KR20070087036A - Resin composition and film forming material containing same - Google Patents

Abstract

The resin composition which can be used suitably for screen printing, and improved the peeling which generate | occur | produces in the resin film edge part after tin plating is provided, and the film formation material containing the same is provided. The resin composition is a resin composition containing (A) resin and (B) inorganic and / or organic filler, and the number average molecular weight of said (A) resin is 22,000-50,000. Moreover, (B) inorganic filler and / or organic filler are disperse | distributed to the resin solution containing the solvent which mixed two or more (A) resin from which a number average molecular weight differs. A film forming material contains the said resin composition.

Description

Resin composition and the film formation material containing the same {RESIN COMPOSITION AND COATING FILM FORMING MATERIAL}

The present invention relates to a resin composition and a film forming material containing the same, in particular, a resin composition having thixotropy suitable for a coating method such as a screen printing machine, a dispenser, a spin coater, and the like, and a film forming material containing the same. .

Recently, in the field of electronic parts, polyimide resins, polyamideimide resins, and polyamide resins are used in place of epoxy resins as resins having excellent heat resistance, electrical properties, and moisture resistance due to miniaturization, thinning, and high speed. have. When these resins have a rigid resin structure and are used for thin film substrates, the base material after curing is largely bent, the cured film lacks flexibility and inferior in flexibility.

Therefore, in order to improve low warpage and flexibility, polyamideimide resins (Patent Document 1, Patent Document 2 and Patent Document 3) modified by plasticizing and low modulus of resin have been proposed. In these resins, in order to improve printability and workability, an inorganic filler, an organic filler, etc. are disperse | distributed to the resin solution. Moreover, in order to improve the adhesiveness of a base material, resin, a filler, and resin, additives, such as various coupling agents and a surface treating agent, are used.

Patent Document 1: Japanese Patent Application Laid-Open No. 62-106960

Patent Document 2: Japanese Patent Application Laid-Open No. 8-12763

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

Disclosure of the Invention

Problems to be Solved by the Invention

However, some of the additives, such as various coupling agents and surface treatment agents, begin to spread to the surface of the film or to the periphery of the film during curing, and the resin film peels off from the circuit board and adversely affects during the adhesion processing of the circuit by the resin or the like afterwards. There was a problem. Accordingly, there has been a demand for a resin composition in which the resin film is not peeled from the circuit board, and the adhesion between the substrate and the resin and the print workability are improved, and a film forming material including the same.

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

Means to solve the problem

The resin composition which concerns on this invention is a resin composition containing (A) resin and (B) inorganic filler and / or organic filler, The number average molecular weight of said (A) resin is 22,000-50,000, It is characterized by the above-mentioned.

Moreover, in the resin composition of this invention, (B) inorganic filler and / or organic filler are disperse | distributed to the resin solution containing the solvent which mixed two or more (A) resin from which a number average molecular weight differs. .

Moreover, in the resin composition of this invention, the said (A) resin has a polycarbonate skeleton, It is characterized by the above-mentioned.

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

Moreover, in the resin composition of this invention, said (A) resin is at least 1 sort (s) chosen from the group which consists of polyimide resin, polyamideimide resin, polyamide resin, and derivatives thereof which have a polycarbonate backbone, It is characterized by the above-mentioned. do.

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, It is characterized by the above-mentioned.

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.

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

Moreover, the resin composition of this invention is characterized by further including an epoxy resin as a hardening | curing agent.

Moreover, the film formation material of this invention is characterized by including the said resin composition.

Effects of the Invention

The resin composition and the film-forming material of the present invention include (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 thus can be suitably used for screen printing, and tin plating. Peeling does not generate | occur | produce in a later film edge part. In addition, the resin composition and the film-forming material of the present invention have thixotropy in addition to the above excellent characteristics, and are overcoat material for electronic parts, liquid sealing material, varnish for enamel wire, varnish for electrical insulation, varnish for laminate and friction. It is effective to obtain highly reliable electronic components that can be suitably used for electronic components such as interlayer insulating films, surface protective films, solder resist films, adhesive layers, etc. in materials varnishes, printed circuit boards, semiconductor devices, flexible wiring boards, and the like. Get

To practice the invention  Best form for

EMBODIMENT OF THE INVENTION Below, one Embodiment of the resin composition and film forming material which concern on this invention is described in detail. In addition, this invention is not limited by this one embodiment.

The resin composition of this invention contains (A) resin and (B) inorganic filler and / or organic filler as an essential component.

[(A) Ingredient: Resin]

As the resin of the component (A), an epoxy resin having a butadiene structure or a silicone structure, a phenol resin, an acrylic resin, a polyurethane, a polybutadiene, a hydrogenated polybutadiene, a polyester, a polycarbonate, a polyether, a polysulfone, a polytetrafluoro Furnace resin, polysilicon, melamine resin, polyamide, polyamideimide, polyimide and the like. These may be used alone or in combination of two or more thereof.

In addition, the resin (A) of the present invention is preferably plasticity and low elastic modulus in order to mainly correspond to a flexible substrate. In order to make (A) resin plasticity and a low elasticity rate, what introduces the component which can improve plasticity in the principal chain of resin is mentioned, for example, resin which has a polybutadiene frame | skeleton, a silicone resin frame | skeleton, and / or a polycarbonate frame | skeleton. Is preferred.

Moreover, in order to improve heat resistance, electrical property, moisture resistance, solvent resistance, and chemical resistance, the introduction of the component which can improve heat resistance in the main chain of resin is mentioned, for example, polyimide, polyamideimide, or polyamide. Or resin which has these frame | skeleton is preferable. Especially, resin which has a polycarbonate frame | skeleton and an imide frame | skeleton is preferable from a viewpoint of plasticization, 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) usually contains a compound having an carboxyl group at its terminal, an acid anhydride, or the like. And / or by reacting with a compound having an isocyanate group at the terminal.

In addition, in this invention, resin containing the imide bond which can be used as (A) component is (a) trivalent polycarboxylic acid which has an acid anhydride group, its derivative (s), and tetravalent poly which has an acid anhydride group It is obtained by making (b) an isocyanate compound or an amine compound react with 1 or more types of compounds chosen from a carboxylic acid.

