WO2016067925A1

WO2016067925A1 - Polycarbonate-imide-based resin paste, and electronic component having solder resist layer, surface protective layer, interlayer dielectric layer, or adhesive layer each obtained by curing said paste

Info

Publication number: WO2016067925A1
Application number: PCT/JP2015/079128
Authority: WO
Inventors: 翔子内山; 智晴栗田
Original assignee: 東洋紡株式会社
Priority date: 2014-10-28
Filing date: 2015-10-15
Publication date: 2016-05-06
Also published as: CN106715590A; JP6699546B2; JPWO2016067925A1; TW201623486A; TWI687492B; KR20170077060A; CN106715590B; KR102285047B1

Abstract

Provided is a polycarbonate-imide-based resin paste which is excellent in terms of (1) solubility in nitrogen-free solvents, (2) low-temperature dryability/curability, (3) low warpage, (4) flexing characteristics, (5) printability, and (6) alkali resistance and in terms of heat resistance, chemical resistance, and electrical property. Also provided is an electronic component having a solder resist layer, surface protective layer, or adhesive layer which is obtained by curing the paste. The polycarbonate-imide-based resin paste comprises component (A), which is a polycarbonate-imide resin obtained from comonomer ingredients essentially including (a) one or more tri- and/or tetravalent polycarboxylic acid derivatives having an acid anhydride group, (b) an acid dianhydride having a polycarbonate skeleton that has a specific structure, and (c) an isocyanate compound or amine compound, component (B), which is an epoxy resin having two or more epoxy groups per molecule, and component (C), which is a filler.

Description

Electronic component having polycarbonate imide resin paste and solder resist layer, surface protective layer, interlayer insulation layer or adhesive layer obtained by curing the paste

The present invention relates to a polycarbonate imide resin paste. Particularly useful for COF (Chip On Film) substrate applications, having excellent heat resistance and flexibility, and suitable for coating methods such as printing presses, dispensers or spin coaters, and obtained by curing the paste. The present invention relates to an electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer.

Generally, polyimide resins are widely used as insulating materials for electric and electronic equipment because they are excellent in heat resistance, insulation and chemical resistance. In particular, it is frequently used as a raw material for COF substrates, and is applied to wiring board materials and mounting substrate materials for electronic devices that require flexibility and small space. For example, device mounting substrates for display devices used for liquid crystal display devices, plasma displays, organic EL displays, etc., inter-board relay cables for smart phones, tablet device terminals, digital cameras, portable game machines, operation switch unit substrates, etc. Alternatively, it is widely used as a coverlay material (circuit protective layer) for these substrates. In particular, in a printed wiring board, a solder resist is widely used as a permanent protective film for circuits. Solder resist is a film formed on the entire surface excluding the part to be soldered of the circuit conductor. When wiring electronic parts on the printed wiring board, it prevents the solder from adhering to unnecessary parts and the circuit. Is used as a protective film to prevent direct exposure to air.

By the way, since the solder resist layer, the surface protective layer or the adhesive layer, which is a component of the COF substrate, is often applied and printed in the form of a solution, a composition comprising a solvent-soluble ring-closing polyimide resin as the material thereof However, conventionally, as a solvent for varnishing a polyimide resin, a high-boiling nitrogen solvent such as N-methyl-2-pyrrolidone has been used. The above high temperature and long time curing process is required, and there is a problem in that the electronic components are thermally deteriorated.

Furthermore, since polyimide resins are generally hard and have a high elastic modulus, when laminated on a substrate such as a film or copper foil, warping or the like occurs due to the difference in elastic modulus, which has a problem in the subsequent process. In addition, the cured film lacks flexibility and has a problem of poor flexibility.

In addition, examples of polyimide resins that are soluble in non-nitrogen solvents and have low warpage and flexibility in which the resin is made flexible and have a low elastic modulus include (Patent Document 1), (Patent Document 2), and the like. Discloses a polysiloxane-modified polyimide resin.

These polysiloxane-modified polyimide resins use an expensive diamine having a dimethylsiloxane bond as a starting material for reducing the elastic modulus, and are inferior in economic efficiency. In addition, as the amount of polysiloxane copolymerized increases, there is a problem that adhesion, solvent resistance, and chemical resistance decrease.

Moreover, the composition which improved the moldability of the resin composition by mixing a fixed amount of polycarbonate resin with a polyimide resin and imparting flexibility is disclosed (Patent Document 3) and (Patent Document 4). . Furthermore, the thermoplastic resin composition which improved the moldability by mixing a polyimide resin, an epoxy resin, and a polycarbonate resin is disclosed (Patent Document 5). These are listed as resins suitable for melt kneading and melt extrusion, and have excellent heat resistance and mechanical strength, but are not soluble in non-nitrogen solvents and have low warpage and flexibility. It's hard to say.

Japanese Patent Laid-Open No. 7-304950 JP-A-8-333455 JP-A-5-320492 JP-A-6-136267 JP-A-62-2758

As can be seen from such examples, in the conventional techniques so far, (1) non-nitrogen solvent solubility (2) low temperature drying / curability (3) low warpage (4) flexibility (5) printing characteristics, 6) A polyimide resin paste applicable as a solder resist layer, a surface protective layer or an adhesive layer that simultaneously satisfies alkali resistance has not been obtained.

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

As component (A), (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (1), and ( c) a polycarbonate imide resin containing an isocyanate compound or an amine compound as an essential copolymer component,
(B) As an ingredient, an epoxy resin having two or more epoxy groups per molecule,
(C) Polycarbonate imide resin paste containing a filler as a component.

(In the general formula (1), m and n are each an integer of 1 or more, and a plurality of m may be the same or different from each other.)

Furthermore, it is preferable to contain a curing accelerator as component (D).

It is preferable that the degree of change of the polycarbonate imide resin paste is 1.2 or more.

