JP6699546B2 - Polycarbonate imide resin paste and electronic component having solder resist layer, surface protection layer, interlayer insulating layer or adhesive layer obtained by curing the paste - Google Patents

Description

  The present invention relates to a polycarbonate imide resin paste. A polycarbonate imide resin paste having excellent heat resistance and flexibility, which is particularly useful for COF (Chip On Film) substrate applications and suitable for a coating method such as a printing machine, a dispenser or a spin coater, and obtained by curing the paste. The present invention relates to an electronic component having a solder resist layer, a surface protection layer, an interlayer insulating layer or an adhesive layer.

  In general, polyimide resins are widely used as insulating materials for electric and electronic devices because they are excellent in heat resistance, insulating properties, chemical resistance and the like. In particular, it is often used as a raw material for COF substrates, and is applied to wiring board materials for electronic devices and mounting board materials that require flexibility and small space. For example, device mounting boards for display devices used in 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, etc., operation switch board Alternatively, it is widely used as a coverlay material (circuit protection layer) for these substrates. Particularly in printed wiring boards, solder resists are widely used as a permanent protective film for circuits. Solder resist is a film that is formed on the entire surface of the circuit conductor excluding the soldering part.It prevents solder from adhering to unnecessary parts when wiring electronic parts to the printed wiring board, 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 constituent element of the COF substrate, is often applied and printed in a solution form, its material is a compound composed of a solvent-soluble closed ring type polyimide resin. However, conventionally, as a solvent for forming a varnish of a polyimide resin, a high boiling point nitrogen solvent such as N-methyl-2-pyrrolidone has been used, and thus 200° C. during drying/curing. The above-mentioned high temperature and long-time curing process is required, and there is a problem that the electronic parts are thermally deteriorated.

  Further, since a polyimide resin is generally hard with a high elastic modulus, when laminated on a substrate such as a film or a copper foil, warpage or the like occurs due to a difference in elastic modulus, which causes a problem in a post process. Further, there is a problem that the cured film lacks flexibility and is inferior in flexibility.

  In addition, examples of the polyimide resin that is soluble in a non-nitrogen solvent and has a low warp and flexibility obtained by making the resin flexible and having a low elastic modulus include, for example, (Patent Document 1) and (Patent Document 2). Discloses a polysiloxane-modified polyimide resin.

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

  Further, a composition in which a molding processability of a resin composition is improved by mixing a polyimide resin with a certain amount of a polycarbonate resin and imparting flexibility is disclosed (Patent Document 3), (Patent Document 4). .. Further, a thermoplastic resin composition having improved moldability by mixing a polyimide resin with 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 although they have excellent heat resistance and mechanical strength, they are not soluble in non-nitrogen solvents and have low warpage and flexibility. It is hard to say.

JP-A-7-304950 Japanese Patent Laid-Open No. 8-333455 JP-A-5-320492 JP, 6-136267, A JP 62-7758 A

  As can be seen from such an example, in the conventional technology so far, (1) non-nitrogen solvent solubility (2) low-temperature drying/curability (3) low warpage (4) flexibility (5) printing characteristics, and ( 6) No polyimide-based resin paste applicable to a solder resist layer, a surface protective layer or an adhesive layer, which simultaneously satisfies alkali resistance, was obtained.

  The present invention has been made against the background of the problems of the related art. That is, the purpose 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 It is an object of the present invention to provide a polycarbonate imide-based resin paste having excellent properties, 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.

（一般式（１）において、ｍおよびｎはそれぞれ１以上の整数であって、複数あるｍは互いに同じであっても異なっていてもよい。）As the 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 copolymerization component,
An epoxy resin having two or more epoxy groups per molecule as the component (B),
A polycarbonate imide resin paste containing a filler as the component (C).

(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.)

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

  The thixotropic degree of the polycarbonate imide-based resin paste is preferably 1.2 or more.

  The polycarbonate imide-based 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-based resin paste according to any one of the above.

  According to the present invention, it has been difficult to satisfy the above requirements at the same time (1) non-nitrogen solvent solubility (2) low temperature drying/curability (3) low warpage (4) flexibility (5) printing characteristics (6) To provide an electronic component having a polycarbonate imide-based resin paste having excellent alkali resistance, heat resistance, chemical resistance, and electrical characteristics, and a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the paste. You can

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

<Polycarbonate imide resin (A) component>
The polycarbonate imide resin (A) used in the present invention will be described. The polycarbonate imide-based resin (A) is (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-based resin having an isocyanate compound or an amine compound as an essential copolymerization component, and preferably the components (a), (b) and (c) as the essential copolymerization components. It is a polycarbonate imide resin.

