechanical properties, cost, etc., in which it is preferable that 50% by weight or more of the total amount is aromatic polyisocyanate. In view of this, 4, A′-diphenylmethane diisocyanate is particularly preferred.

[0041] When compound (b-l) and compound (b-2) are used in combination, the equivalent of compound (b-l) Z compound (b-2) is 0. I / O. 9 to 0.9 / A force of 0.1, more preferably a force of 0.2 / 0.8 to 0.8 / 0.2, more preferably a force of S, 0.3ZO. 7 to 0.7 / 0.3. Is particularly preferred. When the equivalence ratio is within this range, film properties such as good warpage, adhesion and good heat resistance can be obtained.

[0042] The amine compound in the component (b) includes a compound in which the isocyanate group in the isocyanate compound of the component (b) is converted 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-l).

[0043] Further, (a) a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and

The ratio of the tetravalent polycarboxylic acid having Z or an acid anhydride group is such that the ratio of the total number of carboxyl groups and acid anhydride groups in component ( _a ) to the total number of isocyanate groups in component (b) is:

It is preferable to be 0.6 to 1.4, more preferably 0.7 to 1.3, and more preferably 0.8 to 1.2. Particularly preferred. If this ratio is less than 0.6 or more than 1.4, it tends to be difficult to increase the molecular weight of the resin containing the polyimide bond.

[0044] 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)

[Chemical 7]

[0045]

(Wherein R, X, m, n, Y ¹ are as defined above)

A polyamideimide resin having a repeating unit represented by can be obtained.

[0046] When the compound represented by the formula (III) is used as the component (a) and the compound (b-1) is used as the component (b), the following formula (X):

[Chemical 9]

(Wherein R, X, m, n, Y ² are as defined above)

A polyimide resin having a repeating unit represented by can be obtained.

[0047] In the present invention, in the method for producing a resin containing an imide bond used as the component (ii). (A) a trivalent polycarboxylic acid having an acid anhydride group and derivatives thereof, and a tetravalent polycarboxylic acid having an acid anhydride group, and one or more selected compounds, and (b) isocyanine The reaction with the compound or the amine compound can be carried out by heat condensation in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent, while removing the liberated carbon dioxide gas from the reaction system. .

[0048] Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether; sulfur-containing solvents such as Dimethyl sulfoxide, jetyl sulfoxide, dimethyl sulfone, sulfolane; ester solvents such as γ-petit latatotone, cellosolve acetate; ketone solvents such as cyclohexanone, methyl ethyl ketone; aromatic hydrocarbon solvents Examples thereof include toluene and xylene, and these can be used alone or in combination of two or more.

[0049] It is preferable to select and use a solvent that dissolves the produced rosin. After the synthesis, it is preferable to use a suitable paste solvent as it is. In order to carry out the reaction in a homogeneous system with high volatility, low temperature curability, and efficiency, y-peptidactone is most preferable. The amount of the solvent used is preferably 0.8 to 5.0 times (weight ratio) of the resin containing the imide bond to be formed. If it is less than 8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to inability to stir, and if it exceeds 5.0 times, the reaction rate tends to decrease.

[0050] 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 gelling is likely to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.

[0051] If necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium or conorole, or a metalloid compound. . In addition, after completion of the synthesis, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, ratatams, oximes and the like. In addition, as component (A), thermosetting It is preferred to use a phosphatic rosin.

[0052] The number average molecular weight of the coffin obtained in this way is 2 000 to 50,000, preferably 24, 00 to 45,000, more preferably than force S, 26,000 to 40, The power of 000 is particularly preferable. The dispersion degree at that time is preferably 1.5 to 3.5 force, more preferably 2.0 to 3.0. If the number average molecular weight is less than 22,000, the film properties after the tinning tend to deteriorate, and if the number average molecular weight exceeds 50,000, it will dissolve in a non-nitrogen-containing polar solvent. Easily insolubilized during synthesis. In addition, workability tends to be inferior.

[0053] The (A) resin used in the resin composition of the present invention is a mixture of two or more resin having different molecular weights if the number average molecular weight measured by the GPC method is within the above range. From the viewpoint that it is easy to do. 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, which is not preferable.

[0054] In addition, among the cocoons 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 the coconut 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 there is a tendency that the workability of the inorganic filler and Z or organic filler and the screen printing and the like are lowered, which is not preferable.

[0055] The mixing ratio when mixing two or more coffins having different number average molecular weights used in the present invention is not particularly limited as long as the number average molecular weight measured by the GPC method is within the above range. Moreover, the density | concentration of a rosin solution can also be selected without a restriction | limiting.

