CN106715590B

CN106715590B - Polycarbonate imide resin paste and electronic component having solder resist layer, surface protective layer, interlayer insulating layer or adhesive layer obtained by curing the paste

Info

Publication number: CN106715590B
Application number: CN201580048829.1A
Authority: CN
Inventors: 内山翔子; 栗田智晴
Original assignee: Toyobo Co Ltd
Current assignee: Toyobo Co Ltd
Priority date: 2014-10-28
Filing date: 2015-10-15
Publication date: 2022-01-04
Anticipated expiration: 2035-10-15
Also published as: JP6699546B2; WO2016067925A1; TW201623486A; KR20170077060A; KR102285047B1; JPWO2016067925A1; TWI687492B; CN106715590A

Abstract

Provided is a polycarbonate imide resin paste which is (1) soluble in a non-nitrogen solvent, (2) low-temperature drying/curing, (3) low warpage, (4) bendability, (5) printing characteristics, (6) excellent in alkali resistance, and excellent in heat resistance, chemical resistance, and electrical characteristics; and an electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste. A polycarbonate imide resin paste comprising: the resin composition comprises a polycarbonate imide resin as a component (A), an epoxy resin having 2 or more epoxy groups per 1 molecule as a component (B), and a filler as a component (C), wherein the polycarbonate imide resin comprises (a) a tri-and/or tetra-carboxylic acid derivative having an acid anhydride group, (B) an acid dianhydride having a polycarbonate skeleton with a specific structure, and (C) an isocyanate compound or an amine compound as essential copolymerization components.

Description

Polycarbonate imide resin paste and electronic component having solder resist layer, surface protective layer, interlayer insulating layer or adhesive layer obtained by curing the paste

Technical Field

The present invention relates to a polycarbonate imide resin paste. In particular, the present invention relates to a polycarbonate imide resin paste which is useful for COF (Chip On Film) substrate applications, has excellent heat resistance and flexibility, and is suitable for a coating method such as a printer, dispenser, or spinner, and an electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer obtained by curing the paste.

Background

Generally, polyimide resins are widely used as insulating materials for electrical and electronic devices because of their excellent heat resistance, insulating properties, chemical resistance, and the like. In particular, COF substrates are used as a material for a COF substrate in many cases, and are used as a circuit board material and a mounting substrate material for electronic devices which require flexibility and a small space. For example, the present invention is widely used in device-mounting substrates for display devices used in liquid crystal display devices, plasma displays, organic EL displays, and the like, inter-substrate relay cables for smartphones, tablet terminals, digital cameras, portable game machines, and the like, operation switch unit substrates, and coating materials (protective layers for circuits) for these substrates. In particular, in printed wiring boards, solder resists are widely used as permanent protective coatings for circuits. The solder resist forms a coating film on the entire surface of the circuit conductor except for the soldered portion, and serves as a protective coating film for preventing solder from adhering to an unnecessary portion and preventing the circuit from being directly exposed to air when the electronic component is wired on the printed circuit board.

However, a compound containing a solvent-soluble closed-loop polyimide resin is proposed as a material for a solder resist layer, a surface protective layer, or an adhesive layer which is a component of a COF substrate, because it is often applied and printed in the form of a solution, but since a high-boiling nitrogen-based solvent such as N-methyl-2-pyrrolidone has been conventionally used as a solvent for forming a varnish of a polyimide-based resin, a curing process at a high temperature of 200 ℃ or higher for a long time is required at the time of drying and curing, and there is a problem that thermal degradation of an electronic component occurs.

Further, since the polyimide resin is generally hard and has a high elastic modulus, when it is laminated on a substrate such as a film or a copper foil, warpage or the like occurs due to a difference in the elastic modulus, and therefore, there is a problem in a subsequent step. Further, there is a problem that the cured film lacks flexibility and is poor in bendability.

Further, as a polyimide-based resin having low warpage and flexibility, which is soluble in a non-nitrogen-based solvent and obtained by making the resin flexible and having a low elastic modulus, for example, (patent document 1), (patent document 2) and the like disclose polysiloxane-modified polyimide-based resins.

These polysiloxane-modified polyimide resins are poor in economical efficiency because they use expensive diamines having dimethylsiloxane bonds as starting materials for the purpose of reducing the elastic modulus. Further, there is a problem that the adhesion, solvent resistance and chemical resistance are reduced as the amount of the polysiloxane copolymer is increased.

Further, compositions in which a certain amount of polycarbonate resin is mixed with polyimide resin to impart flexibility thereto and thereby the molding processability of the resin composition is improved are disclosed (patent documents 3 and 4). Further, there is disclosed a thermoplastic resin composition having improved molding processability, which is obtained by mixing a polyimide resin, an epoxy resin and a polycarbonate resin (patent document 5). These resins are listed as resins suitable for melt kneading and melt extrusion, and although they are excellent in heat resistance and mechanical strength, they are insoluble in nitrogen-free solvents and hardly have low warpage and flexibility.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 7-304950

Patent document 2: japanese laid-open patent publication No. 8-333455

Patent document 3: japanese laid-open patent publication No. 5-320492

Patent document 4: japanese laid-open patent publication No. 6-136267

Patent document 5: japanese laid-open patent publication No. 62-7758

Disclosure of Invention

Problems to be solved by the invention

As is clear from the above-mentioned examples, there has been no heretofore known polyimide resin paste which satisfies the requirements of (1) solubility in a non-nitrogen solvent, (2) drying/curing properties at low temperatures, (3) low warpage, (4) bendability, (5) printing properties, and (6) alkali resistance, and is suitable for use as a solder resist, a surface protective layer, or an adhesive layer.

The present invention was made in view of the problems of the prior art. That is, an object of the present invention is to provide a polycarbonate imide resin paste which is (1) soluble in a non-nitrogen solvent, (2) low-temperature drying/curing, (3) low warpage, (4) flexible, (5) excellent in printing characteristics, (6) excellent in alkali resistance, and excellent in heat resistance, chemical resistance and electrical characteristics, and an electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste.

Means for solving the problems

A polycarbonate imide resin paste comprising: a polycarbonate imide resin comprising, as essential copolymerization components, (a) a ternary and/or quaternary polycarboxylic acid derivative having an acid anhydride group, (B) an acid dianhydride having a polycarbonate skeleton represented by the general formula (1), and (C) an isocyanate compound or an amine compound, as a component (a), an epoxy resin having 2 or more epoxy groups per 1 molecule as a component (B), and a filler as a component (C).

(in the general formula (1), m and n are each an integer of 1 or more, and m's are optionally the same as or different from each other.)

Preferably, a curing accelerator is further contained as the component (D).

The thixotropic index of the polycarbonate imide resin paste is preferably 1.2 or more.

The polycarbonate imide-based resin paste according to any one of the preceding, which is for COF.

An electronic component comprising a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the polycarbonate imide resin paste described in any one of the above.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a polycarbonate imide resin paste which is not easily satisfied in the past (1) solubility in a non-nitrogen solvent, (2) drying/curing at low temperature, (3) low warpage, (4) bendability, (5) printing characteristics, (6) excellent alkali resistance, and excellent in heat resistance, chemical resistance, and electrical characteristics; and an electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste.