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

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

According to the present invention, (1) non-nitrogen solvent solubility (2) low temperature drying / curing properties (3) low warpage (4) flexibility (5) printing properties (6) Disclosed is a polycarbonate imide resin paste having excellent alkali resistance and excellent 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. Can do.

Hereinafter, the present invention will be described in detail. The polycarbonate imide resin paste of the present invention is composed of a polycarbonate imide resin (A) as component (A) and an epoxy resin having two or more epoxy groups per molecule (hereinafter referred to as epoxy resin (B) as component (B). ) And (C) component contains an inorganic or organic filler (hereinafter also referred to as filler (C)). The polycarbonate imide resin (A) includes (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an oxalic anhydride group (hereinafter also referred to as component (a)), (b) a general formula ( An essential copolymer of an acid dianhydride having a polycarbonate skeleton represented by 1) (hereinafter also referred to as component (b)) and (c) an isocyanate compound or an amine compound (hereinafter also referred to as component (c)). Ingredients.

<Polycarbonateimide resin (A) component>
The polycarbonate imide resin (A) used in the present invention will be described. The polycarbonate imide resin (A) includes (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, and (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (1). And (c) a polycarbonate imide resin having an isocyanate compound or an amine compound as an essential copolymer component, preferably the components (a), (b) and (c) as essential copolymer components. Polycarbonate imide resin.

<(A) Trivalent and / or tetravalent polycarboxylic acid derivative having acid anhydride group>
As the component (a) constituting the polycarbonate imide resin (A) used in the present invention, a trivalent and / 4 valent acid anhydride group that generally reacts with an isocyanate component or an amine component to form a polyimide resin. The polycarboxylic acid derivative is not particularly limited, 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. For example, trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bisanhydro trimellitate, propylene glycol bisan hydrotrimellitate, 1,4- Alkylene glycol bisan hydrotrimellitate such as butanediol bisanhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis anhydro trimellitate, 3, 3 '-4,4'-benzophenonetetracarboxylic dianhydride, 3,3'-4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, , 4,5,8-Naphthalene Tracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenylsulfonetetracarboxylic 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 (2,3- or 3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2 , 2-bis [4- (2,3- or 3,4-dicarboxyl Phenoxy) phenyl] propane dianhydride, or 1,3-bis (3,4-carboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, and the like.

Further, the aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, but for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic acid 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 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3 ) -Tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2,2,1] heptane-2,3,5,6-tetracarboxylic Acid dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3 -(2,3) -tetracarboxylic dianhydride, dicyclohexyl-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 acid dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, or hexa hydro trimellitic anhydride, and the like.

These trivalent and / or tetravalent polycarboxylic acid derivatives having an acid anhydride group may be used alone or in combination of two or more. In view of heat resistance, transparency, adhesion, solubility, cost, pyromellitic anhydride, trimellitic anhydride, ethylene glycol bisanhydro trimellitate, 3,3'-4,4 ' -Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride are preferred, trimellitic anhydride, and ethylene glycol bisanhydro trimellitate are more preferred.

The amount of copolymerization of component (a) is preferably 10 mol% or more and 90 mol% or less, and more preferably 20 mol% or more and 80 mol% or less, when the total acid component to be reacted is 100 mol%. Preferably, it is 30 mol% or more and 70 mol% or less. If it is less than 10 mol%, flame retardancy, mechanical properties, and heat resistance may not be obtained. If it exceeds 90 mol%, the components (b) and (c) described later cannot be copolymerized in a sufficient amount. Sometimes. Therefore, low warpage and solubility in non-nitrogen solvents may be reduced.

<(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 a common component as a flexible component that imparts low warpage, non-nitrogen solvent solubility, etc. to the polycarbonate polyimide resin (A). Polymerized. By copolymerizing these, the elastic modulus of the polycarbonate imide resin (A) is lowered and the solubility 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. Although an upper limit is not specifically limited, It is preferable that it is 20 or less, More preferably, it is 10 or less. The plurality of m may be the same or different. n is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. Although an upper limit is not specifically limited, It is preferable that it is 20 or less, More preferably, it is 10 or less.

(B) Although it does not specifically limit as a method to manufacture a component, It can synthesize | combine with a well-known reaction method from the chloride of trimellitic anhydride and a polycarbonate diol compound. More specifically, first, a polycarbonate diol compound and a deoxidizing agent are put into a chloride solution of trimellitic anhydride dissolved in a solvent and stirred for 0.5 to 24 hours. The reaction temperature is −20 to 50 ° C., and more preferably 20 to 40 ° C. from the viewpoint of reaction selectivity. As a reaction ratio between the trimellitic anhydride chloride and the polycarbonate diol compound, it is preferable to react 2 mol or more of trimellitic anhydride chloride with respect to 1 mol of the polycarbonate diol compound. The concentration of the solute in the reaction is preferably 5 to 80% by weight, more preferably 40 to 60% by weight. After completion of the reaction, the precipitated hydrochloride is filtered off, and the solvent is concentrated to give an acid dianhydride having a polycarbonate skeleton represented by the general formula (1) (hereinafter referred to as a polycarbonate skeleton-containing tetracarboxylic dianhydride). Say).

Examples of the method for producing the polycarbonate diol compound include transesterification between a diol as a raw material and carbonates, and a dehydrochlorination reaction between a diol as a raw material and phosgene. Although it does not specifically limit as carbonate which is a raw material, For example, dialkyl carbonates, such as a dimethyl carbonate and a diethyl carbonate, are mentioned.

As the diol, a linear diol compound having two hydroxyl groups can be used. Although not particularly limited, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like can be mentioned.

As a commercial product of the polycarbonate diol compound that can be used in the present invention, Duranor series manufactured by Asahi Kasei Chemicals Corporation and the like can be mentioned. For example, DURANOL (registered trademark) -T5650E (Asahi Kasei Chemicals Co., Ltd. polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 500), DURANOL-T5651 (Asahi Kasei Chemicals Co., Ltd.) Polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 1,000, DURANOL-T5652 (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation: 1,5-pentanediol / 1,6- Hexanediol, number average molecular weight of about 2,000) and the like.