The trivalent polycarboxylic acid and derivatives thereof having an acid anhydride group of component (a) are not particularly limited, for example, formulas (I) and (II):

[Tue 1]

[Tue 2]

(Formula (I) and (Ⅱ) of, R 'is an alkyl group or a phenyl group of hydrogen, carbon number of 1~10, Y ¹ _{is, -CH 2 -, -CO-, -SO} 2 -, or -O- to be)

The compound represented by can be used.

From the viewpoint of heat resistance, cost, and the like, trimellitic anhydride is particularly preferable. Although tetravalent polycarboxylic acid which has an acid anhydride group is not specifically limited, For example, Formula (III):

[Tue 3]

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

[Tue 4]

Tetracarboxylic dianhydride represented by These can be used individually or in combination of 2 or more types.

In addition to these, aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid, sublinic acid, sebacic acid, decanic acid, dodecaneic acid, dimer acid, etc.) and aromatic dicarboxylic acid may be used as acid components. (Isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) etc. can be used together. In this case, amide bonds are also formed in the molecular chain.

Isocyanate compound of (b) component is a formula (V), for example:

[Tue 5]

(In formula, several R is respectively independently a C1-C18 alkylene group, m and n are each independently an integer of 1-20.)

The diisocyanate represented by can be used (hereinafter, referred to as (b-1) compound).

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

[Tue 6]

(In formula, R is an independently C1-C18 alkylene group and m is an integer of 1-20.)

Carbonate diols represented by the formula, and the formula:

ONC-X-NCC (Ⅶ)

(Wherein X is a divalent organic group)

It is obtained by making diisocyanate represented by these react.

Examples of the diisocyanates of formula (i) include arylene groups such as a phenylene group substituted with an alkylene group having 1 to 20 carbon atoms or a lower alkyl group having 1 to 5 carbon atoms such as an unsubstituted or methyl group. . Carbon number of an alkylene group becomes like this. More preferably, it is 1-18. The group which has two aromatic rings, such as a diphenylmethane-4,4'- diyl group and a diphenylsulfone-4,4'- diyl group, is also preferable.

Examples of the carbonate diols represented by the above formula (VI) include α, ω-poly (hexamethylenecarbonate) diol, α, ω-poly (3-methyl-pentamethylenecarbonate) diol, and the like. As what is mentioned, brand name PLCCEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, 220ML etc. by Daicel Chemical Co., Ltd. are mentioned. These can be used individually or in combination of 2 or more types.

Moreover, as diisocyanate represented by said formula (i), For example, diphenylmethane-2,4'- diisocyanate; 3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenyl Methane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2 ' Or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'-, 4,3'-, 5,2'- , 5,3'-, 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-3, 3'- diisocyanate; diphenylmethane-3,4'- diisocyanate; diphenyl ether-4,4'- diisocyanate; benzophenone-4,4'- diisocyanate; diphenylsulfone-4,4'- Diisocyanate; toylene-2,4-diisocyanate; toylene-2,6-diisocyanate; m-xylylenediisocyanate; ｐ-xylylenediisocyanate; naphthalene-2,6-diisocyanate; 4,4 ' -[2,2bis (4-phenoxyphenyl) propane] diisocyanate etc. are mentioned. In these diisocyanates, it is preferable to use the aromatic polyisocyanate which has a bivalent aromatic ring in Formula (i). These can be used individually or in combination of 2 or more types.

Moreover, as diisocyanate represented by a formula, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isohorone diisocyanate, 4,4'- within the range of the objective of this invention. Aliphatic or alicyclic isocyanates such as dicyclohexyl methane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate, or a trifunctional or higher polyisocyanate can be used. The diisocyanate represented by Formula (i) may use what was stabilized with the blocking agent required in order to avoid a change in day and night. Examples of the blocking agent include alcohols, phenols, and oximes, but there is no particular limitation.

The blending ratio of the carbonate diols represented by the formula (VI) with the diisocyanates represented by the formula (i) is such that the ratio of the number of hydroxyl groups and the number of isocyanate groups is made to be isocyanate group / hydroxyl group = 1.01 or more. desirable.

The reaction between the carbonate diols represented by the above formula (VI) and the diisocyanates represented by the formula (i) can be carried out in the presence of a solvent-free or organic solvent. It is preferable to make reaction temperature into 60-200 degreeC, More preferably, it is 80-180 degreeC. Reaction time can be suitably selected by the magnitude | size of a batch, reaction conditions employ | adopted, etc .. For example, it can be made into 2 to 5 hours on the flask scale of 1-5 L (liter).

It is preferable that the number average molecular weight of the isocyanate compound of the compound (b-1) obtained in this way is 500-10,000, It is more preferable that it is 1,000-9,500, It is especially preferable that it is 1,500-9,000. If the number average molecular weight is less than 500, the warpage property tends to deteriorate. If the number average molecular weight is more than 10,000, the reactivity of the isocyanate compound decreases and the polyimide resin tends to be difficult to form.

In addition, in this specification, a number average molecular weight is measured by gel permeation chromatography (BP), and it is set as the value converted using the analytical curve of standard polystyrene. In addition, the number average molecular weight and dispersion degree of this invention are defined as follows.

a) number average molecular weight (Mn);

M _n = ∑ (N _i M _i ) / N _i = ∑X _i M _i

(X _i = mole fraction of molecules of molecular weight M _i = N _i / ∑N _i )

b) weight average molecular weight

M _w = ∑ (N _i M _i ² ) / ∑N _i M _i = ∑W _i M _i

(W _i = Weight fraction of molecules of molecular weight M _i = N _i M _i / ∑N _i M _i )

c) molecular weight distribution (dispersity)

Dispersion = M _w / M _n

As an isocyanate compound of (b) component, compounds (henceforth a compound (b-2)) other than a compound (b-1) can also be used. As a compound (b-2), if it is an isocyanate compound other than a compound (b-1), it will not specifically limit, For example, diisocyanate represented by Formula (iii), trivalent or more polyisocyanate, etc. are mentioned. These can be used individually or in combination of 2 or more types. The preferable range of the number average molecular weight of the isocyanate compound of compound (b-2) is the same as that of said compound (b-1).