<(a) Trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group>
As the component (a) constituting the polycarbonate imide resin (A) used in the present invention, trivalent and quaternary valences having an acid anhydride group, which generally react 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, and examples thereof include trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bisanhydrotrimellitate, propylene glycol bisanhydrotrimellitate, 1,4- Alkylene glycol bis-anhydro trimellitates such as butane diol bis-anhydro 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, 1 ,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3, 3',4,4'-diphenylsulfone 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(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-dicarboxyphenoxy)phenyl]propane dianhydride, or 1,3-bis(3,4-dicarboxyphenyl) )-1,1,3,3-Tetramethyldisiloxane dianhydride and the like.

  The aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, but examples thereof include butane-1,2,3,4-tetracarboxylic dianhydride and pentane-1,2,4,5-tetracarboxylic acid. Dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-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 acid dianhydride, dicyclohexyl-3,4,3′,4′-tetracarboxylic acid dianhydride, bicyclo[2,2,1]heptane-2, 3,5,6-Tetracarboxylic acid dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic acid 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 dianhydride, bicyclo[2,2,2] ] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride and the like can be mentioned.

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

  The copolymerization amount of the 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 components to be reacted are 100 mol%. It is preferably 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, and if it is more than 90 mol %, the components (b) and (c) described later cannot be copolymerized in a sufficient amount. Sometimes. Therefore, the low warpage property and the solubility in a non-nitrogen solvent may decrease.

<(b) Acid dianhydride having a polycarbonate skeleton represented by the general formula (1)>
The component (b), which constitutes the polycarbonate imide resin (A) used in the present invention, is a flexible component which imparts low warpage, non-nitrogen solvent solubility and the like to the polycarbonate polyimide resin (A). Polymerized. By copolymerizing these, the elastic modulus of the polycarbonate imide-based resin (A) decreases and the solubility stability in the non-nitrogen-based solvent used as the polymerization solvent increases.

一般式（１）において、ｍは１以上であることが好ましく、より好ましくは２以上であり、さらに好ましくは４以上である。上限は特に限定されないが、２０以下であることが好ましく、より好ましくは１０以下である。複数のｍは、それぞれ同一でも、異なっていてもよい。ｎは１以上であることが好ましく、より好ましくは２以上であり、さらに好ましくは３以上である。上限は特に限定されないが、２０以下であることが好ましく、より好ましくは１０以下である。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, more preferably 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. The upper limit is not particularly limited, but is preferably 20 or less, more preferably 10 or less.

  The method for producing the component (b) is not particularly limited, but 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 deoxidizing agent are put into a chloride solution of trimellitic anhydride dissolved in a solvent, and the mixture is stirred for 0.5 to 24 hours. The reaction temperature is −20 to 50° C., more preferably 20 to 40° C. from the viewpoint of reaction selectivity. As the reaction ratio of the chloride of trimellitic anhydride and the polycarbonate diol compound, it is preferable to react with 1 mol of the polycarbonate diol compound and 2 mol or more of chloride of the trimellitic anhydride. The solute concentration in the reaction is preferably 5 to 80% by weight, more preferably 40 to 60% by weight. After the completion of the reaction, the precipitated hydrochloride is filtered off and the solvent is concentrated to obtain an acid dianhydride having a polycarbonate skeleton represented by the general formula (1) of interest (hereinafter, also referred to as a polycarbonate skeleton-containing tetracarboxylic acid dianhydride). Can be obtained.

  Examples of the method for producing the polycarbonate diol compound include transesterification between a raw material diol and carbonic acid esters, and dehydrochlorination reaction between a raw material diol and phosgene. The carbonic acid ester as a raw material is not particularly limited, but examples thereof include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

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

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

  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, when the total acid component is 100 mol%. It is particularly preferable that the amount is 30 mol% or more and 70 mol% or less. If it is less than 10 mol %, the elastic modulus may not be sufficiently reduced, warpage may occur when laminated, and the solubility in a non-nitrogen solvent may be reduced. Therefore, the resin may precipitate 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 the flexibility (mechanical properties) and heat resistance may decrease.

<(c) Isocyanate compound or amine compound>
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 aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate, Or the polyamine corresponding to these is mentioned. Aromatic polyisocyanates or aromatic polyamines are 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, diphenylmethane-3,4'-diisocyanate, diphenylether-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'-[2,2 Bis(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 and the like can be mentioned. Considering 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 preferable, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate (o-tolidine diisocyanate, TODI) and tolylene-2,4-diisocyanate (TDI) are more preferable. These may be used alone or in combination of two or more. When an aromatic polyamine is used, a polyamine corresponding to the above 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 one of the isocyanate compounds is 100 mol %. When a diamine compound corresponding to the isocyanate is used instead of the isocyanate, the polyamic acid is used as a precursor of the polycarbonate polyimide resin. When a polyamic acid-containing paste is applied to a substrate such as COF (Chip On Film) via a polyamic acid, it is usually necessary to imidize at a high temperature of about 200° C. or higher, and COF may be thermally deteriorated. Yes, and may be limited in terms of equipment. In the present invention, since only the isocyanate compound containing TODI is used as the amine component, it can be processed at a lower temperature than the polyamic acid-containing paste, 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 be further copolymerized with aliphatic, alicyclic or aromatic polycarboxylic acids, if necessary, within a range that does not impair the intended performance. 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-dimethyleicosanedioic acid, fumaric acid Examples of the alicyclic dicarboxylic acid such as maleic acid, dimer acid and hydrogenated dimer acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,2-cyclohexane. 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 and stilbenedicarboxylic acid. These dicarboxylic acids may be used alone or in combination of two or more kinds. Considering heat resistance, adhesiveness, solubility, cost and the like, sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid and isophthalic acid are preferable.