Detailed Description

The present invention will be described in detail below. The polycarbonate imide resin paste of the present invention contains: the polycarbonate imide resin (a) is the component (a), the epoxy resin having 2 or more epoxy groups per 1 molecule (hereinafter, also referred to as epoxy resin (B)) is the component (B), and the inorganic or organic filler (hereinafter, also referred to as filler (C)) is the component (C). The polycarbonate imide resin (a) contains, as essential copolymerization components, (a) a tri-and/or tetra-basic polycarboxylic acid derivative having an acid anhydride group (hereinafter also referred to as component (a)), (b) an acid dianhydride having a polycarbonate skeleton represented by general formula (1) (hereinafter also referred to as component (b)), and (c) an isocyanate compound or an amine compound (hereinafter also referred to as component (c)).

< component (A) of the polycarbonate imide resin >

The polycarbonate imide resin (A) used in the present invention will be described. The polycarbonate imide resin (a) is a polycarbonate imide resin containing, as essential copolymerization components, (a) a ternary and/or quaternary polycarboxylic acid derivative having an acid anhydride group, (b) an acid dianhydride represented by the general formula (1) having a polycarbonate skeleton, and (c) an isocyanate compound or an amine compound, and is preferably a polycarbonate imide resin containing, as essential copolymerization components, the above-mentioned component (a), (b) and (c).

[ a ] A ternary and/or quaternary polycarboxylic acid derivative having an acid anhydride group ]

The component (a) constituting the polycarbonate imide resin (a) used in the present invention is not particularly limited as long as it is a tri-and/or tetra-carboxylic acid derivative having an acid anhydride group, which is generally reacted with an isocyanate component and an amine component to form a polyimide resin, and an aromatic polycarboxylic acid derivative, an aliphatic polycarboxylic acid derivative or an alicyclic polycarboxylic acid derivative can be used.

The aromatic polycarboxylic acid derivative is not particularly limited, and examples thereof include: alkylene glycol bis (anhydrotrimellitate) such as trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bis (anhydrotrimellitate), propylene glycol bis (anhydrotrimellitate), 1, 4-butanediol bis (anhydrotrimellitate), hexanediol bis (anhydrotrimellitate), polyethylene glycol bis (anhydrotrimellitate), and polypropylene glycol bis (anhydrotrimellitate), 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-pyrene tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl sulfone tetracarboxylic dianhydride, m-terphenyl-3, 3 ', 4,4 ' -tetracarboxylic dianhydride, 4,4 ' -oxydiphthalic dianhydride, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (2, 3-or 3, 4-dicarboxyphenyl) propane dianhydride, 2, 2-bis [4- (2, 3-or 3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 1,1,3,3, 3-hexafluoro-2, 2-bis [4- (2, 3-or 3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) -1,1,3, 3-tetramethyldisiloxane dianhydride, or the like.

The aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, and examples thereof include: butane-1, 2,3, 4-tetracarboxylic dianhydride, pentane-1, 2,4, 5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohex-1-ene-2, 3,5, 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2),5, 6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2),5, 6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2),5, 6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2),3, 4-tetracarboxylic dianhydride, pentane-1, 2,4, 5-tetracarboxylic dianhydride, cyclobutane-tetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohexane-1-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3, 1-3, 6-tetracarboxylic dianhydride, 1-ethylcyclohex-1-ene-3- (2), 5, 6-tetracarboxylic dianhydride, 1-tetracarboxylic dianhydride, and 1-ethylcyclohexane-1- (1,2, 3, 4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3),3, 4-tetracarboxylic dianhydride, 1, 3-dipropylcyclohexane-1- (2,3),3- (2,3) -tetracarboxylic dianhydride, bicyclohexyl-3, 4,3 ', 4' -tetracarboxylic dianhydride, bicyclo [2,2,1] heptane-2, 3,5, 6-tetracarboxylic dianhydride, Bicyclo [2,2,2] octane-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride, or the like.

These tri-and/or tetra-carboxylic acid derivatives having an acid anhydride group may be used alone, or 2 or more thereof may be used in combination. In view of heat resistance, transparency, adhesion, solubility, cost, and the like, pyromellitic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, and 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride are preferable, and trimellitic anhydride and ethylene glycol bis (anhydrotrimellitate) are more preferable.

The copolymerization amount of the component (a) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, and particularly preferably 30 mol% or more and 70 mol% or less, when the total acid components to be reacted are assumed to be 100 mol%. If the amount is less than 10 mol%, flame retardancy, mechanical properties and heat resistance may not be obtained, and if the amount is more than 90 mol%, components (b) and (c) to be described later may not be copolymerized in a sufficient amount. Therefore, the warpage is low and the solubility in a non-nitrogen solvent is lowered in some cases.

[ b ] acid dianhydride having a polycarbonate skeleton represented by the general formula (1) >

The component (b) constituting the polycarbonate imide resin (a) used in the present invention is copolymerized as a flexible component for imparting low warpage, non-nitrogen solvent solubility, and the like to the polycarbonate imide resin (a). By copolymerizing these, the elastic modulus of the polycarbonate imide resin (a) is lowered, and the solubility stability in a non-nitrogen solvent used as a polymerization solvent is increased.

The component (b) is an acid dianhydride having a polycarbonate skeleton represented by the general formula (1).

In the general formula (1), m is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more. The upper limit is not particularly limited, but is preferably 20 or less, and more preferably 10 or less. The plurality of m may be the same as or different from each other. n is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. The upper limit is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.

The method for producing the component (b) is not particularly limited, and it can be synthesized from a chloride of trimellitic anhydride and a polycarbonate diol compound by a known reaction method. More specifically, first, a polycarbonate diol compound and a deoxidizer are added to a chloride solution of trimellitic anhydride obtained by dissolving in a solvent, and the mixture is stirred for 0.5 to 24 hours. The reaction temperature is preferably from-20 to 50 ℃ and more preferably from 20 to 40 ℃ from the viewpoint of reaction selectivity. The reaction ratio of the chloride of trimellitic anhydride to the polycarbonate diol compound is preferably 2 moles or more of the chloride of trimellitic anhydride per 1 mole of the polycarbonate diol compound. The concentration of the solute in the reaction is preferably 5 to 80 wt%, more preferably 40 to 60 wt%. After the reaction is completed, the precipitated hydrochloride is filtered off, and the solvent is concentrated to obtain the target acid dianhydride having a polycarbonate skeleton represented by general formula (1) (hereinafter, also referred to as polycarbonate skeleton-containing tetracarboxylic dianhydride).

Examples of the method for producing the polycarbonate diol compound include: transesterification of a diol as a raw material with a carbonate, dehydrochlorination of a diol as a raw material with phosgene. The carbonate as a raw material is not particularly limited, and examples thereof include: dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

As the diol, a linear diol compound having 2 hydroxyl groups can be used. Examples of the solvent include, but are not limited to: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and the like.

Commercially available products of the polycarbonate diol compound which can be used in the present invention include: DURANOL series manufactured by Asahi Kasei Chemicals K.K.K.K.. Examples thereof include: DURANOL (registered trademark) -T5650E (polycarbonate diol: 1, 5-pentanediol/1, 6-hexanediol, manufactured by Asahi Kasei corporation, having a number average molecular weight of about 500), DURANOL-T5651 (polycarbonate diol: 1, 5-pentanediol/1, 6-hexanediol, manufactured by Asahi Kasei corporation, having a number average molecular weight of about 1000), DURANOL-T5652 (polycarbonate diol: 1, 5-pentanediol/1, 6-hexanediol, manufactured by Asahi Kasei corporation, having a number average molecular weight of about 2000), and the like.