In particular, it is preferable to use a compound (b-1) and a compound (b-2) together from a heat resistant point. Moreover, when using a compound (b-1) and a compound (b-2) each independently, it is preferable to use a compound (b-1) from a point of flexibility, curvature, etc. as a protective film for flexible wiring boards.

As compound (b-2), it is preferable that 50-100 weight% of the total amount is aromatic polyisocyanate, and considering the balance of heat resistance, solubility, mechanical characteristics, cost aspect, etc., 4,4'- diphenylmethane di Isocyanates are particularly preferred.

When using compound (b-1) and compound (b-2) together, it is preferable to set it as 0.1 / 0.9-0.9 / 0.1 by the equivalence ratio of compound (b-1) / compound (b-2), and it is 0.2 / 0.8 It is more preferable to set it as -0.8 / 0.2, and it is especially preferable to set it as 0.3 / 0.7-0.7 / 0.3. If the equivalent ratio is in this range, the film | membrane characteristics, such as favorable curvature, adhesiveness, and favorable heat resistance, can be acquired together.

As an amine compound in (b) component, the compound which converted the isocyanate group in the isocyanate compound of said (i) component to an amino group is mentioned. Conversion of an isocyanate group to an amino group can be performed by a known method. The preferable range of the number average molecular weight of an amine compound is the same as that of said compound (b-1).

In addition, the compounding ratio of the trivalent polycarboxylic acid or its derivative (s) and / or tetravalent polycarboxylic acid which has an acid anhydride group of (a) component is (a) with respect to the total number of isocyanate groups in (b) component The ratio of the total number of carboxyl groups and acid anhydride groups in the component is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, and particularly preferably 0.8 to 1.2. When this ratio is less than 0.6 or more than 1.4, it exists in the tendency which becomes difficult to make molecular weight of resin containing a polyimide bond high.

Moreover, when a compound (b-1) is used as a compound represented by Formula (I) as (a) component, and (b) component, following formula (XIII):

[Tue 7]

Wherein R, X, m and n are as defined above.

Polyamideimide resin having a repeating unit represented by can be obtained.

Moreover, when a compound (b-1) is used as a compound represented by Formula (II) as (a) component, and (b) component, following formula (I):

[Tue 8]

Wherein R, X, m, n, and Y ¹ are as defined above.

Polyamideimide resin having a repeating unit represented by can be obtained.

Moreover, when using the compound represented by Formula (III) as a component (a), and the compound (b-1) as a component (b), following Formula (X):

[Tue 9]

Wherein R, X, m, n, and Y ² are as defined above.

The polyimide resin which has a repeating unit represented by can be obtained.

(A) Trivalent polycarboxylic acid which has an acid anhydride group, its derivative (s) in the manufacturing method of resin containing the imide bond used as (A) component, and tetravalent polycarbon which has an acid anhydride group in this invention. The reaction of at least one compound selected from an acid with (b) an isocyanate compound or an amine compound is carried out by heating condensation while removing free carbon dioxide from the reaction system in the presence of an organic solvent, preferably a non-nitrogen polar solvent. This can be done by letting.

Examples of the non-nitrogen polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; Containing sulfur solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; Ester solvents such as α-butyrolactone, a vertical acetate solution; Ketone solvents such as cyclohexanone, methylethylketone; Aromatic hydrocarbon solvents such as toluene, xylene, and the like, and these can be used alone or in combination of two or more thereof.

It is preferable to select and use the solvent which melt | dissolves the resin to produce | generate. It is preferable to use what is suitable as a solvent of a paste as it is after synthesis | combination. (Gamma) -butyrolactone is the most preferable in order to provide high volatility, low temperature hardenability, and to perform reaction in a uniform system efficiently. It is preferable that the usage-amount of a solvent shall be 0.8-5.0 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 there exists a tendency for synthesis to become difficult by stirring inability, and when it exceeds 5.0 times, there exists a tendency for reaction rate to fall.

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 degreeC, reaction time will become too long, and if it exceeds 210 degreeC, a three-dimensionalization reaction will arise during reaction and gelatinization will occur easily. 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 carried out in the presence of a catalyst such as a metal such as a tertiary amine, an alkali metal, an alkaline earth metal, tin, zinc, titanium, cobalt, or a semimetal compound. In addition, after completion | finish of synthesis, the isocyanate group of the resin terminal can also be blocked by blocking agents, such as alcohol, lactam, and oxime. Moreover, it is preferable to use a thermosetting resin as (A) component.

Thus, the number average molecular weight of resin obtained is 22,000-50,000, It is more preferable that it is 24,000-45,000, It is especially preferable that it is 26,000-40,000, The dispersion degree at that time has preferable 1.5-3.5, 2.0-3.0 This is more preferable. If the number average molecular weight is less than 22,000, the film property after tin plating tends to be lowered. If the number average molecular weight is more than 50,000, it is difficult to dissolve in a non-nitrogen-based polar solvent and easily insoluble during synthesis. In addition, workability tends to be inferior.

(A) resin used by the resin composition of this invention is preferable from a viewpoint that it is easy to synthesize | combine mixing two or more resin from which molecular weight differs as long as the number average molecular weight measured by the PPC method is in the said range. It is preferable that the difference of this molecular weight has a 5,000 or more difference by a number average molecular weight. If the difference in number average molecular weight is less than 5,000, the adhesive effect tends to be difficult to be obtained, which is not preferable.

Moreover, it is preferable that minimum molecular weight is 20,000 or more in number average molecular weight among resin of another number average molecular weight. When the number average molecular weight is less than 20,000, the moisture resistance and the heat resistance tend to decrease, which is not preferable. On the other hand, in resin of other number average molecular weight, it is preferable that a maximum molecular weight is less than 50,000 in a number average molecular weight. When the number average molecular weight exceeds 50,000, the viscosity of the resin is increased, and workability such as mixing property and screen printing of the inorganic filler and / or organic filler tends to decrease, which is not preferable.

The mixing ratio when mixing two or more resins with 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 PPC method is within the above range. In addition, the concentration of the resin solution can also be selected without limitation.