  In addition to the component (b), another flexible component may be copolymerized, if necessary, as long as the desired performance is not impaired. For example, aliphatic/aromatic polyester diols (manufactured by Toyobo Co., Ltd., trade name VYLON (registered trademark) 220), aliphatic/aromatic polycarbonate diols (manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark) )-CD220, Kuraray Co., Ltd., trade name Kuraray Polyol C-1015N, C-2015N, etc., Asahi Kasei Chemicals Co., Ltd., trade name Duranol (registered trademark) T5650E, T5650J, T5651, T5652, etc.), polycaprolactone diol (Manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark)-220, etc.), carboxy-modified acrylonitrile butadiene rubber (manufactured by Ube Industries, Ltd., trade name HyproCTBN1300×13, etc.), polydimethylsiloxanediol, poly Examples thereof include polysiloxane derivatives such as methylphenylsiloxane diol and carboxy-modified polydimethylsiloxanes.

  As the method for producing the polycarbonate imide resin (A), a method for producing from a polycarboxylic acid component ((a) component and (b) component) having an acid anhydride group and an isocyanate component ((c) component) (isocyanate) Method) or a polycarboxylic acid component ((a) component and (b) component) having an acid anhydride group and an amine component ((c) component) are reacted to form an amic acid, and then the ring is closed (direct method). There are known methods such as. The isocyanate method is industrially advantageous.

  In the case of the isocyanate method, the compounding amounts of the component (a), the component (b), and the component (c) are such that the ratio of the number of acid anhydride groups to the number of isocyanate groups is 0.8 to 1. It is preferable to set it to 2. If it is less than 0.8, it may be difficult to increase the molecular weight of the polycarbonate imide-based resin (A), heat resistance and flexibility may be deteriorated, and the coating film may be brittle. On the other hand, if it is higher than 1.2, the viscosity of the polycarbonate imide resin (A) may be high, and the plate separation may be poor at the time of printing when it is made into 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, in the presence of at least one organic solvent selected from the group consisting of an ether solvent, an ester solvent, a ketone solvent and an aromatic hydrocarbon solvent, for example, carbon dioxide gas liberated by the isocyanate method is generated. It is preferable to carry out 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). , Ester-based solvents, for example, γ-butyrolactone, cellosolve acetate, etc., ketone-based solvents, for example, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, etc., aromatic hydrocarbon-based solvents, for example, toluene, xylene, Solvesso, etc. 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 generated polycarbonate imide resin (A), and it is suitable as a solvent for the polycarbonate imide resin paste as it is after polymerization. It is more preferable to use one. By doing so, complicated operations such as solvent replacement are eliminated, and it becomes possible to manufacture at low cost. The boiling point of the solvent is preferably 140°C or higher and 230°C or lower. If the temperature is lower than 140° C., the solvent may volatilize during the polymerization reaction. In addition, for example, when screen printing is performed, the solvent may volatilize quickly and plate clogging may occur. If it exceeds 230°C, it may be difficult to impart low-temperature drying/curability. [Gamma]-butyrolactone, cyclohexanone, diglyme, or triglyme is preferable because it has relatively high volatility, low-temperature drying/curability can be imparted, varnish stability is excellent, and the reaction can be efficiently performed in a homogeneous system.

  The amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) of the polycarbonate imide resin (A) to be produced, and more preferably 0.9 to 2.0 times. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the stirring tends to make it difficult to synthesize, 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, decomposition of the monomer components may occur during the reaction. Further, gelation is likely to occur due to a three-dimensional reaction. The reaction temperature may be carried out in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions adopted, especially the reaction concentration.

  In the case of the isocyanate method, in order to accelerate the reaction, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo[2,2,2]octane), DBU (1,8-diazabicyclo[5,4,0] ]-7-undecene) and the like amines, lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride, alkali metal such as potassium fluoride, alkaline earth metal compounds or titanium, cobalt, It 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)>
As an example of the method for producing the polycarbonate imide resin (A), it can be obtained by subjecting the component (a), the component (b), and the component (c) to a condensation reaction (polyimidization). Hereinafter, the method for producing the polycarbonate imide-based resin of the present invention will be exemplified, but the present invention is not limited thereto.