[0056] 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 epoxy resin as a curing agent include bisphenol A type epoxy resin (trade name Epi Coat 828 manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol F type epoxy resin (Toto Kasei Co., Ltd.) Product name YDF—170, etc.), phenol novolac type epoxy resin (Oka Shell Epoxy Co., Ltd. product name Epicoat 152, 154; Nippon Kayaku Co., Ltd. product name EPPN-201; Dow Chemical Company name DEN—438 etc.), o—Crezo novolak type epoxy resin (manufactured by Nippon Iyaku Co., Ltd.) EOCN—125S, 103S, 104S, etc.), polyfunctional epoxy resin (trade name Eponl031S manufactured by Yuka Shell Epoxy Co., Ltd .; product name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd.) Trade name Denacol EX—611, EX—614, EX-614B, EX—622, EX—512, EX—521, EX—421, EX—411, EX—32 1, etc.), amine type epoxy resin Fat (trade name Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd .; product name YH434 manufactured by Tohto Kasei Co., Ltd .; trade name manufactured by Mitsubishi Gas Chemical Co., Ltd. TETRAD—X, TERRAD—C; Product name GAN manufactured by Sumitomo Chemical Co., Ltd. Product name ELM-120 manufactured by Sumitomo Chemical Co., Ltd., epoxy resin containing heterocyclic ring (product name Alaldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd.), alicyclic Epoxy resin (UCL's ERL4234, 4299, 4221, 4206, etc.), etc. It can be used in combination on. 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.

[0057] 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 based on the total amount of the resin containing the imide bond as the component (A). Examples of such epoxy compounds include n-butyl daricidyl ether, phenol glycidyl ether, dibromophenol glycidyl ether, dib-mouthed mocresyl glycidyl ether, and the like. In addition, alicyclic epoxy compounds such as 3,4 epoxycyclohexenole and methinole (3,4-epoxycyclohexane) canoleoxylate can be used.

[0058] The amount of the epoxy resin used is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and still more preferably 100 parts by weight of the resin containing the imide bond as the component (A). 3 to 40 parts by weight. When the amount of the epoxy resin is less than 1 part by weight, the curability, solvent resistance, chemical resistance and moisture resistance tend to decrease, and when it exceeds 50 parts by weight, the heat resistance and viscosity stability decrease. There is a tendency.

[0059] As a method of adding the epoxy resin, the added epoxy resin may be dissolved in the same organic solvent that dissolves the resin containing the imide bond as the component (A) and the force may be added. Alternatively, it may be added directly. [0060] Component (B): inorganic fine particles and Z or organic fine particles]

Inorganic fine particles and Z or organic fine particles used as the component (B) in the present invention may be dispersed in the thermosetting resin or thermosetting resin solution of the component (A) to form a paste. There is no particular limitation.

[0061] Examples of the inorganic fine particles include silica (SiO 2), alumina (Al 2 O 3), titanium (TiO 2),

2 2 3 2 Tantalum oxide (Ta 2 O 3), zirconium oxide (ZrO 2), silicon nitride (Si 2 N 2), barium titanate (B

2 5 2 3 4

aOTiO), barium carbonate (BaCO), lead titanate (PbOTiO), zirconate titanate

2 3 2

Lead (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3), spinel

twenty three

(MgO -Al O), mullite (3A1 O '2SiO), cordierite (2Mg02Al O / 5Si

2 3 2 3 2 2 3

O), talc (3Mg04SiO · Η Ο), aluminum titanate (TiO— Al 2 O 3), yttria

2 2 2 2 2 3 containing zirconia (γ Ο— ZrO), barium silicate (Ba08SiO), boron nitride (ΒΝ),

2 3 2 2

Calcium carbonate (CaCO), calcium sulfate (CaSO), zinc oxide (ZnO), titanate

3 4

Gnesium (MgOTiO), barium sulfate (BaSO), organic bentonite, carbon (C), etc.

twenty four

These can be used, and one or more of these can also be used.

[0062] Among these, it is preferable to contain barium sulfate from the viewpoint of improving the state of the coating film end after tinning. Moreover, it is preferable to contain barium sulfate, talc, and silica from the viewpoint of improving electrical characteristics.

[0063] 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, the viewpoint of heat resistance and mechanical properties, preferably polyimide resin or its precursor, polyamideimide resin or its precursor, or polyamide resin fine particles are used.