The amount of copolymerization of component (b) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, when the total acid component is 100 mol%. It is particularly preferably 30 mol% or more and 70 mol% or less. If it is less than 10 mol%, the elastic modulus may not be sufficiently reduced, and warping may occur when laminated, and the solubility in non-nitrogen solvents may be reduced. Therefore, the resin may be deposited within 5 months at 5 ° C to 30 ° C. On the other hand, when it exceeds 90 mol%, the above-mentioned component (a) and the component (c) described later cannot be contained in a sufficient amount, so that 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 is an aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate, Or the polyamine corresponding to these is mentioned. An aromatic polyisocyanate or an aromatic polyamine is preferably used. Specific examples of aromatic polyisocyanates include, but are not 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, diphenylme -3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate (TDI), tolylene- 2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate, 3,3' Or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'- Diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate Sulfonates, and the like. In consideration of heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4′-diisocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, 3,3′- or 2,2 ′ -Dimethylbiphenyl-4,4'-diisocyanate is preferred, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate (o-tolidine diisocyanate, TODI) and tolylene-2,4-diisocyanate (TDI) are more preferred. These can be used alone or in combination of two or more. Moreover, when using an aromatic polyamine, the polyamine corresponding to the said aromatic polyisocyanate can be used.

When the amine component used in the polycarbonate imide resin (A) of the present invention is 100 mol%, it is preferable that any one of the isocyanate compounds is 100 mol%. When a diamine compound corresponding to the isocyanate is used instead of the isocyanate, it passes through a polyamic acid as a precursor of the polycarbonate polyimide resin. When passing through a polyamic acid, it is necessary to imidize at a high temperature of about 200 ° C. or more after applying a paste containing polyamic acid to a substrate such as COF (Chip On Film), which may cause thermal degradation of COF. Yes, and there may be restrictions on equipment. In the present invention, since only an isocyanate compound containing TODI is used as an amine component, it can be treated at a lower temperature than a polyamic acid-containing paste, and there is no such problem, which is preferable.

<Other acid components>
The polycarbonate imide-based resin (A) used in the present invention may be further copolymerized with aliphatic, alicyclic, or aromatic polycarboxylic acids as necessary as long as the target performance is not impaired. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosane diacid, fumaric acid Examples of alicyclic dicarboxylic acids such as maleic acid, dimer acid, hydrogenated dimer acid and the like include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane, and the like. Examples of aromatic dicarboxylic acids such as dicarboxylic acid and 4,4′-dicyclohexyldicarboxylic acid include isophthalic acid. Terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, stilbene 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, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferable.

Further, in addition to the component (b), other flexible components may be copolymerized as necessary within the range not impairing the intended performance. For example, aliphatic / aromatic polyester diols (trade name VYLON (registered trademark) 220 manufactured by Toyobo Co., Ltd.), aliphatic / aromatic polycarbonate diols (produced by Daicel Chemical Industries, Ltd., trade name PLACEL (registered trademark)) ) -CD220, manufactured by Kuraray Co., Ltd., trade names Kuraray polyol C-1015N, C-2015N, etc., manufactured by Asahi Kasei Chemicals Corporation, trade names Duranol (registered trademark) T5650E, T5650J, T5651, T5652, etc.), polycaprolactone diol (Daicel Chemical Industries, Ltd., trade name PLACEL (registered trademark) -220, etc.), carboxy-modified acrylonitrile butadiene rubbers (Ube Industries, Ltd., trade name HyproCTBN1300 × 13, etc.), polydimethylsiloxane diol, poly Examples thereof include polysiloxane derivatives such as methylphenylsiloxane diol and carboxy-modified polydimethylsiloxanes.

As a method for producing the polycarbonate imide resin (A), a method (isocyanate) produced from a polycarboxylic acid component having an acid anhydride group (component (a) and component (b)) and an isocyanate component (component (c)). Method), or a method of reacting a polycarboxylic acid component having an acid anhydride group (components (a) and (b)) with an amine component (component (c)) to form an amic acid, followed by ring closure (direct method) There are known methods. Industrially, the isocyanate method is advantageous.

In the case of the isocyanate method, the amount of component (a), component (b), and component (c) is such that the ratio of the number of acid anhydride groups to the number of isocyanate groups is: number of isocyanate groups / number of acid anhydride groups = 0.8 to 1. 2 is preferable. If it is less than 0.8, it may be difficult to increase the molecular weight of the polycarbonate imide resin (A), heat resistance and flexibility may be lowered, and the coating film may be brittle. On the other hand, when the viscosity is higher than 1.2, the viscosity of the polycarbonate imide resin (A) may be increased, and the separation of the plate may be deteriorated at the time of printing when the ink is formed.

The polymerization reaction of the polycarbonate imide resin (A) used in the present invention is preferably performed in a non-nitrogen solvent. Specifically, in the presence of one or more organic solvents selected from the group consisting of ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents, for example, in the isocyanate method, carbon dioxide that is liberated is generated. It is preferable to carry out the heat condensation while removing from the reaction system.

The solvent is not particularly limited, but examples of ether solvents include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), and triethylene glycol diethyl ether (ethyl triglyme). Examples of ester solvents include γ-butyrolactone and cellosolve acetate; examples of ketone solvents include methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; examples of aromatic hydrocarbon solvents include toluene, xylene, and sorbeso. Can be mentioned. These may be used alone or in combination of two or more.