  After the components (a), (b), (c), the polymerization catalyst and the polymerization solvent are added to the reaction vessel and dissolved, the mixture is stirred under a nitrogen stream at 80 to 190°C, preferably 100 to 180°C. After reacting for 5 hours or more, the desired polycarbonate imide resin (A) can be obtained by diluting with a polymerization solvent to an appropriate solvent viscosity 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 0. It has a molecular weight corresponding to a logarithmic viscosity of 2 to 1.5 dl/g. If the logarithmic viscosity is less than 0.1 dl/g, the heat resistance may be reduced or the coating film may be brittle. Moreover, the tackiness of the paste is strong and the plate separation may be deteriorated. On the other hand, if it exceeds 2.0 dl/g, it becomes difficult to dissolve in the solvent and it tends to become insoluble during polymerization. In addition, the viscosity of the varnish becomes high, which makes handling difficult, and the adhesion to the substrate may deteriorate.

  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 the temperature is lower than 20°C, the heat resistance may be insufficient and the resin may be blocked. The upper limit is not particularly limited, but is preferably 300° C. or lower from the viewpoint of solvent solubility.

<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, but for example, bisphenol A type epoxy resin such as jER (registered trademark) 828,1001 manufactured by Mitsubishi Chemical Co., Ltd., product name ST manufactured by Tohto Kasei Co., Ltd. -Hydrogenated bisphenol A type epoxy resin such as 2004 and 2007, trade name YDF-170 manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy such as 2004, trade name YDB-400 and 600 manufactured by Toto Kasei Co., Ltd. Brominated bisphenol A type epoxy resin, trade name jER (registered trademark) 152, 154 manufactured by Mitsubishi Chemical Corporation, phenol novolac type epoxy resin, trade name jER (registered trademark) 157S65 manufactured by Mitsubishi Chemical Corporation, Bisphenol A novolac type epoxy resin such as 157S70, trifunctional phenol type epoxy resin such as jER (registered trademark) 1032H60 manufactured by Mitsubishi Chemical Co., Ltd., trade name EPPN (registered trademark) manufactured by Nippon Kayaku Co., Ltd.- 201, BREN (registered trademark), phenol novolac type epoxy resin such as product name DEN-438 manufactured by Dow Chemical Co., product name YDCN-702, 703 manufactured by Tohto Kasei Co., Ltd., product manufactured by Nippon Kayaku Co., Ltd. Name EOCN (registered trademark)-125S, 103S, 104S and other o-cresol novolac type epoxy resins, Toto Kasei Co., Ltd. trade name YD-171 and other flexible epoxy resins, Yuka Shell Epoxy Co., Ltd. Trade name Epon1031S, Ciba Specialty Chemicals Co., Ltd. trade name Araldite (registered trademark) 0163, Nagase Chemtec Co., Ltd. trade name Denacol (registered trademark) EX-611, EX-614, EX-622. , EX-512, EX-521, EX-421, EX-411, EX-321 and other multifunctional epoxy resins, Yuka Shell Epoxy Co., Ltd. trade name Epikote (registered trademark) 604, Tohto Kasei Co., Ltd. Product name YH-434 manufactured by Mitsubishi Gas Chemical Co., Inc., product name TETRAD (registered trademark)-X, TETRAD-C manufactured by Nippon Kayaku Co., Ltd. product name GAN manufactured by Sumitomo Chemical Co., Ltd. Amine type epoxy resin such as name ELM-120, heterocyclic ring-containing epoxy resin such as Araldite (registered trademark) PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Celoxide (registered name) manufactured by Daicel Chemical Industries, Ltd. Trademark) 2021, EHPE (registered trademark) 3150, alicyclic epoxy resin such as ERL4234 manufactured by UCC, trade name Epiclon (registered trademark) manufactured by Dainippon Ink and Chemicals, Inc. ) Bisphenol S type epoxy resin such as EXA-1514, triglycidyl isocyanurate such as TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd., and bixylenol such as YX-4000 manufactured by Yuka Shell Epoxy Co., Ltd. Type epoxy resin, bisphenol type epoxy resin such as trade name YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd., and the like, and these may be used alone or in combination of two or more kinds.

  Among these epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins having more than two epoxy groups in one molecule, and o-cresol novolak type epoxy resins are preferable. Further, the amine type epoxy resin is a non-halogen type, and is preferable in terms of compatibility with the polycarbonate imide type resin (A), solvent resistance, chemical resistance, and improvement of moisture resistance.

  The epoxy resin (B) used in the present invention is used in an amount of preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 3 to 100 parts by mass of the polycarbonate imide resin (A). 30 parts by mass. If the compounding 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 if it exceeds 50 parts by mass, low warpage property, mechanical properties, The heat resistance, varnish stability and compatibility with the polycarbonate imide resin (A) tend to decrease.