[0064] The heat-resistant resin as organic fine particles can be produced as follows.

First, polyimide resin can be obtained by reacting (a) an aromatic tetracarboxylic dianhydride and (b) an aromatic diamine compound.

[0065] (a) As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, 2, 2' , 3, 3 '— Bisphenol tetracarboxylic dianhydride, 2, 2', 3, 3 '— Biphenyl tetracarboxylic dianhydride, 2, 3, 3,, 4, — Biphenyltetra Carboxylic dianhydride, 2, 2-bis (3,4-dicar Boxyphenyl) propane dianhydride, 1, 1 bis (3,4 dicarboxyphenyl) ethane anhydride, bis (2, 3 dicarboxyphenyl) methane dianhydride, bis (3,4 dicarboxylic) Boxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3, 4, 9, 10 perylenetetracarboxylic dianhydride, bis (3,4 dicarboxyphenol- 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 Naphthalene tetracarboxylic dianhydride, 1, 2, 4, 5 Naphthalene tetracarboxylic dianhydride, 1, 4, 5, 8 Naphthalene Tetracarboxylic dianhydride, 2,6 dichloronaphthalene 1,4,5,8-tetracarboxylic dianhydride, 2,7 dichloronaphthalene 1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7 terachlornaphthalene 1, 4, 5, 8—tetracarboxylic dianhydride, phenanthrene 1, 8, 9, 10—tetracarboxylic dianhydride, bis (3,4-dicarboxyphene Dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenol silane dianhydride, bis (3,4-dicarboxyphenyl) diphenyl silane dianhydride, 1, 4 Bis (3,4 dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3 Bis (3,4 dicarboxyphenyl) — 1, 1, 3, 3-tetramethyldicyclohexane dianhydride P-Lenbis (trimellitic acid monoester anhydride), 2, 2 bis (3,4 dicarboxyl) -Hexafluoropropane dianhydride, 2, 2 bis {4 (3,4-dicarboxyphenoxy) phenol} hexafluoropropane dianhydride, 2, 2 bis { 4— (3,4 Dicarboxyphenoxy) phenol} propane dianhydride, 4, 4 bis (3,4 Dicarboxyphenoxy) diphenylsulfide dianhydride, 1, 4 bis (2 to hydroxy) Xafluoroisopropyl) 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 (no trimellitate) Water), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (otatamethylene) bis (tri 1,9— (nonamethylene) bis (trimellitic anhydride), 1,10— (decamethylene) bis (trimellitic anhydride), 1,12— (dodecamethylene) bis (trimellitic anhydride), 1 , 16- (Hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), etc., and these may be used in combination.

[0066] The (a) aromatic tetracarboxylic dianhydride may be a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride, depending on the purpose. It can be used within a range not exceeding mol%. Such tetracarboxylic dianhydrides include, for example, ethylene tetracarboxylic dianhydride, 1, 2, 3, 4 butanetetracarboxylic dianhydride, pyrazine 2, 3, 5, 6-tetracarboxylic dianhydride. Anhydride, 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 acid Dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, bis {exobicyclo [2, 2, 1] heptane 2,3 dicarboxylic anhydride} sulfone, bicyclo (2, 2, 2) Oct (7) —EN-2, 3, 5, 6-tetracarboxylic dianhydride, 5- (2,5 dioxotetrahi (Drofuryl) 3-methyl-3-cyclohexane 1,1,2 dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like.