In the case of resin containing said imide bond, in order to improve thermosetting, you may add various epoxy resins other than (A) component. As an epoxy resin as a hardening | curing agent, bisphenol A epoxy resin (trade name Epicoat 828 made from Emulsified Cell Epoxy Co., Ltd.), bisphenol F type epoxy resin (trade name KDF-170 by Toto Chemical Co., Ltd.), phenol, for example. Novolak-type epoxy resin (trade name Epicoat 152, 154 of emulsion cell epoxy Co., Ltd .; brand name EP-201 made by Nippon Kayaku Co., Ltd., brand name DE-438 by Dow Chemical Co., Ltd.), o-cresol novolak type Epoxy resin (trade names ECO-125S, 103S, 104S, etc. made by Nihon Kayaku Co., Ltd.), polyfunctional epoxy resin (trade name EEG1031S made by Emulsified Cell Epoxy Co., Ltd .; brand name of Chiba Specialty Chemicals Co., Ltd.) Araldite 0163 (trade name Denacol EV-611, EV-614, EV-614B, EV-622, EV-512, EV-521, EV-421, EV-411, EV-321 manufactured by Nagase Chemical Co., Ltd.); Etc.), amine type epoxy resin (trade name Epicoat 604 by Emulsified Cell Epoxy Co., Ltd.); Trade name W434; trade name TRDAD-X, TERRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd. trade name JAN manufactured by Nippon Kayaku Co., Ltd. trade name ELM-120 manufactured by Sumitomo Chemical Co., Ltd .; Epoxy resins (trade names Araldite Pt810 manufactured by Chiba Specialty Chemicals Co., Ltd.), alicyclic epoxy resins (ERC 4234, 4299, 4221, 4206, etc., manufactured by BC Corporation), etc .; It can be used in combination. Among these epoxy resins, amine epoxy resins having three or more epoxy groups in one molecule are particularly preferred in terms of solvent resistance, chemical resistance, and moisture resistance.

These epoxy resins may contain the epoxy compound which has only one epoxy group in 1 molecule. It is preferable to use such an epoxy compound in 0 to 20weight% of range with respect to resin whole quantity containing the imide bond which is (A) component. Examples of such epoxy compounds include n-butylglycidyl ether, phenylglycidyl ether, dibromo phenylglycidyl ether, dibromocredyl glycidyl ether and the like. Moreover, alicyclic epoxy compounds, such as 3, 4- epoxycyclohexyl and methyl (3, 4- epoxy cyclohexane) carboxylate, can be used.

The usage-amount of these epoxy resins becomes like this. Preferably it is 1-50 weight part, More preferably, it is 2-45 weight part, More preferably, 3-100 weight part with respect to 100 weight part of resin containing the imide bond which is (A) component. 40 parts by weight. When the compounding quantity of an epoxy resin is less than 1 weight part, there exists a tendency for sclerosis | hardenability, solvent resistance, chemical resistance, and moisture resistance to fall, and when it exceeds 50 weight part, there exists a tendency for heat resistance and viscosity stability to fall.

As an addition method of an epoxy resin, you may add the epoxy resin to add after melt | dissolving in the same organic solvent with the organic solvent which melt | dissolves resin containing the imide bond which is (A) component, and may add directly.

[Component (B): Inorganic Fine Particles and / or Organic Fine Particles]

The inorganic fine particles and / or organic fine particles used as the component (i) in the present invention are not particularly limited as long as the inorganic fine particles and / or organic fine particles are dispersed in the thermosetting resin or the thermosetting resin solution of the above-mentioned (A) component to form a paste.

Examples of the inorganic fine particles include silica (SiO ₂ ), alumina (A ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (TA ₂ O ₅ ), zirconia (ZRO ₂ ), silicon nitride (Si ₂ N ₄ ), and titanic acid. Barium (TiO ₂ ), barium carbonate (PA ₃ ), lead titanate (PPO · TiO ₂ ), lead zirconate titanate (PVT), lead zirconate titanate (PLVT), gallium oxide (PA ₂ O ₃ ), spinel ( MgO · Aｌ ₂ O ₃ ), mullite (3Aｌ ₂ O ₃ ㆍ 2SiO ₂ ), cordierite (2MgO · 2Aｌ ₂ O ₃ / 5SiO ₂ ), talc (3MgO4SiO ₂ ㆍ H ₂ O), aluminum titanate (ＴｉＯ) ₂ -A ₂ O ₃ ), yttria-containing zirconia (X ₂ O _3- XR O ₂ ), barium silicate (VAO8SiO ₂ ), boron nitride (EN), calcium carbonate (CaCO ₃ ), calcium sulfate (COSO ₄ ) Zinc oxide, magnesium titanate (MgO · Tio ₂ ), barium sulfate (VASO ₄ ), organic ben Tonight, carbon (C), etc. can be used and these 1 type, or 2 or more types can also be used.

Especially among these, it is preferable to contain barium sulfate from a viewpoint which can make the state of the film edge part after tin plating favorable. Moreover, it is preferable to contain barium sulfate, talc, and a silica from a viewpoint which can also improve electrical characteristics.

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

Heat resistant resin as organic microparticles | fine-particles can be manufactured as follows.

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

(a) As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,2', 3,3'-bisphenyl tetra Carboxylic 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-dicarboxyphenyl) ether dianhydride, benzene -1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride , 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetraca Acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetra Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride Water, Phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane 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 (trimeric acid monoester acid anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Water, 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) diphenylsulfide dianhydride, 1,4- Bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimerate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimerate anhydride), 1,2- (Ethylene) bis (trimerate anhydride), 1,3- (trimethylene) bis (trimerate anhydride), 1,4- (tetramethylene) bis (trimerate anhydride), 1,5- (pentamethylene ) Bis (trimerate anhydride), 1,6- (hexamethylene) bis (trimerate anhydride), 1,7- (heptamethylene) bis (trimerate anhydride), 1,8- (octamethylene) bis (Trimerate anhydride), 1,9- (nonamethylene) bis (trimerate anhydride), 1,10- (decamethylene) bis (trimerate anhydride), 1,12- (dodecamethylene) bis ( Trimellitate anhydride), 1,16- (hexade Methylene) bis (and the like tree Mary Tate anhydride), 1,18- (octa-decamethylene) bis (tri Mary Tate anhydride), it may be used by mixing them.