  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 the epoxy resin (B) to be added in advance may be dissolved in the same solvent as the solvent contained in the polycarbonate imide resin (A) and then added. Alternatively, it may be directly added to the polycarbonate imide resin (A).

<Filler (C) component>
The filler (C) used in the present invention (hereinafter, also simply referred to as the 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 polycarbonate imide-based resin (A) to form a paste and impart thixotropy (thixotropic) to the paste. That is, it is preferably an inorganic or organic filler capable of imparting thixotropy to the polycarbonate imide resin paste of the present invention. Examples of such an inorganic filler 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 ). , Organized bentonite, carbon (C), Organized smectite (trade name Lucentite (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN manufactured by Coop Chemical Co., Ltd.) can be used. These may be used alone or in combination of two or more. From the viewpoint of imparting the 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 20 μm or less, and most preferably 10 μm or less. The average particle diameter (median diameter) here is a value obtained on a volume basis using a laser diffraction/scattering particle size distribution measuring device. If the average particle size exceeds 50 μm, it becomes difficult to obtain a paste having sufficient thixotropy, and the flexibility of the coating film may decrease. When the maximum particle size exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient.

  The organic filler used in the present invention is dispersed in the above polycarbonate imide-based resin solution to form a paste, as long as it can impart thixotropic properties to the paste, polyimide resin particles, benzoguanamine resin particles, epoxy resin Examples thereof include particles.

  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. It is more preferably 2 to 15 parts by mass, and particularly preferably 3 to 12 parts by mass. If the compounding 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, mechanical properties such as flexibility of the coating film and transparency tend to decrease.

<Curing accelerator (D)>
A curing accelerator can be added as the component (D) to the polycarbonate imide resin paste of the present invention in order to further improve 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 above polycarbonate imide resin (A) and 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, imidazole derivatives, acetoguanamine, benzoguanamine and the like. , Guanamines, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polyamines such as polybasic hydrazides, organic acid salts and/or epoxy adducts, triamines Boron fluoride amine complex, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanolamine, N , N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, DBU(1,8 -Tertiary amines such as diazabicyclo[5,4,0]-7-undecene) and DBN (1,5-diazabicyclo[4,3,0]-5-nonene), their organic acid salts and/or tetra Organic phosphines such as phenyl borate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecyltributylphosphonium Chloride, quaternary phosphonium salts such as tetraphenylphosphonium tetraphenylborate, benzyltrimethylammonium chloride, quaternary ammonium salts such as phenyltributylammonium chloride, the polycarboxylic acid anhydride, diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimolybdenum Nate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure (registered trademark) 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Op A cationic photopolymerization catalyst such as Toma-SP-170 (manufactured by ADEKA Corporation), a styrene-maleic anhydride resin, an equimolar reaction product of phenyl isocyanate and dimethylamine, and an organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate. Examples include equimolar reaction products of dimethylamine. You may use these individually or in combination of 2 or more types. Preferably, it is a curing accelerator having latent curability, and it is an organic acid salt of DBU or DBN and/or tetraphenylborate (U-CAT5002 (manufactured by San-Apro Co., Ltd.) or DBU phenol salt (U-CAT SA 1 (San-Apro)). (Manufactured by K.K.), and photocationic polymerization catalysts.

  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-based resin composition and the heat resistance of the coating film may decrease.

<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). Furthermore, if necessary, the component (D) and other compounding ingredients can be preferably compounded in the above proportions. What is obtained by uniformly mixing each of these components with a roll mill, a mixer, three rolls or the like is preferable. The mixing method is not particularly limited as long as sufficient dispersion can be obtained. Kneading with three rolls multiple times is preferred.

  The polycarbonate imide-based resin and paste of the present invention have a viscosity in a Brookfield viscometer (hereinafter, also referred to as B-type viscometer) at 25° C. of preferably 50 dPa·s to 1000 dPa·s, and 100 dPa·s to 800 dPa. The range of s is more preferable. When the viscosity is less than 50 dPa·s, the flow of the paste after printing becomes large and the film thickness tends to be thin. When the viscosity is more than 1000 dPa·s, the transferability of the paste to the base material is deteriorated during printing, scuffing occurs, and voids and pinholes in the printed film tend to increase.

  The degree of thixotropic (thixotropic) is also important. The degree of thixotropy of the polycarbonate imide-based resin paste is preferably 1.2 or more, more preferably 1.5 or more in the measuring method described later. The upper limit is preferably 7.0 or less, and more preferably 6.0 or less. If the degree of rocking is less than 1.2, the flow-out of the paste after printing tends to be large and the film thickness tends to be thin. 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.