When producing the polycarbonate imide resin (A), it is preferable to select and use a solvent that dissolves the polycarbonate imide resin (A) to be produced, and is suitable as a solvent for the polycarbonate imide resin paste after polymerization. More preferably, one is used. By doing so, complicated operations such as solvent replacement are eliminated, and it becomes possible to manufacture at low cost. Further, the boiling point of the solvent is preferably 140 ° C. or higher and 230 ° C. or lower. When the temperature is lower than 140 ° C., the solvent may be volatilized during the polymerization reaction. In addition, when screen printing is performed, for example, the solvent is rapidly volatilized and the plate may be clogged. If it exceeds 230 ° C., it may be difficult to impart low temperature drying / curing properties. Γ-butyrolactone, cyclohexanone, diglyme, or triglyme is preferable for relatively high volatility, imparting low temperature drying / curing property, excellent varnish stability, and conducting the reaction in a homogeneous system efficiently.

The amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio), more preferably 0.9 to 2.0 times that of the polycarbonate imide resin (A) to be produced. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir, and if it exceeds 5.0 times, the reaction rate tends to decrease.

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

In the case of the isocyanate method, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo [2,2,2] octane), DBU (1,8-diazabicyclo [5,4,0] are used to accelerate the reaction. ] -7-undecene), alkali metals such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride, sodium fluoride, alkaline earth metal compounds or titanium, cobalt, The reaction may be carried out in the presence of a catalyst such as a metal such as tin, zinc or aluminum, or a metalloid compound.

<Production of polycarbonate imide resin (A)>
If an example of the manufacturing method of polycarbonate imide-type resin (A) is given, it can obtain by making (a) component, (b) component, and (c) component condense-react (polyimidize). Hereinafter, although the manufacturing method of the polycarbonate imide-type resin of this invention is illustrated, this invention is not limited by this.

The components (a), (b), (c), polymerization catalyst and polymerization solvent are added to the reaction vessel, dissolved, and then stirred at 80 to 190 ° C., preferably 100 to 180 ° C. with stirring in a nitrogen stream. After reacting for 5 hours or more, the target polycarbonate imide resin (A) can be obtained by diluting to an appropriate solvent viscosity with a polymerization solvent and cooling.

The polycarbonate imide resin (A) used in the present invention preferably has a molecular weight corresponding to a logarithmic viscosity of 0.1 to 2.0 dl / g at 30 ° C. in γ-butyrolactone, more preferably It has a molecular weight corresponding to a logarithmic viscosity of 2 to 1.5 dl / g. When the logarithmic viscosity is less than 0.1 dl / g, the heat resistance may be lowered or the coating film may be brittle. In addition, the tackiness of the paste is strong and the release of the plate may worsen. On the other hand, when it exceeds 2.0 dl / g, it becomes difficult to dissolve in a solvent, and it tends to become insoluble during polymerization. In addition, the viscosity of the varnish becomes high and handling becomes difficult, and 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 ° C. or higher, more preferably 60 ° C. or higher. If it is less than 20 degreeC, heat resistance may be insufficient and resin may block. Although an upper limit is not specifically limited, 300 degrees C or less is preferable from a solvent solubility viewpoint.

<Epoxy resin (B) component>
The epoxy resin of component (B) used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups per molecule. The epoxy resin (B) is not particularly limited. For example, bisphenol A type epoxy resin such as trade name jER (registered trademark) 828, 1001 manufactured by Mitsubishi Chemical Corporation, or trade name ST manufactured by Toto Kasei Co., Ltd. -Hydrogenated bisphenol A type epoxy resins such as 2004 and 2007, brand name YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy such as 2004, brand names YDB-400, 600 manufactured by Toto Kasei Co., Ltd. Brominated bisphenol A type epoxy resin, trade name jER (registered trademark) 152, 154 manufactured by Mitsubishi Chemical Co., Ltd., phenol novolak type epoxy resin such as trade name jER (registered trademark) 157S65 manufactured by Mitsubishi Chemical Corporation, Bisphenol A novolac type epoxy resin such as 157S70, trifunctional phenol type epoxy tree such as trade name jER (registered trademark) 1032H60 manufactured by Mitsubishi Chemical Corporation Fat, a phenol novolac type epoxy resin such as Nippon Kayaku Co., Ltd. trade name EPPN (registered trademark) -201, BREN (registered trademark), Dow Chemical Co., Ltd. trade name DEN-438, manufactured by Tohto Kasei Co., Ltd. Trade name YDCN-702, 703, trade name EOCN (registered trademark) -125S, 103S, 104S, etc. manufactured by Nippon Kayaku Co., Ltd., trade name YD, manufactured by Toto Kasei Co., Ltd. -171 and other flexible epoxy resins, Yuka Shell Epoxy Co., Ltd. trade name Epon 1031S, Ciba Specialty Chemicals Co., Ltd. trade name Araldite (registered trademark) 0163, manufactured by Nagase Chemtech Co., Ltd. Product Name Denacol (registered trademark) EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-3 No. 1 polyfunctional epoxy resin, Yuka Shell Epoxy Co., Ltd. trade name Epicoat (registered trademark) 604, Toto Kasei Co., Ltd. trade name YH-434, Mitsubishi Gas Chemical Co., Ltd. trade name TETRAD (Registered trademark) -X, TETRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, and other amine type epoxy resins, Ciba Specialty Chemicals Co., Ltd. Products such as Araldite (registered trademark) PT810 made of heterocyclic ring-containing epoxy resin, Daicel Chemical Industries, Ltd., trade name Celoxide (registered trademark) 2021, EHPE (registered trademark) 3150, UCC ERL4234, etc. Cyclic epoxy resins, bisphenol S-type epoxy resins such as Epicron (registered trademark) EXA-1514 manufactured by Dainippon Ink and Chemicals, manufactured by Nissan Chemical Industries, Ltd. Triglycidyl isocyanurate such as TEPIC (registered trademark), bixylenol type epoxy resin such as trade name YX-4000 manufactured by Yuka Shell Epoxy Co., Ltd., trade name YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd. Examples thereof include bisphenol type epoxy resins, and these may be used alone or in combination of two or more.

Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin having more than two epoxy groups in one molecule, and o-cresol novolak type epoxy resin are preferable. The amine type epoxy resin is non-halogen type, and is preferable in terms of 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, particularly preferably 3 to 100 parts by mass with respect to 100 parts by mass of the polycarbonate imide resin (A). 30 parts by mass. When the blending 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 decrease, and when it exceeds 50 parts by mass, low warpage, mechanical properties, There exists a tendency for heat resistance, varnish stability, and compatibility with a polycarbonate imide-type resin (A) to fall.

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

The addition method of the epoxy resin (B) is not particularly limited, and it may be added after dissolving the epoxy resin (B) to be added in advance in the same solvent as that contained in the polycarbonate imide resin (A). Alternatively, it may be added directly to the polycarbonate imide resin (A).

<Filler (C) component>
The filler (C) used in the present invention (hereinafter also simply referred to as component (C)) is preferably an inorganic or organic filler. The filler (C) is not particularly limited as long as it can be dispersed in the above-mentioned polycarbonate imide resin (A) to form a paste and can impart thixotropic properties (thixotropic properties) to the paste. That is, an inorganic or organic filler that can impart thixotropic properties to the polycarbonate imide resin paste of the present invention is preferable. Examples of such inorganic fillers include silica (SiO ₂ , trade name AEROSIL (registered trademark) manufactured by Nippon Aerosil Co., Ltd.), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), zirconate titanate lead (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O _3), spinel _{_{(MgO · Al 2 O 3)}} , mullite _{_{_{(3Al 2 O 3 · 2SiO 2}}} ), cordierite (2MgO _{_{_{· 2Al 2 O 3 · 5SiO 2}}} ), talc _{_{(3MgO · 4SiO 2 · H 2}} O), aluminum titanate _{_{_{(TiO 2 -Al 2 O 3)}}} , yttria-containing zirconia _{_{_{(Y 2 O 3 -ZrO 2)}}} , silicate Barium (BaO · 8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate ( CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), organic smectite (trade name manufactured by Coop Chemical Co., Ltd.) Tight (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN) and the like can be used, and these may be used alone or in combination of two or more. From the viewpoint of imparting color tone, transparency, mechanical properties and thixotropy of the obtained paste, it is preferable to use silica or lucentite.

The inorganic filler used in the present invention preferably has an average particle size of 50 μm or less and a maximum particle size of 100 μm or less, more preferably an average particle size of 20 μm or less, and most preferably an average particle size of 10 μm or less. The average particle diameter (median diameter) referred to here is a value obtained on a volume basis using a laser diffraction / scattering particle size distribution measuring apparatus. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having sufficient thixotropy, and the flexibility of the coating film may be lowered. When the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient.

The organic filler used in the present invention is not limited as long as it can be dispersed in the above-mentioned polycarbonate imide resin solution to form a paste and can impart thixotropy to the paste. 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 when the component (A) is 100 parts by mass. More preferably, it is 2 to 15 parts by mass, and particularly preferably 3 to 12 parts by mass. If the blending amount of the inorganic or organic filler is less than 1 part by mass, the printability tends to decrease, and if it exceeds 25 parts by mass, the mechanical properties such as the flexibility of the coating film and the transparency tend to decrease.

<Curing accelerator (D)>
To the polycarbonate imide resin paste of the present invention, a curing accelerator can be added as the component (D) in order to further improve the properties such as adhesion, chemical resistance and heat resistance. 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, for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ manufactured by Shikoku Chemicals Co., Ltd. -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, etc. Guanamines, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, and other organic acid salts and / or epoxies thereof Adducts, amine complexes of boron trifluoride, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanol Amine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, DBU ( Tertiary amines such as 1,8-diazabicyclo [5,4,0] -7-undecene) and DBN (1,5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and / Or tetraphenylborate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine Quaternary compounds such as phosphine, triphenylphosphine, tris-2-cyanoethylphosphine, etc., tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, etc. Quaternary ammonium salts such as phosphonium salts, benzyltrimethylammonium chloride, phenyltributylammonium chloride, the polycarboxylic acid anhydride, diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyri Rium hexafluorophosphate, Irgacure (registered trademark) 261 (manufactured by Ciba Specialty Chemicals), Optoma-SP- 170 (manufactured by ADEKA), photocationic polymerization catalyst, styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, organic polyisocyanate such as tolylene diisocyanate, isophorone diisocyanate and dimethylamine, etc. Molar reactants and the like. You may use these individually or in combination of 2 or more types. Preferably, it is a curing accelerator having latent curing properties, such as DBU, DBN organic acid salts and / or tetraphenylborate (U-CAT5002 (manufactured by San Apro Co., Ltd.)), DBU phenol salt (U-CAT SA 1 (Sun Apro). Manufactured by Co., Ltd.), and a cationic photopolymerization catalyst.

The amount of the curing accelerator (D) used is preferably 0 to 20 parts by mass when the component (A) is 100 parts by mass. If it exceeds 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 aforementioned component (A), component (B), and component (C). Further, if necessary, the component (D) and other blending components can be blended preferably in the above proportions. What is obtained by uniformly mixing these components with a roll mill, a mixer, a three roll or the like is preferable. The mixing method is not particularly limited as long as sufficient dispersion can be obtained. Multiple kneading with three rolls is preferred.

The polycarbonate imide resin and paste of the present invention preferably have a viscosity in a Brookfield viscometer (hereinafter also referred to as a B-type viscometer) in the range of 50 dPa · s to 1000 dPa · s at 25 ° C., and 100 dPa · s to 800 dPa. -The range of s is more preferable. When the viscosity is less than 50 dPa · s, there is a tendency for the paste to flow out after printing and the film thickness to be reduced. When the viscosity exceeds 1000 dPa · s, the transferability of the paste to the base material is lowered during printing, and there is a tendency for voids and pinholes in the printed film to increase.