[0067] Next, (b) the aromatic diamine compound includes, for example, o-phendrangeamine, m-farendamamine, p-farendamamine, 3, 3'-diaminodiphenyl ether, 4, 4 ' Diaminodiphenyl ether, 3, 4 '— Diaminodiphenyl ether, 3, 3' — Diaminodiphenylmethane, 3, 4 '— Diaminodiphenylenomethane, 4, 4' Diaminodiphenylmethane, 3, 3 '— Diaminodiph Enyldifluoromethane, 4, 4'-diaminodiphenyl difluoromethane, 3, 3 '— diaminodiphenyl sulfone, 3, 4' — diaminodiphenyl sulfone, 4, 4 '— diaminodiphenyl sulfone, 3, 3' — diaminodiphenol -Rulsulfide, 3, 3 '— Diaminodiphenyl ketone, 3, 4' — Diaminodiphenyl ketone, 4, 4'-Diaminodiphenyl ketone, 2, 2 Bis (3 aminophenol- ) Propane, 2, 2-bis (3, 4 '- Jiaminofue - Le) propane, 2, 2-bis (4 Aminofue - Le) propane, 2, 2-bi (3 aminophenol) hexafluoropropane, 2, 2 bis (3, 4 '— diaminophenol) hexafluoropropane, 2, 2 bis (4-aminophenol) hexafluoro Lopropan, 1,3 bis (3 aminophenol) benzene, 1,4 bis (4 aminophenol) benzen, 3, 3 '-[1,4 phenolic bis (1-methylenoethylidene)] bisa -Phosphorus, 3, 4 '— [1,4 Phelelenbis (1-Methylolethylidene)] bisaline, 4, 4' — [1,4 Phenolenbis (1-Methylethylidene)] Bisalin, 2 , 2 Bis [4- (3-aminophenoxy) phenol] propane, 2,2 Bis [4- (4 aminophenoxy) phenol] propane, 2,2-bis [4- (3-aminophenoxy) phenol ] Hexafluoropropane, 2, 2 bis [4- (4-aminophenoxy) phenol] Hexafluoropropane, bis [4 — (3-aminophenoxy) phenol] sulfide, bis [4- (4-aminophenoxy) phenol] sulfide, bis [4- (3-aminophenoxy) phenol] sulfone, bis [4- (4- Aminophenoxy) phenol] sulfone, etc., may be used as a mixture.

[0068] As the (b) aromatic diamine compound, diamine compounds 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 diaminoheptane, 1,8 diaminooctane, 1 1,9-diaminononane, 1,10 diaminodecane, 1,11-diaminoundecane, 1,3 bis (3 aminopropyl) tetramethyl disiloxane, 1,3 bis (3 aminopropyl) tetramethyl polysiloxane, and the like. From the viewpoint of film characteristics, it is preferable that the above (a) aromatic tetracarboxylic dianhydride and the above (b) aromatic diamine compound are reacted in an approximately equimolar amount.

[0069] 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-imidazolidine. Non-nitrogen-containing compounds; sulfur compounds such as sulfolane and dimethyl sulfoxide; ratatones such as y-butyral rataton, y-valerolataton, y-captora rataton, y heplatataton, a-acetinolet y butyrolataton, ε Dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl Ethers such as (or jetyl, dipropyl, dibutyl) ether, triethylene glycol (or jetyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or jetyl, dipropyl, dibutyl) ether; methyl ethyl ketone, methyl isobutyl Ketones, ketones such as cyclohexanone, and acetophenone; butanol, ethyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene dallicol monomethyl (or monoethyl) Alcohols such as ether; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl acetate sorbacete And esters such as butyl acetate sorb acetate; hydrocarbons such as toluene, xylene, jetylbenzene, and cyclohexane; halogenated hydrocarbons such as trichloroethane, tetochloroethane, and monochrome benzene are used. . These organic solvents are used alone or in combination. In view of solubility, low hygroscopicity, low temperature curability, environmental safety, etc., it is preferable to use ratatones, ethers, ketones and the like.

[0070] 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 polyimide resin is generated. This polyamic acid may be partially imidized and is also included in the polyimide resin precursor.

[0071] The polyimide resin is obtained by dehydrating and ring-closing the reaction product (polyamic acid). Dehydration cyclization can be performed by a method of heat treatment at 120 ° C. to 250 ° C. (thermal imidization) or a method using a dehydrating agent (chemical imidization). In the case of a 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.

[0072] In the method of performing dehydration and ring closure using a dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or benzoic acid, a calpositimide compound such as dicyclohexyl carpositimide, or the like is used as the dehydrating agent. preferable. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, and aminoviridine imidazole may be used. The dehydrating agent or dehydrating catalyst is preferably used in an amount of 1 to 8 mol per mol of the aromatic tetracarboxylic dianhydride. [0073] Polyamideimide resin or a precursor thereof is trimellitic acid anhydride or trimellitic acid anhydride derivative (instead of aromatic tetracarboxylic dianhydride in the production of polyimide resin or precursor thereof). It can be produced using a trivalent tricarboxylic acid anhydride or a derivative thereof such as trimellitic anhydride chloride). In addition, instead of aromatic diamine compounds and other diamine compounds, it can also be produced using diisocyanate compounds in which residues other than amino groups correspond to the diamine compounds. it can. Examples of the diisocyanate compound that can be used include those obtained by reacting the aromatic diamine compound or other diamine compound with phosgene or salt ether.

[0074] Polyamide resin reacts with aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, derivatives of these dichlorides, acid anhydrides, etc. and the above aromatic diamine compounds or other diamine compounds. Can be manufactured.