The copolymerization amount of the component (b) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, and particularly preferably 30 mol% or more and 70 mol% or less, when the total amount of the acid components is 100 mol%. If the amount is less than 10 mol%, the elastic modulus may not be sufficiently lowered, and warpage or a decrease in solubility in a non-nitrogen solvent may occur during lamination. Therefore, the resin may be precipitated within one month at5 to 30 ℃. On the other hand, if it exceeds 90 mol%, the component (a) and the component (c) described later cannot be contained in sufficient amounts, and hence the flexibility (mechanical properties) and heat resistance may be lowered.

< C) isocyanate Compound or amine Compound

The component (c) constituting the polycarbonate imide resin (a) used in the present invention is not particularly limited as long as it is an isocyanate compound or an amine compound, and examples thereof include: aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate, or polyamine corresponding thereto. Preferably, an aromatic polyisocyanate or an aromatic polyamine is used. Specific examples of the aromatic polyisocyanate include, but are not particularly limited to: diphenylmethane-2, 4 ' -diisocyanate, 3,2 ' -or 3,3 ' -or 4,2 ' -or 4,3 ' -or 5,2 ' -or 5,3 ' -or 6,2 ' -or 6,3 ' -dimethyldiphenylmethane-2, 4 ' -diisocyanate, 3,2 ' -or 3,3 ' -or 4,2 ' -or 4,3 ' -or 5,2 ' -or 5,3 ' -or 6,2 ' -or 6,3 ' -diethyldiphenylmethane-2, 4 ' -diisocyanate, 3,2 ' -or 3,3 ' -or 4,2 ' -or 4,3 ' -or 5,2 ' -or 5,3 ' -or 6,2 ' -or 6,3 ' -dimethoxydiphenylmethane-2, 4 '-diisocyanate, diphenylmethane-4, 4' -diisocyanate, diphenylmethane-3, 3 '-diisocyanate, diphenylmethane-3, 4' -diisocyanate, diphenylether-4, 4 '-diisocyanate, benzophenone-4, 4' -diisocyanate, diphenylsulfone-4, 4 '-diisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2, 6-diisocyanate, 4' - [2,2 bis (4-phenoxyphenyl) propane ] diisocyanate, 3 'or 2, 2' -dimethylbiphenyl-4, 4 '-diisocyanate, 3' -or 2,2 '-diethylbiphenyl-4, 4' -diisocyanate, 3 '-dimethoxybiphenyl-4, 4' -diisocyanate, 3 '-diethoxybiphenyl-4, 4' -diisocyanate, and the like. In view of heat resistance, adhesion, solubility, cost, and the like, diphenylmethane-4, 4 '-diisocyanate, toluene-2, 4-diisocyanate, m-xylylene diisocyanate, 3' -or 2,2 '-dimethylbiphenyl-4, 4' -diisocyanate are preferable, and 3,3 '-dimethylbiphenyl-4, 4' -diisocyanate (o-tolidine diisocyanate, TODI) and toluene-2, 4-diisocyanate (TDI) are more preferable. These may be used alone or in combination of 2 or more. In the case of using an aromatic polyamine, a polyamine corresponding to the aromatic polyisocyanate can be used.

The arbitrary isocyanate compound is preferably 100 mol% based on 100 mol% of the amine component used in the polycarbonate imide resin (a) of the present invention. When a diamine compound corresponding to the isocyanate is used in place of the isocyanate, a polyamic acid is passed through as a precursor of the polycarbonate polyimide resin. When polyamic acid is used, a polyamic acid-containing paste must be applied to a substrate such as COF (chip On film), and then imidized at a high temperature of usually about 200 ℃. In the present invention, since only the isocyanate compound containing TODI is used as the amine component, it is possible to perform the treatment at a lower temperature than the paste containing polyamic acid, and the above-mentioned problems do not occur, which is preferable.

< other acid Components >

The polycarbonate imide resin (a) used in the present invention may further contain an aliphatic, alicyclic or aromatic polycarboxylic acid as necessary within a range not impairing the intended performance. Examples of the aliphatic dicarboxylic acid include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid (sebasic acid), sebacic acid (decanedioic acid), dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, 3, 8-dimethylsebacic acid, 3, 7-dimethylsebacic acid, 9, 12-dimethyleicosanedioic acid, fumaric acid, maleic acid, dimer acid, hydrogenated dimer acid and the like, and examples of the alicyclic dicarboxylic acid include 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 4' -dicyclohexyldicarboxylic acid and the like, and examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid and the like, Phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, diphenylethylene dicarboxylic acid, and the like. These dicarboxylic acids may be used alone or in combination of two or more. In view of heat resistance, adhesion, solubility, cost, and the like, sebacic acid, 1, 4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferable.

In addition to the component (b), other flexible components may be further copolymerized as necessary within a range not impairing the target performance. Examples thereof include: aliphatic/aromatic polyester glycols (TOYOBO CO., manufactured by LTD., trade name VYLON (registered trademark) 220), aliphatic/aromatic polycarbonate glycols (manufactured by Daicel Chemical Industries, Co., Ltd., trade name PLACCEL (registered trademark) -CD 220; KURARARARARARAY CO., manufactured by LTD., trade name Kuraray Polyol C-1015N, C-2015N, manufactured by Asahi Kasei Chemical Co., Ltd., trade name Duranol (registered trademark) T5650E, T5650J, T5651, T5652, etc.), polycaprolactone glycols (manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark) -220, etc.), carboxyl-modified acrylonitrile butadiene rubbers (manufactured by Yusha Kasei Co., Ltd., trade name Hyproctbn 1300X 13, etc.), polydimethylsiloxane glycols, polymethylphenylsiloxane glycols, carboxyl-modified polydimethylsiloxanes, and other silicone derivatives.

As a method for producing the polycarbonate imide resin (a), there are known methods such as a method of producing from a polycarboxylic acid component having an acid anhydride group (components (a) and (b)) and an isocyanate component (c) (isocyanate method), and a method of reacting a polycarboxylic acid component having an acid anhydride group (components (a) and (b)) and an amine component (c) to produce an amic acid and then ring-closing the amic acid (direct method). The isocyanate method is industrially advantageous.

In the case of the isocyanate method, the ratio of the number of acid anhydride groups to the number of isocyanate groups is preferably 0.8 to 1.2 in terms of the number of isocyanate groups/the number of acid anhydride groups in the amount of the component (a), the component (b), and the component (c) to be blended. When the molecular weight is less than 0.8, the molecular weight of the polycarbonate imide resin (a) may be difficult to increase, and the heat resistance and flexibility may be reduced or the coating film may be brittle. When the viscosity is higher than 1.2, the viscosity of the polycarbonate imide resin (a) may be high, and plate peeling may be deteriorated when printing is performed in the case of forming an ink.

The polymerization reaction of the polycarbonate imide resin (a) used in the present invention is preferably carried out in a non-nitrogen solvent. Specifically, it is preferably carried out by removing carbon dioxide generated by liberation from the reaction system by, for example, an isocyanate method in the presence of 1 or more organic solvents selected from the group consisting of ether solvents, ester solvents, ketone solvents and aromatic hydrocarbon solvents and condensing the carbon dioxide by heating.

The above solvent is not particularly limited, and examples of the ether solvent include: diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyldiglyme), triethylene glycol dimethyl ether (triglyme), triethylene glycol diethyl ether (ethyltriglyme), and the like; the ester-based solvent includes, for example: gamma-butyrolactone, cellosolve acetate, and the like; examples of the ketone solvent include: methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, and the like; as the aromatic hydrocarbon-based solvent, for example, there may be mentioned: toluene, xylene, Solvesso, and the like. These may be used alone or in combination of two or more.