As said (a) aromatic tetracarboxylic dianhydride, tetracarboxylic dianhydride other than aromatic tetracarboxylic dianhydride can be used according to the objective in the range which does not exceed 50 mol% of aromatic tetracarboxylic dianhydride. As such tetracarboxylic dianhydride, for example, ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, tee Offen-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, pyrrolidin-2,3,4,5-tetra Carboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis {exobicyclo [2,2,1] heptan-2,3-dicarboxylic dianhydride} sulfone, bicyclo- (2 , 2,2) -octo (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrodofuryl) -3-methyl-3-cyclohexane -1,2-dicarboxylic acid anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, etc. are mentioned.

Next, as the (b) aromatic diamine compound, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodi Phenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3 '-Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 4,4'-diaminodi Phenylketone, 2,2-bis (3-aminophenyl) propane, 2,2-bis (3,4'-diaminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2- Bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1, 3-bis 3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 3,3 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4'- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4- Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, etc. may be mentioned, and these may be mixed and used. .

Diamine compounds other than an aromatic diamine compound can be used for the said (b) aromatic diamine compound in the range which does not exceed 50 mol% of an aromatic diamine compound according to the objective. 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, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-aminopropyl ) Tetramethyldisiloxane, 1, 3-bis (3-aminopropyl) tetramethyl polysiloxane, etc. are mentioned. It is preferable at the point of a film | membrane characteristic to make said (a) aromatic tetracarboxylic dianhydride and said (b) aromatic diamine compound react at substantially equimolar.

Reaction of (a) aromatic tetracarboxylic dianhydride and (b) aromatic diamine compound is performed in an organic solvent. As the organic solvent, for example, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro2 (1H) -pyrimidinone, 1 Nitrogen-containing compounds such as, 3-dimethyl-2-imidazolidinone; Sulfur compounds such as sulfolane and dimethyl sulfoxide; lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone and ε-caprolactone; Dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or Ethers such as diethyl, dipropyl and dibutyl) ether; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; Alcohols such as butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl) ether; Phenols such as phenol, cresol and xylenol; Esters such as ethyl acetate, butyl acetate, ethyl vertical solve acetate, and butyl vertical solve acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, monochlorobenzene and the like are used. These organic solvents are used individually or in mixture. In consideration of solubility, low hygroscopicity, low temperature hardenability and environmental safety, it is preferable to use lactones, ethers, ketones and the like.

Reaction temperature is 80 degrees C or less, Preferably it is 0-50 degreeC. As the reaction proceeds, the reaction solution gradually thickens. In this case, polyamic acid which is a precursor of the polyimide resin is produced. You may partially imidize this polyamic acid, and this is also contained in the precursor of polyimide resin.

A polyimide resin is obtained by dehydrating and closing the said reactant (polyamic acid). A dehydration ring can be performed by the method of heat processing at 120 degreeC-250 degreeC (thermal imidation), or the method (chemical imidation) using a dehydrating agent. In the case of the method of heat processing at 120 degreeC-250 degreeC, it is preferable to carry out, removing the water which arises from a dehydration reaction out of a system. At this time, you may azeotropically remove water using benzene, toluene, xylene, etc.

As a dehydrating agent, it is preferable to use acid anhydrides, such as acetic anhydride, propionic anhydride, and benzoic anhydride, carbodiimide compounds, such as dicyclohexyl carbodiimide, as a dehydrating agent. At this time, if necessary, dehydration catalysts such as pyridine, isoquinoline, trimethylamine, and aminopyridinimidazole may be used. It is preferable to use a dehydrating agent or a dehydration catalyst in the range of 1-8 mol with respect to 1 mol of aromatic tetracarboxylic dianhydrides, respectively.

The polyamideimide resin or the precursor thereof is, in the production of the polyimide resin or the precursor thereof, instead of an aromatic tetracarboxylic dianhydride, trimellitic anhydride or trimellitic anhydride derivative (such as chloride of trimellitic anhydride) and the like. It can be manufactured using the trivalent tricarboxylic acid anhydride or derivatives thereof. In addition, instead of an aromatic diamine compound and other diamine compounds, residues other than an amino group can also be manufactured using the diisocyanate compound corresponding to the diamine compound. As a diisocyanate compound which can be used, it may be obtained by making the said aromatic diamine compound or another diamine compound, phosgene, or thionyl chloride react.

The polyamide resin can be produced by reacting derivatives such as aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, their dichlorides and acid anhydrides with the aforementioned aromatic diamine compounds or other diamine compounds.

Examples of the heat resistant resin having an ester bond include polyester resins. Examples of the polyester resins include derivatives such as aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, their dichlorides and acid anhydrides, and 1,4. It may be obtained by making aromatic diol compounds, such as dihydroxy benzene, bisphenol F, bisphenol A, and 4,4'- dihydroxy biphenyl, react.

As the polyamideimide resin, a polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As an aromatic tetracarboxylic dianhydride and an aromatic diamine compound, said thing is used. The molar ratio of the isophthalic acid dihydrazide in the aromatic diamine compound is preferably 1 to 100 mol%. If it is less than 1 mol%, there exists a tendency for the solvent resistance to modified polyamideimide resin to fall, and when there is much content of dihydrazide of isophthalic acid, there exists a tendency for the moisture resistance of the layer formed by the paste of this invention to fall, and it is 10-10. 80 mol% is more preferable, and 20-70 mol% is used especially preferable. This polyamideimide resin can be obtained by carrying out the compounding ratio of an aromatic tetracarboxylic dianhydride and an aromatic diamine compound, an organic solvent used, a synthesis method, etc. similarly to the synthesis | combination of the said polyimide resin.

The trimellitic anhydride and the polyamideimide resin obtained by reacting dicarboxylic acid and a polyisocyanate as needed become easy to become insoluble in an organic solvent by heating, and the organic fine particle which consists of this polyamideimide resin can also be used. About the manufacturing method of this polyamide-imide resin, it can manufacture similarly to the manufacturing method of said polyamide-imide resin.