[0075] Examples of the heat-resistant resin having an ester bond include polyester resin, and examples of the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, dichlorides and acids thereof. There are those obtained by reacting derivatives such as anhydrides with aromatic diol compounds such as 1,4-dihydroxybenzene, bisphenol F, bisphenol A, and 4,4'-dihydroxybiphenol.

[0076] As the polyamideimide resin, polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is used. Preferably used. As the aromatic tetracarboxylic dianhydride and aromatic diamine compound, those described above are used. The molar ratio of Kaoru aromatic Jiamin compounds of isophthalic acid dihydrazide is preferably 1 to 100 mole ^_0/0. 1 mole ^_0/0 Not Mitsurude tend to resistance to dissolution modified polyamideimide榭脂decreases, the tendency for moisture resistance of the layer formed by the paste of the present invention with the content of isophthalic acid dihydrazide often decreases Therefore, 10 to 80 mol% is more preferred, and 20 to 70 mol% is particularly preferred. This polyamideimide resin can be obtained in the same manner as in the synthesis of the polyimide resin, with the compounding ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, the synthesis method, and the like.

[0077] A trimellitic anhydride and, if necessary, a dicarboxylic acid and a polyisocyanate are reacted. The polyamideimide resin obtained in this way tends to be insoluble in organic solvents by heating, and organic fine particles comprising this polyamideimide resin can also be used. About the manufacturing method of this polyamideimide resin, it can manufacture similarly to the manufacturing method of the above-mentioned polyamideimide resin.

[0078] Examples of the fine particle forming method include, for example, a non-aqueous dispersion polymerization method (JP-B-60-48531, JP-A-59-230018), precipitation polymerization method (JP-A-59-108030, Kaisho 60-221425), a method of mechanically pulverizing a modified powder of a resin solution, a method of micronizing under high shear while adding a resin solution to a poor catalyst, and a spray solution of a resin solution. There are a method of obtaining fine particles by drying, a method of forming fine particles of resin having a temperature dependency of solubility in solvents in a detergent or a resin solution.

[0079] As the inorganic fine particles and Z 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 m or less are preferably used. If the average particle diameter exceeds 50 μm, a paste with a thixotropic coefficient of 1.1 or more will be obtained, and if the maximum particle diameter exceeds 100 m, the appearance and adhesion of the coating will be insufficient. Tend. The average particle size is more preferably 30 / zm or less, further preferably 10 m or less, particularly preferably 1 μm or less, and the maximum particle size is more preferably 80 m or less, still more preferably 60 μm or less, Particularly preferably, it is 40 μm or less.

[0080] [Coffin composition]

The resin composition of the present invention can be produced by dissolving the resin (A) as a resin solution in an organic solvent, and dispersing the inorganic fine particles (Z) and organic fine particles (B) as components. it can.

[0081] In the resin composition of the present invention, the content of inorganic fine particles and Z or organic fine particles used as component (B) is preferably 1 to 350 parts by weight with respect to 100 parts by weight of component (A). More preferably, it is 30 to 300 parts by weight, more preferably 50 to 280 parts by weight, and particularly preferably 100 to 250 parts by weight. If the content of component (B) is less than this, the viscosity and thixotropy coefficient of the paste will be low, the stringing of the paste will increase, the flow of paste after printing will increase, and the film thickness will also decrease. It tends to be inferior, and the state and electrical properties of the film edge after the tinning tend to be inferior. In addition, component (B) When the content of is higher than this, the viscosity and thixotropy coefficient of the paste increase, and the transferability of the paste to the substrate tends to decrease, and voids and pinholes in the printed film tend to increase.

[0082] The organic solvent that dissolves the resin (A) is a non-nitrogen-containing polar solvent such as an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether; Sulfur-containing solvents such as dimethyl sulfoxide, jetyl sulfoxide, dimethyl sulfone, sulfolane; ester solvents such as γ-butyroratatone, cellosolve acetate; ketone solvents such as cyclohexanone, methyl ethyl ketone; aromatic hydrocarbons Examples of the solvent include toluene and xylene, and these can be used alone or in combination of two or more. Since the solubility varies depending on the resin produced, select a solvent that can dissolve the resin.

[0083] As a method of dispersing inorganic and cocoon or organic fine particles in a thermosetting rosin solution, roll kneading, mixer mixing, etc., which are usually performed in the paint field, are applied, and sufficient dispersion is performed. If it is a method, it is good.