In the production of the polycarbonate imide resin (a), it is preferable to select and use a solvent for dissolving the produced polycarbonate imide resin (a), and it is more preferable to use a solvent which is suitable as a polycarbonate imide resin paste directly after polymerization. By doing so, the production can be carried out at low cost without complicated operations such as solvent replacement. The boiling point of the solvent is preferably 140 ℃ or higher and 230 ℃ or lower. When the temperature is lower than 140 ℃, not only there is a fear that the solvent may volatilize during the polymerization reaction, but also, in the case of, for example, screen printing, the solvent may volatilize quickly and plate clogging may occur. If the temperature is more than 230 ℃, it may be difficult to impart low-temperature drying/curability. Gamma-butyrolactone, cyclohexanone, diglyme, or triglyme is preferable for the purpose of high volatility, ability to impart low-temperature drying/curability, excellent varnish stability, and efficient reaction in a homogeneous system.

The amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) the polycarbonate imide resin (A) to be produced, and more preferably 0.9 to 2.0 times. When the amount is less than 0.8 times, the viscosity during synthesis tends to be too high, and synthesis tends to be difficult because stirring is impossible, and when the amount is more than 5.0 times, the reaction rate tends to be low.

In the case of the isocyanate method, the reaction temperature is preferably 60 to 200 ℃, more preferably 100 to 180 ℃. If the temperature is less than 60 ℃, the reaction time becomes too long, and if it exceeds 200 ℃, the decomposition of the monomer component may occur during the reaction. In addition, a three-dimensional reaction occurs, and gelation is likely to occur. The reaction temperature may be carried out in multiple stages. The reaction time can be suitably selected depending on the scale of the master batch, the reaction conditions to be used, and particularly the reaction concentration.

In the case of the isocyanate method, the reaction may be accelerated in the presence of an amine such as triethylamine, lutidine, picoline, undecene, triethylenediamine (1, 4-diazabicyclo [2,2,2] octane) or DBU (1, 8-diazabicyclo [5,4,0] -7-undecene), an alkali metal or alkaline earth metal compound such as lithium methoxide, sodium ethoxide, potassium butoxide, potassium fluoride or sodium fluoride, or a catalyst such as a metal or semimetal compound such as titanium, cobalt, tin, zinc or aluminum.

< production of polycarbonate imide resin (A) >

The polycarbonate imide resin (A) can be obtained by subjecting the component (a), the component (b) and the component (c) to a condensation reaction (polyimidization). The method for producing the polycarbonate imide resin of the present invention will be described below, but the present invention is not limited thereto.

The target polycarbonate imide resin (A) can be obtained by adding the component (a), the component (b), the component (c), a polymerization catalyst and a polymerization solvent to a reaction vessel, dissolving them, reacting them at 80 to 190 ℃ and preferably 100 to 180 ℃ for 5 hours or more under a nitrogen gas flow with stirring, diluting them with the polymerization solvent to an appropriate solvent viscosity, and cooling them.

The polycarbonate imide-based resin (A) used in the present invention preferably has a molecular weight corresponding to a logarithmic viscosity of 0.1 to 2.0dl/g, more preferably a molecular weight corresponding to a logarithmic viscosity of 0.2 to 1.5dl/g, in gamma-butyrolactone at 30 ℃. If the logarithmic viscosity is less than 0.1dl/g, the heat resistance may be lowered or the coating film may be brittle. Further, the paste may have a strong viscosity and the plate may be peeled off. On the other hand, if it exceeds 2.0dl/g, the polymer becomes insoluble in a solvent and tends to be insoluble during polymerization. Further, the viscosity of the varnish may be high, making handling difficult, or the adhesion to the substrate may be reduced.

The glass transition temperature of the polycarbonate imide resin (a) used in the present invention is preferably 20 ℃ or higher, and more preferably 60 ℃ or higher. When the temperature is lower than 20 ℃, heat resistance is insufficient and there is a fear that the resin may be stuck. The upper limit is not particularly limited, but from the viewpoint of solvent solubility, 300 ℃ or lower is preferable.

< epoxy resin (B) component >

The epoxy resin of the component (B) used in the present invention is not particularly limited as long as it has 2 or more epoxy groups per 1 molecule. The epoxy resin (B) is not particularly limited, and examples thereof include: bisphenol A type epoxy resins such as trade name jER (registered trademark) 828 and 1001 manufactured by Mitsubishi chemical corporation, hydrogenated bisphenol A type epoxy resins such as trade name ST-2004 and 2007 manufactured by Tokyo chemical corporation, bisphenol F type epoxy resins such as trade name YDF-170 and 2004 manufactured by Tokyo chemical corporation, brominated bisphenol A type epoxy resins such as trade name YDB-400 and 600 manufactured by Tokyo chemical corporation, phenol novolac type epoxy resins such as trade name jER (registered trademark) 152 and 154 manufactured by Mitsubishi chemical corporation, bisphenol A novolac type epoxy resins such as trade name jER (registered trademark) 157S65 and 157S70 manufactured by Mitsubishi chemical corporation, 3-functional phenol type epoxy resins such as trade name jER (registered trademark) 1032H60 manufactured by Mitsubishi chemical corporation, trade name EPPN (registered trademark) 201 manufactured by Nippon chemical corporation, tradename PN (registered trademark), Phenol novolac type EPOXY resins such as DEN-438 which is a trade name manufactured by BREN (registered trademark), Dow Chemical Company, O-cresol novolac type EPOXY resins such as YDCN-702, 703 which is a trade name manufactured by Tokyo Kasei Co., Ltd, EOCN (registered trademark) -125S, 103S, 104S which is a trade name manufactured by Nippon Kasei Co., Ltd, flexible EPOXY resins such as YD-171 which is a trade name manufactured by Tokyo Kasei Co., Ltd, Epion 1031S which is a trade name manufactured by Yuka SHELL KABUSHIKI KAISHA, Araldite (registered trademark) 0163 which is a trade name manufactured by Ciba Specialty Chemicals Inc., Denacol (registered trademark) EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, and other multifunctional EPOXY resins such as Yuze Chemtex Corporation, and EPOAKI (registered trademark) 604 which is a trade name manufactured by Yuka, Trade name YH-434 manufactured by Tokyo Chemicals, trade name TETRAD (registered trademark) -X, TETRAD-C manufactured by Mitsubishi gas Chemical Co., Ltd., GAN manufactured by Nippon Chemicals, amine-type EPOXY resin such as ELM-120 manufactured by Sumitomo Chemical Co., Ltd., heterocycle-containing EPOXY resin such as Araldite (registered trademark) PT810 manufactured by Ciba Specialty Chemicals Inc., bisphenol S-type EPOXY resin such as Celloxide (registered trademark) 1, EHPE (registered trademark) 3150, alicyclic EPOXY resin such as ERL4234 manufactured by UCC, bisphenol S-type EPOXY resin such as EPICLON (registered trademark) EXA-1514 manufactured by Nippon ink Chemical Industries, triglycidyl isocyanurate such as TEURA-4000 manufactured by Nissan Chemical Industries, and KAYIXYX-type EPOXY resin such as KAXYHA-4000 Xxylene, And bisphenol type EPOXY resins such as YL-6056, which is a trade name of YuKA SHELL EPOXY KABUSHIKI KAISHA, and these may be used singly or in combination of 2 or more.