  The polycarbonate imide-based resin composition and paste of the present invention, if necessary, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like commonly known coloring Agents, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine and other known conventional polymerization inhibitors, orben, benton, montmorillonite and other known conventional thickeners, silicone-based, fluorine-based, polymer-based, etc. Antifoaming agent, leveling agent, imidazole-based, thiazole-based, triazole-based, organoaluminum compound, organotitanium compound, organosilane compound and other coupling agents/adhesion-imparting agents, triphenyl phosphate, tricresyl phosphate, triki Silenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis(2,6-xylenyl) phosphate, 2-ethylhexyl phosphate, dimethyl methyl phosphate, resorcinol bis (diphenol A) Phosphorus flame retardants such as bis(dicresyl)phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus, ammonium polyphosphate, triazine, melamine shear Nurate, succinoguanamine, ethylene dimelamine, triguanamine, cyanuric acid triazinyl salt, melem, melam, tris(β-cyanoethyl) isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, nitrogen-based flame retardants such as melam sulfate, Metal salt flame retardants such as potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, polystyrene sulfonate alkali metal salt, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic Hydrated metal flame retardants such as 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, carbonic acid Inorganic flame retardants such as zinc, magnesium carbonate, calcium carbonate, barium carbonate, zinc stannate, flame retardants/flame retardants such as silicone powder, heat stabilizers, antioxidants, lubricants, etc. Agents can be used.

<Cured coating>
The polycarbonate imide-based resin paste of the present invention can be cured, for example, as a solder resist as described below to obtain a cured product. That is, a COF (Chip On Film) substrate formed by plating a resin base material such as a polyimide film with copper, a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, or a curtain coating method. Then, the polycarbonate imide-based resin paste of the present invention is applied in a thickness of 5 to 80 μm, the coating film is pre-dried at 60 to 120° C., and then the main drying is performed 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 base material, electroless plating may be used, or a method of sputtering copper on the resin base material may be used.

  The layer of the polycarbonate imide-based resin paste of the COF substrate obtained in this way becomes a solder resist layer, a surface protective layer or an adhesive layer of the COF substrate. As described above, the polycarbonate imide-based resin paste of the present invention is useful as a film-forming material for overcoat inks for various semiconductor devices and electronic parts, solder resist inks, and can also be used as paints, coating agents, adhesives, etc. .. Here, the solder resist layer is a film that is formed on the entire surface of the circuit conductor excluding the soldering portion, and when wiring electronic components to the printed wiring board, solder is prevented from adhering to unnecessary portions. It is used as a protective coating to prevent direct exposure of the circuit to air as well as to prevent it. The surface protective layer is a layer that is attached to the surface of the circuit member and is used to mechanically and chemically protect the electronic member from the processing step and the use environment. The adhesive layer is used mainly for adhering the metal layer and the film layer and performing a laminating process.

  The following examples are provided to describe the present invention more specifically, 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 viscous tube, and calculated by the following formula.
Logarithmic viscosity (dl/g)=[ln(V1/V2)]/V3
In the above formula, V1 represents the solvent viscosity measured by an Ubbelohde viscous tube, but V1 and V2 were determined from the time taken for the polymer solution and the solvent (N-methyl-2-pyrrolidone) to pass through the capillary of the viscous tube. V3 is the polymer concentration (g/dl).

<Non-nitrogen solvent solubility>
During polymerization of the polycarbonate imide resin (A), the components (a), (b), (c) and γ-butyrolactone are added to the reaction vessel to raise the temperature, and when the internal temperature reaches 100° C. It was evaluated by whether or not ((a) component, (b) component, (c) component) was dissolved.
(Evaluation) ○: Completely dissolved
△: slightly unmelted
×: Almost insoluble

<Preparation 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. A filler (C), a curing accelerator (D), a defoaming agent, and a 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.

<Production of laminated film>
For the laminated film, as a commercially available polyimide base film, trade name Biroflex (registered trademark) (manufactured by Toyobo) and trade name Esperflex (registered trademark) (manufactured by Sumitomo Metal Mining Co., Ltd.) were used.
Polycarbonate imide-based resin paste was applied on a copper circuit (L/S=50/50) obtained by subtractive method from TOYOBO 2-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, substrate 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/sec and dried in an air atmosphere at 80° C. for 6 minutes (screen printing). Then, by heating and curing at 120° C. for 90 minutes, a laminated film having a cover lay (coating) made of a polycarbonate imide-based resin paste was obtained. The coating thickness was 15 μm. Sumitomo Metal Mining COF CCL (trade name Esperflex (registered trademark), copper layer 8 μm, substrate 12.5 μm) also uses the copper circuit (L/S=16/16) obtained by the subtractive method A laminated film was obtained in the same manner as above.