[0084] The resin composition of the present invention includes surfactants such as antifoaming agents and leveling agents, dyes or pigments in order to improve workability during coating and film properties before and after film formation. It is also possible to add colorants such as heat stabilizers, antioxidants, flame retardants, and lubricants.

[0085] The resin composition of the present invention preferably has a viscosity of 25 Pa at 0.5 Pa's to 500 Pa's at a rotational viscometer 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 decrease. If the viscosity exceeds 500 Pa · s, the transferability of the paste to the base material is increased. There is a tendency for voids and pinholes in the printed film to increase with decreasing. On the other hand, if 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 tends to decrease. The viscosity is more preferably 1 to 250, particularly 10 to: LOO is preferable. The thixotropy coefficient is more preferably 1.2 or more, and particularly preferably 1.4 or more.

[0086] Here, the viscosity of the rosin composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U type). Expressed as the viscosity at a rotational speed of lOrpm measured with a sample volume of 0.2 ml or 0.5 ml. The best thixotropy coefficient (TI value) was determined by using an E-type viscometer (Model RE80U, manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 0.2 ml or 0.5 ml measured at lrpm and lOrpm. Apparent viscosity, the ratio of 7} 1 to 7} 10 expressed as 7} 1 / r?

[0087] Further, the 5% thermogravimetric temperature reduction temperature of the cured resin composition of the present invention is preferably 250 ° C or higher. If the 5% thermal weight loss temperature is less than 250 ° C, the cured film may be deformed and decomposed by the heat applied when connecting to rigid wiring boards, IC chips, electronic components or LCD panels. The 5% weight loss temperature is in the same range as the formation of a cured film for measurement of tensile modulus, etc., that is, 80 to 130 ° C, the time for forming a protective film on the surface of a normal flexible wiring board. Heated within this range, a cured film with a film thickness of about 30 m was formed, and the value measured by the TG-DTA method at a temperature increase rate of 10 ° CZ in an air atmosphere.

[0088] The present invention is also suitable 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, thereby forming a protective film. Can be used. In particular, it is suitable for use as a protective film on the surface of a flexible wiring board in which all the wiring pattern portions have been treated. 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 diffusion of the mesh layer and obtaining warpage and flexibility suitable as a protective film. It is not limited, It can also be hardened 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 includes the resin composition described above, and is suitably used in 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.

[0090] The resin composition according to the present invention includes, for example, an overcoat material for electronic components such as semiconductor elements and printed circuit boards, a liquid sealing material, an interlayer insulating film, a surface protective film, a solder resist layer, It is suitably used as an adhesive layer. It can also be used for varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, casting strength, sheet varnish combined with substrates such as glass cloth, varnish for MCL laminate, friction material varnish, etc. . In addition, since the resin coating is excellent in the adhesion between the substrate and the resin and the printing workability without peeling off the circuit board and the like, a highly reliable electronic component can be obtained.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[0092] Example 1

(Synthesis of polymer resin)

Plaxel CD-220 (manufactured by Daicel Engineering Co., Ltd., 1,6-Hexanediol-based polycarbonate diol) Product name) 2000. Og (100 mol), adipic acid 292.0 g (2.00 mol) and xylene 114.6 g were charged, and the temperature was raised to 200 ° C while removing by-product condensed water. did. The mixture was reacted at 200 ° C. for 2 hours to obtain dicarboxylic acid A having an acid value of 49.7 KOHmg Zg.

[0093] Then, 4 liters of 4-, 4-dimethanemethane diisocyanate (10.0 g, 0.60 mol) was added to a 4-liter 4-flasco equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer. In addition, 69.12 g (0.36 mol) of trimellitic anhydride, A541.44 g (0.24 mol) of the dicarboxylic acid obtained in the above synthesis and 760.56 g of γ-butyrolatatane were charged, and the temperature was raised to 160 ° C. The reaction was carried out for 8 hours to obtain a resin having a number average molecular weight of 38,000. 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 viscosity change with a Gardner bubble viscometer. The resulting榭脂was diluted with γ- Petit port Rataton to give the polycarbonate-modified polyamideimide榭脂solution nonvolatile content of 40 by weight ^_0/0.