Among these epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins having more than 2 epoxy groups in 1 molecule, and o-cresol novolac type epoxy resins are preferable. The amine-type epoxy resin is preferably a non-halogen type, and is preferably improved in compatibility with the polycarbonate imide resin (a), solvent resistance, chemical resistance and moisture resistance.

The amount of the epoxy resin (B) used in the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass, based on 100 parts by mass of the polycarbonate imide resin (a). When the amount of the epoxy resin (B) is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance and moisture resistance tend to be lowered, and when it is more than 50 parts by mass, low warpage, mechanical properties, heat resistance, varnish stability and compatibility with the polycarbonate imide resin (a) tend to be lowered.

The epoxy resin (B) used in the present invention may further contain an epoxy compound having only 1 epoxy group in 1 molecule as a diluent.

The method of adding the epoxy resin (B) is not particularly limited, and the epoxy resin (B) added in advance may be dissolved in the same solvent as that contained in the polycarbonate imide resin (a) and then added, or may be directly added to the polycarbonate imide resin (a).

< ingredient (C) of Filler >

Used in the inventionThe filler (C) (hereinafter, also simply referred to as component (C)) is preferably an inorganic filler or an organic filler. The filler (C) is not particularly limited as long as it is dispersed in the polycarbonate imide resin (a) to form a paste and can impart thixotropy (thixotropy) to the paste. That is, an inorganic filler or an organic filler capable of imparting thixotropy to the polycarbonate imide resin paste of the present invention is preferable. As such an inorganic filler, for example, Silica (SiO) can be used₂NIPPON AEROSIL co., trade name AEROSIL (registered trademark) manufactured by ltd.), alumina (Al)₂O₃) Titanium dioxide (TiO)₂) Tantalum oxide (Ta)₂O₅) Zirconium oxide (ZrO)₂) Silicon nitride (Si)₃N₄) Barium titanate (BaO. TiO)₂) Barium carbonate (BaCO)₃) Lead titanate (PbO. TiO)₂) Lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga)₂O₃) Spinel (MgO. Al)₂O₃) Mullite (3 Al)₂O₃·2SiO₂) Cordierite (2 MgO.2Al)₂O₃·5SiO₂) Talc (3 MgO.4SiO)₂·H₂O), aluminum Titanate (TiO)₂-Al₂O₃) Yttria-containing zirconia (Y)₂O₃-ZrO₂) Barium silicate (BaO 8 SiO)₂) Boron Nitride (BN), calcium carbonate (CaCO)₃) Calcium sulfate (CaSO)₄) Zinc oxide (ZnO), magnesium titanate (MgO. TiO)₂) Barium sulfate (BaSO)₄) Organic bentonite, carbon (C), organic montmorillonite (trade name Lucentite (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN, manufactured by Co-op Chemical Co. Silica and Lucentite are preferably used from the viewpoint of imparting color tone, transparency, mechanical properties, and thixotropy to the resulting paste.

The inorganic filler used in the present invention is preferably a filler having an average particle diameter of 50 μm or less and a maximum particle diameter of 100 μm or less, more preferably an average particle diameter of 20 μm or less, and most preferably an average particle diameter of 10 μm or less. The average particle diameter (median diameter) referred to herein is a value determined on a volume basis by a laser diffraction/scattering particle size distribution measuring apparatus. If the average particle size is larger than 50 μm, it may be difficult to obtain a paste having sufficient thixotropy, and the flexibility of the coating film may be reduced. When the maximum particle diameter is larger than 100. mu.m, the appearance and adhesion of the coating film tend to become insufficient.

The organic filler used in the present invention may be any one that is dispersed in the polycarbonate imide resin solution to form a paste and can impart thixotropy to the paste, and examples thereof include: polyimide resin particles, benzoguanamine resin particles, epoxy resin particles, and the like.

The amount of the filler (C) used in the present invention is preferably 1 to 25 parts by mass based on 100 parts by mass of the component (a). More preferably 2 to 15 parts by mass, and particularly preferably 3 to 12 parts by mass. When the amount of the inorganic filler or the organic filler is less than 1 part by mass, the printability tends to be lowered, and when the amount is more than 25 parts by mass, the mechanical properties such as the flexibility of the coating film and the transparency tend to be lowered.

< curing Accelerator (D) >

In order to further improve the properties such as adhesion, chemical resistance, and heat resistance, a curing accelerator may be added as the component (D) to the polycarbonate imide resin paste of the present invention. The curing accelerator (D) used in the present invention is not particularly limited as long as it can accelerate the curing reaction of the polycarbonate imide resin (a) and the epoxy resin (B).

Specific examples of such a curing accelerator (D) include: four national chemical industry Co., Ltd for 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ and other imidazole derivatives, acetoguanamine, benzoguanamine and other guanidine amines, diaminodiphenylmethane, m-xylene diamine, diaminodiphenyl sulfone, dicyandiamide, urea derivatives, melamine, polyhydrazide and other polyamines, their salts of organic acids and/or epoxy, boron trifluoride amine complexes, ethyldiamino-sym-triazine, 2, 4-diamino-sym-triazine, 2, 6-sym-triazine, 6-triazine derivatives, Tertiary amines such as trimethylamine, triethanolamine, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4, 6-tris (dimethylaminophenol), tetramethylguanidine, DBU (1, 8-diazabicyclo [5,4,0] -7-undecene), DBN (1, 5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and/or organic phosphines such as tetraphenylborate, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine, quaternary phosphonium salts such as tri-N-butyl (2, 5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, and tetraphenylphosphonium tetraphenylborate, Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride, the above-mentioned polycarboxylic acid anhydrides, diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4, 6-triphenylthiopyrylium hexafluorophosphate, Irgacure (registered trademark) 261 (manufactured by Ciba Specialty Chemicals inc.), photocationic polymerization catalysts such as OPTOMA-SP-170 (manufactured by ADEKA CORPORATION), styrene-maleic anhydride resins, equimolar reactants of phenyl isocyanate and dimethylamine, equimolar reactants of organic polyisocyanates such as toluene diisocyanate and isophorone diisocyanate and dimethylamine, and the like. These may be used alone or in combination of 2 or more. The curing accelerator having latent curability is preferable, and examples thereof include: organic acid salts and/or tetraphenylborate salts of DBU and DBN (U-CAT5002 (manufactured by San-Apro Ltd.), DBU phenate (U-CAT SA 1 (manufactured by San-Apro Ltd.), and a photo cation polymerization catalyst.

The amount of the curing accelerator (D) is preferably 0 to 20 parts by mass based on 100 parts by mass of the component (A). When the amount is more than 20 parts by mass, the storage stability of the polycarbonate imide resin composition and the heat resistance of the coating film may be lowered.

< polycarbonate imide resin paste >

The polycarbonate imide resin paste of the present invention is a composition containing the above-mentioned component (A), component (B) and component (C). Further, if necessary, the component (D) and other compounding components may be compounded at the preferable ratio. It is preferable to use a material obtained by uniformly mixing these components with a roll mill, a mixer, a triple roll mill, or the like. The mixing method is not particularly limited as long as sufficient dispersion can be obtained. It is preferable to use multiple kneading by a three-roll mill.