As the method of micronization, for example, non-water dispersion polymerization method (Japanese Patent Application Laid-Open No. 60-48531, Japanese Patent Application Laid-Open No. 59-230018), precipitation polymerization method (Japanese Patent Application Laid-Open No. 59-108030, Japanese Patent Application Laid-Open No. 60) -221425), a method of mechanically grinding a powder obtained from a resin solution, a method of finely granulating the resin solution with high shear while adding the resin solution, a method of drying the spray solution of the resin solution to obtain fine particles, There exists a method of depositing fine particles of resin which has solubility temperature dependence with respect to a solvent in detergent or a resin solution.

As the inorganic fine particles and / or the organic fine particles in the present invention, those having a particle size of 50 µm or less in average particle diameter and 100 µm or less in maximum particle diameter are preferably used. If the average particle size exceeds 50 µm, a paste having a thixotropy coefficient of 1.1 or more, which will be described later, becomes difficult to be obtained. If the maximum particle size exceeds 100 µm, the appearance and adhesion of the coating film tend to be insufficient. The average particle diameter is more preferably 30 μm or less, still more 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 it is 40 micrometers or less.

[Resin composition]

The resin composition of this invention can be manufactured by melt | dissolving resin which is (A) component in an organic solvent, making it a resin solution, and disperse | distributing the inorganic fine particles and / or organic microparticles which are (B) component.

In the resin composition of the present invention, the content of the inorganic fine particles and / or organic fine particles to be used as the component (B) is preferably 1 to 350 parts by weight, and 30 to 300 parts by weight based on 100 parts by weight of the component (A). It is more preferable, it is especially preferable to use 50-280 weight part, and it is most preferable to use 100-250 weight part. When the content of the component (B) is smaller than this, the viscosity and thixotropy coefficient of the paste are lowered, the paste connection is increased, the outflow of the paste after printing is large, and the film thickness tends to be thin. The state and the electrical property of the film edge part after tin plating become inferior. In addition, when the content of the component (B) is larger than this, the viscosity and thixotropy coefficient of the paste are increased, the transferability of the paste to the substrate and the voids and pinholes in the printed film are increased. There is this.

As an organic solvent which melt | dissolves resin of (A) component, it is an non-nitrogen type polar solvent, an ether solvent, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether ; Containing sulfur solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; Ester solvents such as γ-butyrolactone, a vertical acetate solution; Ketone solvents such as cyclohexanone, methylethylketone; Aromatic hydrocarbon solvents such as toluene, xylene, and the like, and these may be used alone or in combination of two or more thereof. Since solubility differs by resin to produce | generate, the solvent which can melt | dissolve resin is selected and used.

As a method of disperse | distributing inorganic and / or organic microparticles | fine-particles to the solution of a thermosetting resin, roll kneading | mixing, mixer mixing, etc. which are normally performed in the coating field are applied, and what is necessary is just a method in which sufficient dispersion is performed.

In the resin composition of this invention, in order to improve the workability at the time of coating and the film | membrane characteristic before and after film formation, surfactant, such as an antifoamer, a leveling agent, coloring agents, such as dye or a pigment, a heat stabilizer, antioxidant, a flame retardant, Lubricants can also be added.

It is preferable that the resin composition of this invention is 0.5 Pa.s-500 Pa.s, and thixotropy coefficient is 1.1 or more in 25 degreeC in a rotational viscometer. If the viscosity is less than 0.5 Pa · s, the outflow of the paste after printing tends to be large, and the film thickness tends to become thin. If the viscosity is more than 500 Pa · s, the transferability of the paste to the substrate decreases, and the voids and pinholes in the printed film. This tends to increase. If the thixotropy coefficient is less than 1.1, the actual connection of the paste is increased, and the outflow of the paste after printing is large, and the film thickness also tends to be thin. As for a viscosity, it is more preferable that it is 1-250, and 10-100 are especially preferable. In addition, the thixotropy coefficient is more preferably 1.2 or more, and particularly preferably 1.4 or more.

Here, the viscosity of a resin composition is represented as the viscosity of rotation speed 10 rPam measured by 0.2 ml or 0.5 ml of sample amounts using the E-type viscosity meter (R80 type | mold by the synchronous industry company). In addition, the thixotropy coefficient (TI value) of the paste was measured using an E-type viscometer (REE 80Ｕ type, manufactured by Synthetic Industries, Inc.), and the apparent viscosity of the pastes of 1 rpm and 10 rpm, η1 and η10, measured at a sample volume of 0.2 ml or 0.5 ml. It is expressed as ratio η 1 / η 10.

Moreover, although the resin composition of this invention was used as the cured film, it is preferable that 5% thermogravimetric reduction temperature is 250 degreeC or more. If the 5% thermogravimetric reduction temperature is less than 250 ° C, the cured film may deform and decompose due to the heat applied during connection with a rigid wiring board, an IC chip, an electronic component, or an LCD panel. Further, the 5% weight loss temperature is heated in the same range as the generation of the cured film for measuring the tensile modulus of elasticity or the like, that is, 80 to 130 ° C., within the range of time for forming the protective film on the surface of the ordinary flexible wiring board, A cured film having a film thickness of about 30 μm is formed, and a value measured by the TV-DTA method is performed at an elevated temperature rate of 10 ° C./min in an air atmosphere.

After this screen-printing the said resin composition on the wiring pattern of a flexible wiring board further, it thermosets, forms a cured film, and can use it suitably for the flexible wiring board used as a protective film. In particular, it is suitable for the protective film use of the surface of the flexible wiring board in which the whole wiring pattern part was plated. The conditions for thermosetting are preferably 80 ° C to 130 ° C, particularly preferably 90 ° C to 120 ° C, from the viewpoint of preventing diffusion of the plating layer and obtaining adequate bendability and flexibility as a protective film. For example, it can also be hardened in 50-200 degreeC, especially 50-140 degreeC. The heating time is from 60 to 150 minutes, preferably from 80 to 120 minutes, from the viewpoint of preventing diffusion of the plating layer and obtaining adequate bendability and flexibility as a protective film, but is not limited to this range, but is from 1 to 1,000. It can also harden | cure in minutes, for example, 5-300 minutes, especially 10-150 minutes.