<Low temperature drying/curability>
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 would be 20 μm. Then, after drying at a temperature of 120° C. for 90 minutes, it was peeled from the polypropylene film. After dissolving 0.125 g of the peeled film 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 by the following formula and evaluated.
Gel fraction (%)=weight after dissolution in solvent/initial mass×100
(Evaluation) ○: Gel fraction ≧85%
X: Gel fraction less than 85%

<Degree of change (thixo ratio)>
The Brookfield BH rotational viscometer was used for the measurement in the following procedure. 90 ml of the polycarbonate imide-based resin paste was placed in a wide-mouth type light-shielding bottle (100 ml), and the liquid temperature was adjusted to 25° C.±0.5° C. using a constant temperature water bath. Then, after stirring 40 times using a glass rod for 12 to 15 seconds, a predetermined rotor was installed, the mixture was left standing for 5 minutes, and then the scale when rotated at 10 rpm for 3 minutes was read to calculate the viscosity. did. Similarly, it was calculated by the following formula from the value of viscosity measured at 25° C. and 1 rpm.
Thickness=viscosity (1 rpm)/viscosity (10 rpm)

<Printing characteristics>
The polycarbonate imide resin paste was screen-printed by the method described in the section <Production of Laminated Film> to evaluate the printability.
(Evaluation) Good: The plate releasability is good and the printing surface is flat.
Δ: Plate separation property is poor, or unevenness is seen on the printed surface
X: Plate separation property is poor and unevenness is seen on the printed surface

<Low warpage>
The obtained laminated film was cut into 10 cm×10 cm. A sample that had been conditioned at 25° C. and 65% RH for 24 hours was placed on a horizontal glass plate in a downward convex state, and the average of the heights of the four corners was evaluated.
(Judgment) O: Height less than 2 mm
Δ: Height of 2 mm or more and less than 10 mm
X: 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 were generated was recorded.
(Judgment) ⊚: No cracks were generated after bending 250 times or more
◯: No crack is generated after bending 200 times or more
×: Cracks occurred less than 200 times

<Line insulation resistance>
The line insulation resistance (Ω) was measured when a DC voltage of 500 V×1 minute was applied to the obtained laminated film. 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 in accordance with JIS-C6481 (1996) and observed for appearance abnormalities such as peeling and swelling.
(Judgment) ○: No abnormal appearance
△: Slightly abnormal appearance
×: Abnormal appearance on the entire surface

<Adhesion>
In accordance with JIS-K5600-5-6 (1999), 100 cross-cuts having a size of 1 mm were made on the obtained laminated film, and a peeling test was performed with cellophane tape to evaluate the peeled state of the cross-cuts.
(Judgment) O: No peeling at 100/100
Δ: 70 to 99/100
X: 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, more preferably 3H or higher.

<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 would be 20 μm. Then, after drying at a temperature of 120° C. for 90 minutes, it was peeled from the polypropylene film. The obtained evaluation sample was immersed in a 10 wt% sodium hydroxide aqueous solution at 40° C. for 3 hours and then taken out to evaluate and evaluate the state of the coating film.
(Judgment) ○: No abnormal appearance
△: Slightly abnormal appearance
X: The coating film is swollen, dropped, or dissolved

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

(Production Example 2)
60.0 g (0.04 mol) of the component (b) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 16.4 g of ethylene glycol bisanhydrotrimellitate (TMEG). (0.04 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) 0. 08 g was added and dissolved in 97.9 g of γ-butyrolactone. Then, the mixture was reacted under a nitrogen stream at 80° C. to 190° C. for 6 hours with stirring, and then 83.9 g of γ-butyrolactone was added for dilution, and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-1 was obtained.

(Production Example 3)
60.0 g (0.04 mol) of the component (b) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 16.4 g of ethylene glycol bisanhydrotrimellitate (TMEG). (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. Then, the mixture was reacted at 80° C. to 190° C. for 6 hours with stirring under a nitrogen stream, and then 82.3 g of γ-butyrolactone was added to dilute the mixture and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-2 was obtained.

(Production Example 4)
90.0 g (0.06 mol) of the component (b) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, and 8.2 g of ethylene glycol bisanhydrotrimellitate (TMEG). (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. Then, under a nitrogen stream, while stirring, the mixture was reacted at 80°C to 190°C for 6 hours, 101.1 g of γ-butyrolactone was added to dilute, and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-3 was obtained.

(Production Example 5)
(B) component 120.0 g (0.08 mol) synthesized in Production Example 1, trimellitic anhydride 3.8 g (0.02 mol), o-trizine diisocyanate (TODI) 21.1 g (0 0.08 mol), 2,4-tolylene diisocyanate (TDI) 3.4 g (0.02 mol), and 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) 0.08 g as a polymerization catalyst. And was dissolved in 139.6 g of γ-butyrolactone. After that, while reacting at 80° C. to 190° C. for 6 hours with stirring under a nitrogen stream, 119.7 g of γ-butyrolactone was added to dilute, and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-4 was obtained.