The polycarbonate imide resin and the paste of the present invention preferably have a viscosity at 25 ℃ in the range of 50 to 1000 dpas, more preferably 100 to 800 dpas, as measured with a brookfield viscometer (hereinafter also referred to as a B-type viscometer). When the viscosity is less than 50 dpas, the flow-out of the paste after printing becomes large and the film thickness tends to be thin. When the viscosity is more than 1000 dPas, the transferability of the paste to a substrate during printing is reduced, blurring occurs, and voids and pinholes in a printed film tend to increase.

The thixotropic index (thixotropy) is also important. The thixotropic index of the polycarbonate imide resin paste is preferably 1.2 or more, and more preferably 1.5 or more in the measurement method described later. The upper limit is preferably 7.0 or less, and more preferably 6.0 or less. When the thixotropic index is less than 1.2, the paste after printing tends to flow out more and the film thickness tends to be thin. When the amount is more than 7.0, the paste tends not to flow. The thixotropic index can be adjusted as the compounding amount of the (C) ingredient as the thixotropic index-imparting agent.

The polycarbonate imide resin composition and the paste of the present invention may contain, as required, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, known and commonly used polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, and phenothiazine, known and commonly used thickeners such as ORBEN, bentonite, and montmorillonite (montmorillonite), defoaming agents such as organosilicon-based, fluorine-based, and polymer-based, leveling agents, imidazole-based, thiazole-based, triazole-based, organoaluminum compounds, organotitanium compounds, coupling agents/adhesion-imparting agents such as organosilane compounds, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyldiphenyl phosphate, xylyldiphenyl phosphate, and tolylbis (2, 6-xylyldiphosphate), 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis (bisphenol A bis (xylyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, phosphorus flame retardants such as red phosphorus, ammonium polyphosphate, triazine, melamine cyanuric acid, succinoguanamine, ethylene bis (melamine), triguanamine, triazine cyanurate salt, melem, melam, tris (. beta. -cyanoethyl) isocyanurate, acetoguanamine, guanamine sulfate, melem sulfate, melam sulfate and nitrogen flame retardants such as melam sulfate, potassium diphenylsulfone-3-sulfonate, aromatic sulfimide metal salts, metal salt flame retardants such as alkali metal salts of polystyrene sulfonate, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, Examples of the flame retardant include inorganic flame retardants such as barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide, inorganic flame retardants such as silica, alumina, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, and zinc stannate, flame retardants/flame retardant aids such as silicone powder, heat stabilizers, antioxidants, and lubricants.

< cured coating film >

The polycarbonate imide resin paste of the present invention can be cured as a solder resist, for example, in the following manner to obtain a cured product. Specifically, the polycarbonate imide resin paste of the present invention is applied to a COF (chip On film) substrate formed by plating copper On a resin substrate such as a polyimide film in a thickness of 5 to 80 μm by a screen printing method, a spray coating method, a roll coating method, an electrostatic coating method, a curtain coating method or the like, and the coating film is pre-dried at 60 to 120 ℃ and then is subjected to main drying at 120 to 200 ℃. The drying may be carried out in air or in an inert atmosphere. Here, the method of plating copper on the resin substrate may be electroless plating or sputtering copper on the resin substrate.

The layer of the polycarbonate imide resin paste of the COF substrate obtained in this manner is used as a solder resist layer, a surface protective layer, or an adhesive layer of the COF substrate. The polycarbonate imide resin paste of the present invention is useful as a coating film-forming material for a top coating ink or a solder resist ink for a semiconductor device or various electronic components, and also useful as a coating material, a coating agent, an adhesive, and the like. Here, the solder resist layer forms a coating film on the entire surface of the circuit conductor except for the soldered portion, and serves as a protective coating film for preventing solder from adhering to an unnecessary portion and preventing the circuit from being directly exposed to air when the electronic component is wired on the printed circuit board. The surface protective layer is attached to the surface of the circuit member and used for mechanical protection or chemical protection of the electronic member from a processing step or a use environment. The adhesive layer is mainly used when a metal layer and a film layer are bonded together and then bonded together.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples at all. The measurement values described in the examples are values measured by the following methods.

< logarithmic viscosity >

The polycarbonate imide resin (A) was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration became 0.5 g/dl. The solution viscosity and the solvent viscosity of the solution were measured at 30 ℃ using a black tube and calculated by the following formulas.

Logarithmic viscosity (dl/g) ═ ln (V1/V2) ]/V3

In the above formula, V1 represents the solvent viscosity measured by a black tube, and V1 and V2 were obtained from the time taken for the polymer solution and the solvent (N-methyl-2-pyrrolidone) to pass through a capillary tube as a viscosity tube. In addition, V3 is the polymer concentration (g/dl).

< solubility in non-Nitrogen-based solvent >

When the polycarbonate imide resin (A) was polymerized, the reaction vessel was charged with the component (a), the component (b), the component (c) and gamma-butyrolactone, and the temperature was raised, and when the internal temperature reached 100 ℃, evaluation was made as to whether or not the raw materials (the component (a), the component (b) and the component (c)) dissolved.

(evaluation) O: completely dissolve

And (delta): slightly dissolved and remained

X: is substantially insoluble

< preparation of polycarbonate imide resin paste >

The polycarbonate imide resin composition is obtained by adding the epoxy resin (B) to the polycarbonate imide resin (A) and diluting the mixture with gamma-butyrolactone. Adding filler (C), curing accelerator (D), defoaming agent and leveling agent into the solution. This solution was roughly kneaded, and then kneaded repeatedly 3 times using a high-speed three-roll mill, thereby obtaining a polycarbonate imide resin paste in which a filler was uniformly dispersed.

< preparation of laminated film >

The laminate film was used as a commercially available base film made of polyimide, with a trade name of Bio-Flex (registered trademark) (TOYOBO co., ltd., product), and a trade name of S' perlex (registered trademark) (submitomo Metal Mining co., ltd., product).

On a copper circuit (L/S: 50/50) obtained from 2-layer CCL (trade name Bio-Flex (registered trademark), copper foil 18 μm, substrate 20 μm) manufactured by TOYOBO co., ltd., product name) by subtractive method, a polycarbonate imide-based resin paste was printed in a predetermined pattern with an SUS screen (MURAKAMI co., product 150 mesh, manufactured by ltd., emulsion thickness 30 μm) at a printing speed of 5 cm/sec, and dried at 80 ℃ for 6 minutes in an air atmosphere (screen printing). Then, the film was cured by heating at 120 ℃ for 90 minutes to obtain a laminated film to which a cover layer (coating film) formed of a polycarbonate imide resin paste was applied. The thickness of the coating was 15 μm. When CCL for COF manufactured by suttomo Metal Mining co., ltd (trade name S' perlex (registered trademark), copper layer 8 μm, and base material 12.5 μm) was used, a laminated film was obtained in the same manner as described above using a copper circuit obtained by a subtractive method (L/S16/16).

< Low temperature drying/curing >

The polycarbonate imide resin paste was applied to a polypropylene film having a thickness of 100 μm by an applicator so that the thickness after drying became 20 μm. Subsequently, the polypropylene film was dried at 120 ℃ for 90 minutes and then peeled off. After 0.125g of the peeled film was dissolved in 25ml of N-methyl-2-pyrrolidone at 100 ℃ for 2 hours, the solvent was filtered off with a glass filter. The remaining gel fraction was vacuum-dried at 150 ℃ for 10 hours or more, and the gel fraction was calculated and evaluated by the following formula.