[Film forming material]

The resin composition of this invention contains the resin composition mentioned above, and is used suitably for coating methods, such as screen printing, a dispenser, a spin coat, as a film formation material of various electrical appliances and electronic components. In particular, it is suitably used for screen printing.

The resin composition according to the present invention is suitably used as, for example, an overcoat material for an electronic component, a liquid encapsulating material, an interlayer insulating film, a surface protective film, a solder resist layer, an adhesive layer, or the like, for example, in the field of semiconductor devices and printed circuit boards. It can also be used for varnishes for enameled wire, impregnated varnishes for electric insulation, varnishes for sheets combined with base materials such as mold varnishes, mica, glass crosses, varnishes for MLC laminated sheets, varnishes for friction materials, and the like. In addition, since the resin film does not peel off from the circuit board or the like and is excellent in adhesion between the substrate and the resin and print workability, highly reliable electronic parts are obtained.

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

Example  One

[Synthesis of Polymer Resin]

In a 3-liter four-necked flask equipped with a stirrer, a cooling tube with an oil separator, a nitrogen introduction tube, and a thermometer, Plaque Cell CD-220 (trade name of 1,6-hexanediol polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.) 2000.0 g (100 mol), adipic acid 292.0 g (2.00 mol), and 114.6 g of xylene were thrown in, and it heated up to 200 degreeC, removing the by-product condensate on the way. It was made to react at 200 degreeC for 2 hours, and the dicarboxylic acid A of acid value 49.7OHHgg / g was obtained.

Subsequently, 150.0 g (0.60 mol) of 4,4'-diphenylmethane diisocyanate and 69.12 g (0.36 mol) of trimellitic anhydride were put into a 2-liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. And 541.44 g (0.24 mol) of dicarboxylic acid A and 760.56 g of γ-butyrolactone obtained in the above synthesis were added thereto, and the mixture was heated to 160 ° C. 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 change of viscosity by a Gardner bubble viscometer. The obtained resin was diluted with (gamma) -butyrolactone, and the polycarbonate modified polyamideimide resin solution of 40 weight% of non volatile matters was obtained.

[Synthesis of low molecular weight resin]

Except having heated up to 160 degreeC and making it react for 7 hours, the low molecular resin of the number average molecular weight 29,000 and 40 weight% of non volatile matters was obtained by operation similar to the synthesis of polymer resin.

20% of the obtained polycarbonate modified polyamideimide resin solution of which the number average molecular weight is 29,000, and 80% of the polycarbonate modified polyamideimide resin solution which has the number average molecular weight of 38,000 are mixed, and it is a solvent process liquid with respect to 100 weight part of resin powders. 0.3 weight part of 1 weight part and silicone type antifoamer (A) (the Shin-Etsu Chemical Co., Ltd. brand name: SUS-603) was mix | blended, and it stirred at 20 degreeC for 10 minutes. 30 parts by weight of barium sulfate (trade name: B-30, manufactured by Sakai Chemical Co., Ltd.) is further blended, and solvents such as γ-butyrolactone are added if necessary, and the mixture is stirred at 50 ° C for 1 hour. EV-1004 (Emulsified Cell Epoxy Co., Ltd.) 20 weight part of brand names and bisphenol-A epoxy resins are further added, and it stirred at 20 degreeC for 1 hour, and also mix | blends 0.2 weight part of silicone type antifoamers (B) (Brand name: US-603 made by Shin-Etsu Chemical Co., Ltd.), and 20 degreeC It stirred for 30 minutes at and obtained the polycarbonate modified polyamideimide resin composition.

<Measurement of number average molecular weight and weight average molecular weight of resin>

The gel permeation chromatography (BP) converted the calibration curve using standard polystyrene. Measurement conditions of the PCC are shown below.

(PCC condition)

Pump: Hitachi L-6000 Type [Hitachi Corporation]

Detector: Hitachi L-4000 Type ＵＶ [Hitachi Corporation]

Column: Ｇｅｌｐａｃｋ SL-S300MD-5 (2 in total) (Hitachi Chemicals, Inc., trade name)

Eluent: DMF / THF = 1/1 + phosphoric acid (0.06M) + lithium bromide (0.06M)

Example  2

In Example 1, except that the number average molecular weights of the polycarbonate modified polyamideimide resin were 25,000 and 32,000, the reaction was carried out in exactly the same manner as in Example 1, except that the polycarbonate modified polyamideimide resin was produced. A composition was obtained.

Example  3

Except having produced and used the number average molecular weights of 23,000 and 29,000 polycarbonate modified polyamideimide resin in Example 1, operation similar to Example 1 was performed and the polycarbonate modified polyamideimide resin composition was obtained.

Example  4

In Example 1, polycarbonate modified polyamideimide resin was carried out in exactly the same manner as in Example 1 except that the number average molecular weights of the polycarbonate-modified polyamideimide resin were 36,000 and 42,000. A 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 were mixed to 100 parts by weight of the resin powder. 1 part by weight of the solvent treatment liquid and 0.3 part by weight of the silicone antifoaming agent (A) (trade name: US-603 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and stirred at 20 ° C for 10 minutes. 100 parts by weight of barium sulfate (trade name: B-30, manufactured by Sakai Chemical Co., Ltd.), 20 parts by weight of talc (trade name: Micro Ace P-3, manufactured by Nippon Taruk Co., Ltd.), and silica (trade name: AEROSISL380, manufactured by Nippon Aerosol Co., Ltd.) ), 10 parts by weight of a mixture, a solvent such as γ-butyrolactone are added if necessary, and the mixture is stirred at 50 ° C for 1 hour, and 10 parts by weight of an amine epoxy resin (trade name: DH-434L) The mixture was stirred at 20 ° C for 1 hour, further mixed with 0.2 parts by weight of a silicone antifoaming agent (B) (trade name: US-603 manufactured by Shin-Etsu Chemical Co., Ltd.), stirred at 20 ° C for 30 minutes to form a polycarbonate-modified polyamideimide resin composition. Got.