Stability (thixotropic properties) is also important. The degree of change of the polycarbonate imide resin paste is preferably 1.2 or more, 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. If the degree of change is less than 1.2, the flow of paste after printing increases and the film thickness tends to be reduced. If it exceeds 7.0, the paste tends not to flow. The thixotropic degree can be adjusted by the blending amount of the component (C) as a thixotropic agent.

For the polycarbonate imide resin composition and paste of the present invention, known and commonly used colorings such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Agents, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, and other known and conventional polymerization inhibitors, such as olben, benton, and montmorillonite, known and commonly used thickeners, silicone-based, fluorine-based, polymer-based, etc. Antifoaming agent, leveling agent, imidazole, thiazole, triazole, coupling agent such as organoaluminum compound, organotitanium compound, organosilane compound, adhesion promoter, triphenyl phosphate , Tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis (2,6-xylenyl) phosphate, 2-ethylhexyl phosphate, dimethylmethyl Phosphoric flame retardants such as phosphate, resorcinol bis (diphenol A bis (dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus , Ammonium polyphosphate, triazine, melamine cyanurate, succinoguanamine, ethylenedimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) isocyanate Nitrogen flame retardants such as rate, acetoguanamine, guanyl melamine sulfate, melem sulfate, melam sulfate, metal salt flame retardants such as potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, and alkali metal polystyrene sulfonate Hydrated metal flame retardants such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide, silica, aluminum oxide, 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 Conventional additives such as inorganic flame retardants such as magnesium carbonate, calcium carbonate, barium carbonate, zinc stannate, flame retardants / flame retardants such as silicone powder, heat stabilizers, antioxidants, and lubricants Can be used.

<Curing coating>
For example, the polycarbonate imide resin paste of the present invention can be cured as a solder resist as follows to obtain a cured product. That is, methods such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. on COF (Chip On Film) substrates formed by plating copper on resin substrates such as polyimide films Then, the polycarbonate imide resin paste of the present invention is applied to a film thickness of 5 to 80 μm, the coating film is pre-dried at 60 to 120 ° C., and then dried at 120 to 200 ° C. Drying may be in air or in an inert atmosphere. Here, as a method of plating copper on the resin substrate, electroless plating may be used, or a method of sputtering copper on the resin substrate may be used.

The layer of the polycarbonate imide resin paste of the COF substrate thus obtained becomes a solder resist layer, a surface protective layer or an adhesive layer of the COF substrate. As described above, the polycarbonate imide resin paste of the present invention is useful as a film forming material for semiconductor elements, overcoat inks for various electronic components, solder resist inks, and can also be used as paints, coating agents, adhesives, and the like. . Here, the solder resist layer is a film formed on the entire surface excluding the part to be soldered of the circuit conductor, and when wiring electronic parts on the printed wiring board, the solder adheres to unnecessary parts. It is used as a protective coating that prevents the circuit from being directly exposed to air. The surface protective layer is used for mechanically and chemically protecting the electronic member from a processing step or a use environment by being attached to the surface of the circuit member. The adhesive layer is mainly used when a metal layer and a film layer are bonded and a bonding process is performed.

In order to describe the present invention more specifically, examples are given below, but the present invention is not limited to the examples. In addition, the measured value described in the Example is measured by the following method.

<Logarithmic viscosity>
The polycarbonate imide resin (A) was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.5 g / dl. The solution viscosity and solvent viscosity of the solution were measured at 30 ° C. with an Ubbelohde type viscosity tube and calculated according to the following formula.
Logarithmic viscosity (dl / g) = [ln (V1 / V2)] / V3
In the above formula, V1 represents the solvent viscosity measured with an Ubbelohde viscosity tube, and V1 and V2 were determined from the time required for the polymer solution and the solvent (N-methyl-2-pyrrolidone) to pass through the capillary of the viscosity tube. V3 is the polymer concentration (g / dl).

<Non-nitrogen solvent solubility>
During polymerization of polycarbonate imide resin (A), ingredients (a), (b), (c) and γ-butyrolactone are added to the reaction vessel and the temperature is raised. When the internal temperature reaches 100 ° C., the raw material It evaluated by whether ((a) component, (b) component, (c) component) melt | dissolved.
(Evaluation) ○: Completely dissolved △: Slightly undissolved ×: Almost insoluble

<Production of polycarbonate imide resin paste>
The epoxy resin (B) was added to the polycarbonate imide resin (A) and diluted with γ-butyrolactone to obtain a polycarbonate imide resin composition. Filler (C), curing accelerator (D), antifoaming agent and leveling agent were added to this solution. This solution was roughly kneaded and then kneaded three times using a high-speed three-roll to obtain a polycarbonate imide resin paste in which the filler was uniformly dispersed.

<Preparation of laminated film>
As the laminated film, as a commercially available polyimide base film, trade name Viroflex (registered trademark) (manufactured by Toyobo) and trade name Esperflex (registered trademark) (manufactured by Sumitomo Metal Mining) were used.
A polycarbonate imide resin paste is applied onto a copper circuit (L / S = 50/50) obtained by a subtractive method from Toyobo's two-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, base material 20 μm). A predetermined pattern was printed with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., emulsion thickness 30 μm) at a printing speed of 5 cm / second, and dried in an air atmosphere at 80 ° C. for 6 minutes (screen printing). Then, the laminated film which gave the coverlay (coating) which consists of a polycarbonate imide-type resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. When using CCL for COF (trade name Esperflex (registered trademark), copper layer 8μm, base material 12.5μm) manufactured by Sumitomo Metal Mining, the copper circuit (L / S = 16/16) obtained by the subtractive method is used. And a laminated film was obtained as described above.