Gel fraction (%). percent weight after dissolution of solvent/initial mass x 100

(evaluation) O: the gel rate is more than or equal to 85 percent

X: the gel rate is less than 85 percent

< thixotropic index (thixotropic ratio) >

The measurement was carried out using a Brookfield BH type rotary viscometer in the following manner. 90ml of a polycarbonate imide resin paste was put in a wide-mouthed light-shielding bottle (100ml), and the liquid temperature was adjusted to 25 ℃. + -. 0.5 ℃ in a constant-temperature water bath. Subsequently, the mixture was stirred for 12 to 15 seconds for 40 times with a glass rod, and then a predetermined rotor was set, and after standing for 5 minutes, the scale was read at 10rpm for 3 minutes to calculate the viscosity. Similarly, the viscosity was calculated from the value of the viscosity measured at 25 ℃ and 1rpm by the following formula.

Thixotropic index viscosity (1 rpm)/viscosity (10rpm)

< printing characteristics >

The printability of the polycarbonate imide resin paste when screen printing was performed by the method described in the above section < production of laminated film >.

(evaluation) O: good plate releasability and a flat printing surface

And (delta): poor plate releasability or unevenness observed on the printing surface

X: poor plate releasability and unevenness observed on the printing surface

< Low warpage >

The resulting laminated film was cut into 10cm × 10 cm. The sample conditioned at 25 ℃ and 65% RH for 24 hours was placed on a horizontal glass plate in a downwardly convex state, and the average height of the four corners was evaluated.

(determination) O: height less than 2mm

And (delta): the height is more than 2mm and less than 10mm

X: the height is more than 10mm

< flexibility >

The obtained laminated film was evaluated according to JIS-C-6471 (1995). The load was 300g and the diameter of the mandrel bar was 0.38mm, and the presence or absence of cracks was confirmed, and the number of bending times when cracks occurred was recorded.

(judgment) verygood: no crack occurred at more than 250 times of bending

O: no crack occurred in more than 200 times of bending

X: less than 200 times of cracking

< line insulation resistance >

The line insulation resistance value (Ω) when a dc voltage of 500V × 1 min was applied to the obtained laminated film was measured. It can be said that the higher the value, the better.

< solder Heat resistance >

The obtained laminate film was immersed in a solder bath at 260 ℃ for 30 seconds in accordance with JIS-C6481(1996), and the presence or absence of appearance abnormality such as peeling and swelling was observed.

(determination) O: no appearance abnormality

And (delta): slight appearance abnormality

X: the whole surface has appearance abnormality

< adhesion >

The obtained laminated film was formed into a checkerboard pattern of 1mm at 100 spots according to JIS-K5600-5-6(1999), and a peeling test by Cellotape was performed to evaluate the state of peeling of the checkerboard pattern.

(determination) O: at 100/100 without peeling

△：70～99/100

×：0～69/100

< Pencil hardness >

The obtained laminated film was evaluated in accordance with JIS-K5600-5-4 (1999). The pencil hardness is preferably 2H or more, and more preferably 3H or more.

< alkali resistance >

The polycarbonate imide resin paste was applied to a polypropylene film having a thickness of 100 μm by an applicator so that the thickness after drying became 20 μm. Subsequently, the polypropylene film was dried at 120 ℃ for 90 minutes and then peeled off. The obtained evaluation sample was immersed in a 10 wt% aqueous sodium hydroxide solution at 40 ℃ for 3 hours and then taken out, and the state of the coating film was evaluated.

(determination) O: no appearance abnormality

And (delta): slight appearance abnormality

X: swelling and falling off or dissolving in the coating film

Production example 1 (b) Synthesis of acid dianhydride having polycarbonate skeleton represented by the general formula (1)

Trimellitic anhydride (TMA)167g (0.87 mol) and thionyl chloride were charged into a reaction vessel and reacted to synthesize a chloride of trimellitic anhydride. Then, 183g (0.87 mol) of a chloride of trimellitic anhydride and 434g (0.43 mol) of DURANOLT5651 (available from Asahi chemical Co., Ltd., molecular weight 1000) as a diol compound were esterified in toluene at 30 ℃ to synthesize a tetracarboxylic dianhydride having a polycarbonate skeleton.

Production example 2

60.0g (0.04 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 16.4g (0.04 mol) of ethylene glycol bis (anhydrotrimellitate) (TMEG), 26.4g (0.1 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and the mixture was dissolved in 97.9g of γ -butyrolactone. Then, 83.9g of γ -butyrolactone was added thereto and diluted to room temperature after reacting the mixture at 80 to 190 ℃ for 6 hours under nitrogen gas flow with stirring, thereby obtaining brown and viscous polycarbonate imide resin solution a-1 having 35 mass% of nonvolatile components.

(production example 3)

60.0g (0.04 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 16.4g (0.04 mol) of ethylene glycol bis (anhydrotrimellitate) (TMEG), 21.1g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 3.4g (0.02 mol) of 2, 4-Tolylene Diisocyanate (TDI), 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and 96.1g of the compound was dissolved in γ -butyrolactone. Then, after reacting the resulting mixture at 80 to 190 ℃ for 6 hours under stirring in a nitrogen gas stream, 82.3g of gamma-butyrolactone was added, and the mixture was diluted and cooled to room temperature to obtain a brown and viscous polycarbonate imide resin solution A-2 having 35 mass% of nonvolatile components.

Production example 4

90.0g (0.06 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 8.2g (0.02 mol) of ethylene glycol bis (anhydrotrimellitate) (TMEG), 21.1g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 3.4g (0.02 mol) of 2, 4-Tolylene Diisocyanate (TDI), 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and dissolved in 117.9g of γ -butyrolactone. Then, 101.1g of gamma-butyrolactone was added thereto and diluted to room temperature after reacting the mixture at 80 to 190 ℃ for 6 hours under nitrogen gas flow with stirring, thereby obtaining brown and viscous polycarbonate imide resin solution A-3 having 35 mass% of nonvolatile components.

Production example 5

120.0g (0.08 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 21.1g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 3.4g (0.02 mol) of 2, 4-Tolylene Diisocyanate (TDI), 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and the mixture was dissolved in 139.6g of γ -butyrolactone. Then, 119.7g of γ -butyrolactone was added thereto and diluted to room temperature after reacting the mixture at 80 to 190 ℃ for 6 hours under nitrogen gas flow with stirring, thereby obtaining brown and viscous polycarbonate imide resin solution a-4 having 35 mass% of nonvolatile components.

(production example 6)

90.0g (0.06 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 8.2g (0.02 mol) of ethylene glycol bis (anhydrotrimellitate) (TMEG), 25.0g (0.1 mol) of 4, 4-diphenylmethane diisocyanate (MDI) as a diisocyanate, 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst, and 118.3g of gamma-butyrolactone were added and dissolved therein. Then, 101.4g of gamma-butyrolactone was added thereto and diluted to room temperature after reacting the mixture at 80 to 190 ℃ for 6 hours under nitrogen gas flow with stirring, thereby obtaining brown and viscous polycarbonate imide resin solution A-5 having 35 mass% of nonvolatile components.

Production example 7

75.0g (0.05 mol) of the component (b) synthesized in production example 1, 3.8g (0.02 mol) of trimellitic anhydride, 12.3g (0.03 mol) of ethylene glycol bis (anhydrotrimellitate) (TMEG), 26.4g (0.1 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, and 0.08g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and dissolved in 108.8g of γ -butyrolactone. Then, 93.2g of gamma-butyrolactone was added thereto and diluted to room temperature after reacting the mixture at 80 to 190 ℃ for 6 hours under nitrogen gas flow with stirring, thereby obtaining brown and viscous polycarbonate imide resin solution A-6 having 35 mass% nonvolatile components.