[0094] [Synthesis of low molecular weight resin]

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

[0095] Polycarbonate-modified polyamideimide resin solution having a number average molecular weight of 29,000 obtained 20% and a polycarbonate-modified polyamideimide resin solution with a number average molecular weight of 38,000 are mixed with 80%, and 1 part by weight of the solvent treatment solution is added to 100 parts by weight of the resin, and a silicone-based antifoaming agent. (A) 0.3 part by weight (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred at 20 ° C. for 10 minutes. In addition, 30 parts by weight of barium sulfate (product name: B-30, manufactured by Sakai Chemical Industry Co., Ltd.) is blended, and if necessary, a solvent such as γ-petit mouth rataton is added and stirred at 50 ° C for 1 hour. Add 20 parts by weight of Ep-1004 (trade name, bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), stir at 20 ° C for 1 hour, and further silicone antifoam (B) 0.2 part by weight (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended and stirred at 20 ° C. for 30 minutes to obtain a polycarbonate-modified polyamideimide resin composition.

[0096] <Measurement of number average molecular weight and weight average molecular weight of coconut oil>

The calibration linear force using standard polystyrene was also converted 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 type UV [manufactured by Hitachi, Ltd.]

Column: Gelpack GL— S300MDT— 5 (2 in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.) Eluent: DMFZTHF = lZl + phosphoric acid (0.06M) + lithium bromide (0.06M)

[0097] Example 2

In Example 1, polycarbonate-modified polyamideimide resin having number average molecular weights of 25,000 and 32,000 was prepared by adjusting the reaction time. A polycarbonate-modified polyamideimide resin composition was obtained.

[0098] Example 3

Except that the number average molecular weights of the polycarbonate-modified polyamideimide resin were 23,000 and 29,000 were prepared and used in Example 1, exactly the same operation as in Example 1 was carried out. An imide resin composition was obtained.

[0099] Example 4

In Example 1, the number average molecular weight of the polycarbonate-modified polyamideimide resin is 36, Except that 000 and 42,000 were prepared by adjusting the reaction time, the same operation as in Example 1 was performed to obtain a polycarbonate-modified polyamideimide resin composition.

[0100] Example 5

20% of the polycarbonate-modified polyamide imide resin solution having a number average molecular weight of 29,000 obtained in Example 1 and 80% of the polycarbonate modified polyamide imide resin solution having a number average molecular weight of 38,000 are mixed. 100 parts by weight of fat, 1 part by weight of solvent treatment solution, silicone antifoam (A) (trade name: KS-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by weight The mixture was stirred at 20 ° C for 10 minutes. Furthermore, 100 parts by weight of barium sulfate (product name: B-30 manufactured by Sakai Chemical Industry Co., Ltd.), 20 parts by weight of talc (product name: Microace P-3 manufactured by Nippon Talc Co., Ltd.) and silica (manufactured by Nippon Aerosil Co., Ltd.) Product name: 10 parts by weight of AEROSIL380) is mixed, and if necessary, a solvent such as γ-petit mouth rataton is added and stirred at 50 ° C for 1 hour. Furthermore, amine type epoxy resin (Toto Kasei Co., Ltd.) Product name: YH—434L) was added in an amount of 10 parts by weight, and the mixture was stirred at 20 ° C. for 1 hour. Further, a silicone-based antifoaming agent (B) (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KS—603) was added to the product. 2 parts by weight was blended and stirred at 20 ° C for 30 minutes to obtain a polycarbonate-modified polyamideimide resin composition.

[0101] Example 6

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

[0102] Comparative Example 1

In Example 1, polycarbonate-modified polyamideimide resin having number average molecular weights of 15,000 and 23,000 was prepared by adjusting the reaction time. A polycarbonate-modified polyamideimide resin composition was obtained.

[0103] The properties 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.

[0104] State of film edge after sparrow

The obtained polycarbonate-modified polyamideimide resin composition is printed on a 35 m copper foil. A 30 mm square is printed at a printing speed of lOOmmZsec using a printing machine (Neurong Co., Ltd. product name: LS-34GX) and a mesh plate (Murakami Co., Ltd. 150 mesh), and heated and cured at 120 ° C for 60 minutes in an air atmosphere. A polycarbonate-modified polyamideimide resin film was obtained. The obtained polycarbonate-modified polyamideimide resin film is immersed in a tincture solution (product 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 crushing and drying for 30 minutes with a hot air circulating dryer at 100 ° C, the resin coating around the polycarbonate-modified polyamideimide resin coating on the copper foil with a universal projector (Nikon Corporation magnification 50x) The peeling state of was observed. A non-peeled resin film was marked with ◯, a film with slight peeling was marked with Δ, and a film with peeling was marked with X.