Example  6

The polycarbonate-modified polyamideimide resin was carried out in exactly the same manner as in Example 1 except that the number average molecular weight of the polycarbonate-modified polyamideimide resin was prepared in Example 1, and the reaction time was adjusted to 32,000. A composition was obtained.

Comparative example  One

The polycarbonate-modified polyamide-imide resin composition was carried out in exactly the same manner as in Example 1 except that the number average molecular weights of the polycarbonate-modified polyamide-imide resins in Example 1 were prepared by adjusting the reaction time. Got.

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.

Film end state after tin plating

On the 35-micrometer copper foil, the obtained polycarbonate modified polyamideimide resin composition was 30 mm each at a printing speed of 100 mm / sec by a printing machine (trade name: LS-34K, manufactured by Neulong Co., Ltd.) and a mesh plate (150 mesh manufactured by Murakami Co., Ltd.). Was printed and heat-hardened at 120 degreeC under air atmosphere for 60 minutes, and the polycarbonate modified polyamideimide resin film was obtained. The obtained polycarbonate-modified polyamideimide resin film was immersed in a 70 ° C. tin plating solution (trade name: LT-34 manufactured by Seaflyfist Co., Ltd.) for 3 minutes, and then immersed in ion exchanged water at 80 ° C. for 10 minutes to obtain 100 ° C. hot air. After drying for 30 minutes in a circulation dryer, the peeling state of the resin film of the periphery of the polycarbonate modified polyamideimide resin film on copper foil was observed with the universal projection machine (50 times the magnification by Nikon Corporation). The resin film without peeling was made into (circle), the thing with some peeling was (triangle | delta) and the thing with peeling was made into x.

Electrical properties

The obtained polycarbonate modified polyamideimide resin composition was coated on a polyimide substrate with a line width of 15 μm and a space width of 15 μm to form a comb-shaped copper electrode. (150 mesh manufactured by Murakami Co., Ltd.) was printed at a printing speed of 100 mm / sec, and heat-cured at 120 ° C. for 60 minutes under an air atmosphere to obtain a polyimide base comb electrode with a polycarbonate-modified polyamideimide resin film. The obtained polycarbonate modified polyamideimide resin film-coated polyimide base comb-type electrode was subjected to a continuous resistance measuring instrument (trade name: manufactured by IMM Corporation) and an unsaturated pressure cooker (trade name: HASCP-422R8). The resistance was measured on condition of temperature 110 degreeC, humidity 85%, applied voltage 40V, and application time 100 hours.

Each of three samples was produced and measured about the polycarbonate modified polyamideimide resin composition obtained in Examples 1-6 and Comparative Example 1. After 100 hours of voltage application, the resistance values of all three samples were 1 × 10 ^-6 Ω or higher, and the two samples were 1 × 10 ^-6 Ω or higher, and the one sample was 1 × 10 ^-6 Ω or higher. "C" and the thing of all three samples which were less than 1x10 <^{-6> (} ohm) were evaluated as "D.

Printability

On the glass plate of 2 mm, the obtained polycarbonate modified polyamideimide resin composition was printed by printing machine (Nelong Co., Ltd. brand name: LS-34 ') and a mesh board (150 mesh manufactured by Murakami Co., Ltd.) at 100 mm / sec, and printing a 100 mm angle. It heat-hardened for 60 minutes at 120 degreeC under air atmosphere, and obtained the polycarbonate modified polyamide-imide resin film. The obtained polycarbonate modified polyamideimide resin film was observed with a universal projection machine (20 times magnification made by Nikon Corporation), and delamination of the cures and the ends of the resin film was observed. The resin film without the distortion of the casing and the edge part was made into (circle), and the thing with the distortion of the curse and the edge part was made into x.

* The characteristic when two kinds of resins are mixed

* Example 6 is the physical property of 1 type of resin, and the comparative example 1 is a characteristic at the time of mixing 2 types of resin.

From the above result, the following was judged.

In Examples 1-6, since resin with a number average molecular weight of 22,000-50,000 is used, it is excellent in print workability, without peeling to the film edge part after tin plating.

Moreover, in Examples 1-5, the film edge state after tin plating was favorable, and the electrical characteristic was also favorable substantially. Print workability was favorable except Example 4. On the other hand, in the comparative example 1, it was confirmed that the casing and the edge part were distorted at the film edge part 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, dispensers, and spin coats as film forming materials for various electrical products and electronic parts. In addition, it has excellent printing workability without causing peeling on the coated end portion after tin plating, and has overcoat material for electronic parts, liquid sealing material, varnish for enameled wire, varnish for electrical insulation, varnish for laminated sheet, varnish for friction material, It is useful for electronic parts, such as an interlayer insulation film, a surface protective film, a soldering resist film, an adhesive layer, etc. in a printed circuit board field, etc., and a semiconductor element containing these.

Claims (10)

The resin composition containing (A) resin and (B) inorganic filler and / or organic filler, The number average molecular weight of said (A) resin is 22,000-50,000, The resin composition characterized by the above-mentioned. (B) Inorganic filler and / or organic filler are disperse | distributed to the resin solution containing the solvent which mixed two or more (A) resin from which a number average molecular weight differs, The resin composition characterized by the above-mentioned. The resin composition according to claim 1 or 2, wherein the resin (A) has a polycarbonate skeleton. The said (A) resin has an imide bond, The resin composition of any one of Claims 1-3 characterized by the above-mentioned. The said (A) resin is at least 1 chosen from the group which consists of a polyimide resin, polyamideimide resin, polyamide resin, and derivatives thereof which have a polycarbonate backbone. It is a species, The resin composition characterized by the above-mentioned. 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, The resin of any one of Claims 1-5. Composition. The said (B) inorganic filler and / or organic filler contain barium sulfate, The resin composition of any one of Claims 1-6 characterized by the above-mentioned. The resin composition according to claim 7, wherein the (B) inorganic filler and / or organic filler further comprises silica and talc. The resin composition according to any one of claims 1 to 8, further comprising an epoxy resin as a curing agent. The resin composition of any one of Claims 1-9 containing the resin composition of any one of Claims 1-9.