(example 1)

10 parts by mass of JeR154 (trade name of phenol novolac epoxy resin, manufactured by Mitsubishi chemical) was added to 100 parts by mass of nonvolatile components in the polycarbonate imide resin solution A-1 used in production example 2, and the mixture was diluted with γ -butyrolactone. Further, 3.0 parts by mass of Lucite SEN (synthetic montmorillonite Co., Ltd.) as a filler, 1.0 part by mass of Ucat5002 (manufactured by San-Apro Ltd.) as a curing accelerator, 0.9 part by mass of BYK-054 (manufactured by BYK Co., Ltd.) as an antifoaming agent, 1.9 parts by mass of BYK-354 (manufactured by BYK Co., Ltd.) as a leveling agent, and 0.5 part by mass of BYK-E410 (manufactured by BYK Co., Ltd.) as a rheology control agent were added to the mixture to obtain a polycarbonate imide resin composition. The composition was roughly kneaded, and then kneaded repeatedly 3 times using a high-speed three-roll mill, thereby obtaining a polycarbonate imide resin paste (1) of the present invention in which a filler was uniformly dispersed and which had thixotropy. After adjusting the viscosity with gamma-butyrolactone, the solution had a viscosity of 232 poise and a thixotropic index of 1.48. The polycarbonate imide resin paste (1) of the present invention was printed in a predetermined pattern on a copper circuit (L/S: 50/50) obtained by subtractive method from 2-layer CCL (product name Bio-Flex (registered trademark), copper foil 18 μm, substrate 20 μm) manufactured by TOYOBO co., ltd., with a SUS screen (MURAKAMI co., product 150 mesh, emulsion thickness 30 μm) at a printing speed of 5 cm/sec, and dried at 80 ℃ for 6 minutes in an air atmosphere. Then, the COF substrate to which a coating layer (coating film) formed of a polycarbonate imide resin paste was applied was obtained by heat curing at 120 ℃ for 90 minutes (evaluation sample 1). The thickness of the coating was 15 μm. The evaluation results are shown in table 1.

(examples 2 to 9)

Pastes were prepared in the same manner as in example 1 except that the solutions of the polycarbonate imide resin (a) and the components (B) to (D) were used as described in table 1, and then, evaluation samples 2 to 9 were prepared. The evaluation results are shown in table 1.

(examples 10 and 11)

A polycarbonate imide resin paste of the present invention was printed in a predetermined pattern at a printing speed of 5 cm/sec using an SUS screen (murakaco., ltd., 150 mesh, 30 μm emulsion thickness) on a copper circuit (L/S ═ 16/16) obtained by subtractive method using CCL (trade name S' perlex (registered trademark), copper layer 8 μm, substrate 12.5 μm for COF manufactured by Sumitomo Metal Mining co., ltd., product) with a printing speed of 5 cm/sec, except that the solution of the polycarbonate imide resin (a) and the components (B) to (D) were each as described in table 1, and the paste was prepared in the same manner as in example 1. Then, the COF substrate was cured by heating at 120 ℃ for 90 minutes, to which a coating layer (coating film) formed of a polycarbonate imide resin paste was applied (evaluation samples 10 and 11). The thickness of the coating was 15 μm. The evaluation results are shown in table 1.

Comparative example 1

28.8g (0.1 mol) of trimellitic anhydride, 31.7g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 5.2g (0.02 mol) of 2, 4-Toluene Diisocyanate (TDI), 0.11g of 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added, and dissolved in 52.5g of γ -butyrolactone. Then, the mixture is reacted at 80 to 190 ℃ under a nitrogen stream with stirring. However, gamma-butyrolactone was insoluble and blurred in the solution (A-6). The evaluation results are shown in table 2.

Comparative example 2

A paste was prepared in the same manner as in example 1, except that the polycarbonate imide resin solution a-3 obtained in production example 3 and jER154 (trade name of phenol novolac epoxy resin, manufactured by mitsubishi chemical corporation) were used without mixing. Since the epoxy resin is not blended, the paste is not sufficiently cured, and the solder heat resistance and alkali resistance are reduced. The evaluation results are shown in table 2.

Comparative example 3

A paste was prepared in the same manner as in example 1, except that the polycarbonate imide resin solution a-3 obtained in production example 3 and no filler were used. Since no filler was compounded, the thixotropy was insufficient, and screen printing could not be performed. Therefore, a laminated film sample for evaluation cannot be produced.

[ Table 1]

[ Table 2]

Industrial applicability

The polycarbonate imide resin paste obtained by the present invention has both excellent heat resistance and flexibility as a film-forming material. Therefore, the ink is useful not only for top coating inks and solder resist inks for various electronic components such as COF substrates, but also for a wide range of electronic devices as a coating material, a coating agent, an adhesive, and the like, and is expected to contribute greatly to the industrial field.

Claims

1. A polycarbonate imide resin paste for a solder resist, which contains: a polycarbonate imide resin as component (A), an epoxy resin having 2 or more epoxy groups per 1 molecule as component (B), and a thixotropic property-imparting filler as component (C),

the polycarbonate imide resin comprises (a) a tri-and/or tetra-carboxylic acid derivative having an acid anhydride group, (b) an acid dianhydride represented by the general formula (1) having a polycarbonate skeleton, and (c) an isocyanate compound as essential copolymerization components,

in the general formula (1), m and n are each an integer of 1 or more, and m are each optionally the same or different,

wherein (c) the isocyanate compound is diphenylmethane-4, 4 ' -diisocyanate, toluene-2, 4-diisocyanate, m-xylylene diisocyanate, 3 ' -dimethylbiphenyl-4, 4 ' -diisocyanate, or 2,2 ' -dimethylbiphenyl-4, 4 ' -diisocyanate,

the filler (C) is an inorganic filler having an average particle diameter of 50 μm or less and a maximum particle diameter of 100 μm or less.

2. A polycarbonate imide resin paste for a solder resist according to claim 1, wherein (a) the tri-and/or tetra-basic polycarboxylic acid derivative having an acid anhydride group is pyromellitic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, or 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride.

3. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, wherein the copolymerization amount of the component (a) is 10 mol% or more and 90 mol% or less, assuming that all acid components are 100 mol%.

4. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, wherein the copolymerization amount of the component (b) is 10 mol% or more and 90 mol% or less, assuming that all acid components are 100 mol%.

5. A polycarbonate imide-based resin paste for a solder resist according to claim 1 or 2, wherein the logarithmic viscosity of the polycarbonate imide-based resin (a) at 30 ℃ in γ -butyrolactone is from 0.1dl/g to 2.0 dl/g.

6. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, wherein the glass transition temperature of the polycarbonate imide resin (a) is 20 ℃ or higher and 300 ℃ or lower.

7. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, wherein the amount of the epoxy resin (B) used is 1 to 50 parts by mass per 100 parts by mass of the polycarbonate imide resin (a).

8. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, further comprising a curing accelerator as the component (D).

9. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, which has a thixotropic index of 1.2 or more.

10. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, wherein the viscosity measured with a brookfield viscometer is in the range of 50 to 1000dPa s at 25 ℃.

11. A polycarbonate imide resin paste for a solder resist according to claim 1 or 2, which is used for COF.

12. An electronic component comprising a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the polycarbonate imide resin paste for a solder resist according to any one of claims 1 to 11.