<Low temperature drying / curability>
The polycarbonate imide resin paste was applied to a polypropylene film having a thickness of 100 μm with an applicator so that the thickness after drying was 20 μm. Subsequently, after drying for 90 minutes at a temperature of 120 ° C., the film was peeled off from the polypropylene film. After 0.125 g of the peeled film was dissolved in 25 ml of N-methyl-2-pyrrolidone at 100 ° C. for 2 hours, the solvent was filtered off with a glass filter. The remaining gel content was vacuum-dried at 150 ° C. for 10 hours or more, and the gel fraction was calculated and evaluated by the following formula.
Gel fraction (%) = weight after solvent dissolution / initial mass × 100
(Evaluation) ○: Gel fraction ≧ 85%
X: Gel fraction less than 85%

<Fluctuation (thixo ratio)>
Using a Brookfield BH rotational viscometer, the measurement was performed in the following procedure. 90 ml of a polycarbonate imide resin paste was placed in a wide-mouthed light-shielding bottle (100 ml), and the liquid temperature was adjusted to 25 ° C. ± 0.5 ° C. using a constant temperature water bath. Next, after stirring 40 times for 12-15 seconds using a glass rod, install the prescribed rotor, let stand for 5 minutes, then read the scale when rotated for 3 minutes at 10 rpm, and calculate the viscosity did. Similarly, it calculated by the following formula from the viscosity value measured at 25 ° C. and 1 rpm.
Deflection = viscosity (1 rpm) / viscosity (10 rpm)

<Printing characteristics>
The printability when the polycarbonate imide resin paste was screen-printed by the method described in the section <Preparation of laminated film> was evaluated.
(Evaluation) ○: The release property is good and the printing surface is flat. Δ: The release property is poor, or unevenness is observed on the printing surface. ×: The release property is poor and unevenness is seen on the printing surface. Be

<Low warpage>
The obtained laminated film was cut into 10 cm × 10 cm. A sample conditioned for 24 hours at 25 ° C. and 65% RH was placed on a horizontal glass plate in a convex state, and the average height of the four corners was evaluated.
(Judgment) ○: less than 2 mm in height Δ: height of 2 mm or more and less than 10 mm ×: height of 10 mm or more

<Flexibility>
The obtained laminated film was evaluated according to JIS-C-6471 (1995). The load was 300 g, the diameter of the mandrel was 0.38 mm, the presence or absence of cracks was confirmed, and the number of bendings when the cracks occurred was recorded.
(Judgment) ◎: No cracking when bent 250 times or more ○: No cracking when bending 200 times or more ×: Crack generated after less than 200 times

<Insulation resistance between lines>
The insulation resistance value (Ω) between lines when a DC voltage of 500 V × 1 minute was applied to the obtained laminated film was measured. The higher the number, the better.

<Solder heat resistance>
The obtained laminated film was immersed in a solder bath at 260 ° C. for 30 seconds according to JIS-C6481 (1996), and the presence or absence of appearance abnormality such as peeling or swelling was observed.
(Judgment) ○: No appearance abnormality △: Slight appearance abnormality ×: Overall appearance abnormality

<Adhesion>
In accordance with JIS-K5600-5-6 (1999), the obtained laminated film was made with 100 1 mm grids and subjected to a peel test using cello tape to evaluate the peeled state of the grids.
(Judgment) ○: No peeling at 100/100 Δ: 70 to 99/100
×: 0 to 69/100

<Pencil hardness>
The obtained laminated film was evaluated according to JIS-K5600-5-4 (1999). The pencil hardness is preferably 2H or higher, and more preferably 3H or higher.

<Alkali resistance>
The polycarbonate imide resin paste was applied to a 100 μm thick polypropylene film with an applicator so that the thickness after drying was 20 μm. Subsequently, after drying for 90 minutes at a temperature of 120 ° C., the film was peeled off from the polypropylene film. The obtained evaluation sample was immersed in a 10% by weight aqueous sodium hydroxide solution at 40 ° C. for 3 hours and then taken out, and the state of the coating film was evaluated.
(Judgment) ○: No appearance abnormality △: Slight appearance abnormality ×: Swelling or dropping off of coating film or dissolved

(Production Example 1) (b) Synthesis of acid dianhydride having a polycarbonate skeleton represented by general formula (1) A reaction vessel was charged with 167 g (0.87 mol) of trimellitic anhydride (TMA) and thionyl chloride. The trimellitic anhydride chloride was synthesized by reaction. Next, 183 g (0.87 mol) of trimellitic anhydride chloride and 434 g (0.43 mol) of Duranol T5651 (Asahi Kasei Co., Ltd., molecular weight 1000) as a diol compound are esterified in toluene at 30 ° C. Thus, a polycarbonate skeleton-containing tetracarboxylic dianhydride was synthesized.

(Production Example 2)
The component (b) 60.0 g (0.04 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (TMEG) 16.4 g synthesized in Production Example 1 (0.04 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as the diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) 0. 08 g was added and dissolved in 97.9 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 83.9 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-1.

(Production Example 3)
The component (b) 60.0 g (0.04 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (TMEG) 16.4 g synthesized in Production Example 1 (0.04 mol), 21.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, 3.4 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1 as a polymerization catalyst , 8-diazabicyclo [5,4,0] -7-undecene (DBU) (0.08 g) was added and dissolved in 96.1 g of γ-butyrolactone. Thereafter, the mixture was reacted for 6 hours at 80 ° C. to 190 ° C. with stirring in a nitrogen stream, diluted by adding 82.3 g of γ-butyrolactone, and cooled to room temperature, whereby the solution was cooled to room temperature to give a brown viscous viscosity of 35% by mass. To obtain a polycarbonate imide resin solution A-2.

(Production Example 4)
The component (b) 90.0 g (0.06 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (TMEG) 8.2 g synthesized in Production Example 1 (0.02 mol), 21.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, 3.4 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1 as a polymerization catalyst , 8-diazabicyclo [5,4,0] -7-undecene (DBU) (0.08 g) was added and dissolved in 117.9 g of γ-butyrolactone. Thereafter, the mixture was reacted for 6 hours at 80 ° C. to 190 ° C. with stirring under a nitrogen stream, diluted by adding 101.1 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-3.