(Production Example 6)
90.0 g (0.06 mol) of the component (b) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, and 8.2 g of ethylene glycol bisanhydrotrimellitate (TMEG). (0.02 mol), 4,4-diphenylmethane diisocyanate (MDI) 25.0 g (0.1 mol) as a diisocyanate, 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) as a polymerization catalyst. 0.08 g was added and dissolved in 118.3 g of γ-butyrolactone. After that, while reacting at 80° C. to 190° C. for 6 hours under stirring in a nitrogen stream, 101.4 g of γ-butyrolactone was added to dilute, and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-5 was obtained.

(Production Example 7)
75.0 g (0.05 mol) of component (b) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, and 12.3 g of ethylene glycol bisanhydrotrimellitate (TMEG). (0.03 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) 0. 08 g was added and dissolved in 108.8 g of γ-butyrolactone. After that, while reacting at 80° C. to 190° C. for 6 hours under stirring in a nitrogen stream, 93.2 g of γ-butyrolactone was added to dilute the mixture, and the mixture was cooled to room temperature to give a brown solid with a nonvolatile content of 35% by mass. A tough polycarbonate imide resin solution A-6 was obtained.

(Example 1)
To 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2, 10 parts by mass of jER154 (trade name of phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation) was added, and γ-butyrolactone was added. Diluted with. Further, 3.0 parts by mass of Lucentite SEN (synthetic smectite manufactured by Coop Chemical Co., Ltd.) as a filler, 1.0 part by mass of Ucat5002 (manufactured by San Apro Co., Ltd.) as a curing accelerator, and BYK-054 (as a defoaming agent) 0.9 parts by mass of BYK-Chemie Co., Ltd., 1.9 parts by mass of BYK-354 (manufactured by BIC-Chemie Co., Ltd.) as a leveling agent, and 0.1 part of BYK-E410 (manufactured by 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 roughly kneaded, and then repeatedly kneaded three times using a high-speed three-roll, to uniformly disperse the filler and to have thixotropic properties. Polycarbonate imide resin paste (1) of the present invention Got When the viscosity was adjusted with γ-butyrolactone, the solution viscosity was 232 poise and the thixotropic degree was 1.48. Polycarbonate imide of the present invention on a copper circuit (L/S=50/50) obtained by a subtractive method from a two-layer CCL manufactured by Toyobo (trade name: Viroflex (registered trademark), copper foil 18 μm, substrate 20 μm) The resin paste (1) 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/sec to form a predetermined pattern, and dried at 80° C. for 6 minutes in an air atmosphere. Then, by heating and curing at 120° C. for 90 minutes, a COF substrate (evaluation sample 1) having a cover lay (coating) made of a polycarbonate imide-based resin paste was obtained. The coating thickness was 15 μm. The evaluation results are shown in Table 1.

(Examples 2 to 9)
Evaluation samples 2 to 9 were prepared 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) described in Table 1 were used. did. The evaluation results are shown in Table 1.

(Examples 10 and 11)
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, CCL for COF manufactured by Sumitomo Metal Mining Co., Ltd. Polycarbonate imide resin paste of the present invention on a copper circuit (L/S=16/16) obtained by subtractive method from (trade name Esperflex (registered trademark), copper layer 8 μm, substrate 12.5 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/sec and dried at 80° C. for 6 minutes in an air atmosphere. Then, by heating and curing at 120° C. for 90 minutes, a COF substrate (evaluation samples 10 and 11) having a cover lay (coating) made of a polycarbonate imide-based resin paste was obtained. The coating thickness 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 diisocyanate, 5.2 g of 2,4-tolylene diisocyanate (TDI) (0. 02 mol) and 0.11 g of 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) as a polymerization catalyst were added and dissolved in 52.5 g of γ-butyrolactone. Then, the mixture was reacted at 80°C to 190°C under a nitrogen stream while stirring. However, it did not dissolve in γ-butyrolactone and haze occurred in the solution (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 that 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 in. Since the epoxy resin was not mixed, the paste was not sufficiently cured, 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 that 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 prepared.

  The polycarbonate imide-based 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 parts such as COF substrates, and can also be used in a wide range of electronic devices as paints, coating agents, adhesives, etc., making a great contribution to the industry. There is expected.

Claims (4)

As the 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 copolymerization component,
An epoxy resin having two or more epoxy groups per molecule as the component (B),
As a component (C), a filler ,
A polycarbonate imide-based resin paste containing , as the component (D), a curing accelerator having latent curability .

(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.) The polycarbonate imide-based resin paste according to claim 1 , which has a thixotropic degree of 1.2 or more. The polycarbonate imide-based resin paste according to claim 1 or 2 , which is for COF. The solder resist layer formed by curing a polycarbonate imide resin paste according to any one of claims 1 to 3 electronic component having a surface protective layer or an adhesive layer.