[0105] Electrical characteristics

The resulting polycarbonate-modified polyamideimide resin composition was printed on a polyimide substrate so as to cover the comb-shaped copper electrode with a line width of 15 μm and a space width of 15 μm. Product name: LS-34GX) and mesh plate (Murakami Co., Ltd. 150 mesh) printed at a printing speed of lOOmmZsec, heated and cured at 120 ° C for 60 minutes in an air atmosphere, and polyimide with polyamide-modified polyamideimide resin coating A base comb type electrode was obtained. Polyimide base material comb-shaped electrode with obtained polycarbonate-modified polyamide-imide resin coating was used as a continuous resistance measuring instrument (trade name: Ion Migration Tester, manufactured by IMV Corporation)

MIG-8600) and unsaturated pressure pressure force (trade name: HA ST PC—422R8D, manufactured by Hirayama Seisakusho Co., Ltd.) The resistance was measured.

[0106] For the polycarbonate-modified polyamideimide resin compositions obtained in Examples 1 to 6 and Comparative Example 1, three samples were prepared and measured. After voltage application after 100 hours, what resistance value was 3 samples all 1 X 10- ⁶ Ω or more "A", those two samples was over 1 X 10- ⁶ Ω or more "Β" 1 sample was evaluated as was 1 X 10- ⁶ Omega or "C", what was less than 3 Sanpunore all 1 X 10- ⁶ Omega as "D".

[0107] Printing workability

The obtained polycarbonate-modified polyamideimide resin composition is placed on a 2 mm glass plate. A 100 mm square is printed at a printing speed of lOOmmZsec and heated at 120 ° C for 60 minutes in an air atmosphere using a printing machine (trade name: LS-34GX, manufactured by Neurong Co., Ltd.) and a mesh plate (150 mesh, manufactured by Murakami Corporation). Curing was performed to obtain a polycarbonate-modified polyamideimide resin film. The obtained polycarbonate-modified polyamide-imide resin film was observed with a universal projector (magnification 20 × manufactured by Nicon Corporation), and the resin film was observed for defects and chipped edges. The resin film without burrs or chipping at the edges was marked with ◯, and those with burrs or chipping at the edges were marked with X.

[0108] [Table 1]

table 1

* Characteristics when two kinds of resins are mixed

[0109] [Table 2] Table 2

* Example 6 is the physical properties of one kind of resin, Comparative Example 1 is

This is a characteristic when two kinds of resins are mixed.

[0110] From the above results, the following was found. In Examples 1 to 6, since the resin having a number average molecular weight of 2 000 to 50, 000 is used, the printing workability is excellent without causing peeling at the edge of the coating after the tinning.

[0111] Further, in Examples 1 to 5, the state of the film edge after the tinning was good, and the electric characteristics were generally good. The printing workability was good except in Example 4. On the other hand, in Comparative Example 1, scraping or chipping of the end portion was observed at the end of the film after the tinning.

Industrial applicability

[0112] As described above, the resin composition and 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 electrical products and electronic parts. . In addition, it is excellent in printing workability without causing peeling at the coating edge after splintering, overcoat material for electronic parts, liquid sealing material, varnish for enameled wire, varnish for electrical insulation, for laminates It is useful for electronic parts such as varnishes, varnishes for friction materials, interlayer insulating films, surface protective films, solder resist films, adhesive layers, etc. in the printed circuit board field, and semiconductor elements containing them.

Claims

The scope of the claims

[1] A resin composition comprising (A) a resin and (B) an inorganic filler and Z or an organic filler, wherein the number average molecular weight of the resin (A) is 2 000-50, 000 A resin composition characterized by being.

[2] Number average molecular weight is different (A) A resin containing a solvent in which two or more resins are mixed, and (B) an organic filler and Z or an organic filler are dispersed. Composition.

[3] The resin composition according to claim 1 or 2, wherein the resin (A) has a polycarbonate skeleton.

[4] The (A) rosin has an imide bond, among the claims 1 to 3,

V, slippery composition according to item 1.

[5] 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 a derivative power thereof. The greaves composition according to any one of claims 1 to 4.

[6] The content of the (B) inorganic filler and Z or organic filler is 1 to 350 parts by weight with respect to 100 parts by weight of the (A) resin. Of item 5,

V, slippery composition according to item 1.

[7] The resin composition according to any one of [1] to [6], wherein the (B) inorganic filler and Z or organic filler contain barium sulfate.

[8] The resin composition according to [7], wherein the (B) inorganic filler and Z or organic filler further contain silica and talc.

[9] The resin composition according to any one of claims 1 to 8, further comprising an epoxy resin as a curing agent.

[10] A film forming material comprising the resin composition according to any one of claims 1 to 9.