(Production Example 5)
The component (b) 120.0 g (0.08 mol), trimellitic anhydride 3.8 g (0.02 mol) synthesized in Production Example 1 and diisocyanate o-tolidine diisocyanate (TODI) 21.1 g (0 .08 mol), 3.4 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst. Was dissolved in 139.6 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 119.7 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-4.

(Production Example 6)
The component (b) 90.0 g (0.06 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (TMEG) 8.2 g synthesized in Production Example 1 (0.02 mol), 2,5-diphenylmethane diisocyanate (MDI) 25.0 g (0.1 mol) as the diisocyanate, and 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) as the polymerization catalyst 0.08 g was added and dissolved in 118.3 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring under a nitrogen stream, diluted by adding 101.4 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-5.

(Production Example 7)
Component (b) 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (TMEG) 12.3 g synthesized in Production Example 1 (0.03 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as the diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) 0. 08 g was added and dissolved in 108.8 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 93.2 g of γ-butyrolactone, and cooled to room temperature, whereby a brown viscous solution having a nonvolatile content of 35% by mass was obtained. To obtain a polycarbonate imide resin solution A-6.

(Example 1)
10 parts by mass of jER154 (trade name of phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation) is added to 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2, and γ-butyrolactone is added. Diluted with Furthermore, 3.0 parts by mass of Lucentite SEN (synthetic smectite manufactured by Corp Chemical Co.) as a filler, 1.0 part by mass of Ucat 5002 (manufactured by San Apro Co., Ltd.) as a curing accelerator, and BYK-054 (as an antifoaming agent) 0.9 parts by mass of BYK-Chemie Co., Ltd., 1.9 parts by mass of BYK-354 (Bic Chemie Co., Ltd.) as a leveling agent, and 0. BYK-E410 (Bic Chemie Co., Ltd.) as a rheology control agent. 5 parts by mass was added to obtain a polycarbonate imide resin composition. The composition is first kneaded roughly, and then kneaded three times using a high-speed three-roll, whereby the filler is uniformly dispersed and the polycarbonate imide resin paste (1) of the present invention having thixotropic properties Got. When the viscosity was adjusted with γ-butyrolactone, the solution viscosity was 232 poise and the throttling rate was 1.48. Polycarbonate imide of the present invention on a copper circuit (L / S = 50/50) obtained by a subtractive method from Toyobo's two-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, base material 20 μm) A predetermined pattern was printed on the resin-based resin paste (1) with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., emulsion thickness 30 μm) at a printing speed of 5 cm / second, and dried in an air atmosphere at 80 ° C. for 6 minutes. Then, the COF board | substrate (evaluation sample 1) which gave the coverlay (coating) which consists of a polycarbonate imide-type resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. The evaluation results are shown in Table 1.

(Examples 2 to 9)
Preparation of evaluation samples 2 to 9 after preparing a paste in the same manner as in Example 1 except that the polycarbonate imide resin (A) solution and the components (B) to (D) shown in Table 1 were used. did. The evaluation results are shown in Table 1.

(Examples 10 and 11)
A paste was prepared in the same manner as in Example 1 except that the polycarbonate imide resin (A) solution and the components (B) to (D) listed in Table 1 were used, and then the CCL for COF manufactured by Sumitomo Metal Mining was used. (Product name Esperflex (registered trademark), copper layer 8 μm, base material 12.5 μm) on a copper circuit (L / S = 16/16) obtained by a subtractive method, the polycarbonate imide resin paste of the present invention Was printed with a SUS mesh plate (Murakami Co., Ltd. 150 mesh, emulsion thickness 30 μm) at a printing speed of 5 cm / sec and dried in an air atmosphere at 80 ° C. for 6 minutes. Then, the COF board | substrate (evaluation samples 10 and 11) which gave the coverlay (coating) which consists of a polycarbonate imide-type resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. The evaluation results are shown in Table 1.

(Comparative Example 1)
28.8 g (0.1 mol) of trimellitic anhydride, 31.7 g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 5.2 g (0. 02 mol), 0.11 g of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) was added as a polymerization catalyst and dissolved in 52.5 g of γ-butyrolactone. Thereafter, the reaction was carried out at 80 ° C. to 190 ° C. with stirring in a nitrogen stream. However, it did not dissolve in γ-butyrolactone, and the solution became hazy (A-6). The evaluation results are shown in Table 2.

(Comparative Example 2)
Example 1 except that the polycarbonate imide resin solution A-3 obtained in Production Example 3 was used and jER154 (trade name of phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation) was not blended. A paste was prepared in the same manner as above. Since the epoxy resin was not blended, the curing of the paste was insufficient, and the solder heat resistance and alkali resistance were lowered. 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 was used and no filler was added. Since no filler was blended, the thixotropy was insufficient and screen printing was impossible. Therefore, a laminated film sample for evaluation could not be produced.

The polycarbonate imide resin paste obtained by the present invention has both excellent heat resistance and flexibility as a film forming material. For this reason, it is useful for overcoat inks and solder resist inks for various electronic components such as COF substrates, and it can be used in a wide range of electronic equipment as paints, coating agents, adhesives, etc. There is expected.

Claims

As component (A), (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (1), and ( c) a polycarbonate imide resin containing an isocyanate compound or an amine compound as an essential copolymer component,
(B) As an ingredient, an epoxy resin having two or more epoxy groups per molecule,
(C) Polycarbonate imide resin paste containing a filler as a component.

(In general formula (1), m and n are each an integer of 1 or more, and a plurality of m may be the same or different.)
The polycarbonate imide resin paste according to claim 1, further comprising a curing accelerator as component (D).
The polycarbonate imide resin paste according to claim 1 or 2, wherein the degree of change is 1.2 or more.
The polycarbonate imide resin paste according to any one of claims 1 to 3, which is used for COF.
An electronic component having a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the polycarbonate imide resin paste according to any one of claims 1 to 4.