WO2019244600A1

WO2019244600A1 - Polycarbonate-imide resin and paste including same

Info

Publication number: WO2019244600A1
Application number: PCT/JP2019/021726
Authority: WO
Inventors: 翔子内山; 啓介松尾
Original assignee: 東洋紡株式会社
Priority date: 2018-06-22
Filing date: 2019-05-31
Publication date: 2019-12-26
Also published as: JP7310808B2; JPWO2019244600A1

Abstract

Provided is a polycarbonate-imide resin which satisfies all of (1) solubility in nitrogen-free solvents, (2) low warpage, (3) flex resistance, and (4) resistance to high temperatures and high humidities and which is usable for forming solder resist layers, surface-protective layers, or adhesive layers. The polycarbonate-imide resin (A) is characterized by comprising a component represented by specific structural formula (1) and a component represented by specific structural formula (2), the sum of the component represented by specific structural formula (1) and the component represented by specific structural formula (2) being 45 mol% or greater when all components are taken as 200 mol%.

Description

Polycarbonate imide resin and paste using the same

The present invention relates to a polycarbonate imide resin and a paste using the same. Particularly useful for COF (Chip \ On \ Film) substrate applications, it has excellent heat resistance and flexibility and is suitable for a coating method such as a printing machine, a dispenser or a spin coater, and a polycarbonate imide resin paste obtained by curing the paste. Electronic component having a solder resist layer, a surface protective layer, or an adhesive layer.

ポリイミド Generally, polyimide resins are widely used as insulating materials for electric and electronic equipment because of their excellent heat resistance, insulation properties, chemical resistance, and the like. In particular, it is often used as a raw material of a COF substrate, and is applied to a wiring board material and a mounting substrate material of an electronic device that requires flexibility and small space. For example, a device mounting board for a display device used for a liquid crystal display device, a plasma display, an organic EL display, and the like, a relay cable between boards for a smartphone, a tablet device terminal, a digital camera, a portable game machine, and the like, an operation switch section board Or, it is widely used as a coverlay material (a protective layer of a circuit) for these substrates. In particular, in printed wiring boards, solder resists are widely used as permanent protective films for circuits. Solder resist is a film that is formed on the entire surface of the circuit conductor except for the part to be soldered.When wiring electronic components on printed wiring boards, it prevents solder from adhering to unnecessary parts and Is used as a protective coating 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 compound comprising a solvent-soluble ring-closing polyimide resin as its material. Has been proposed. However, since a high-boiling nitrogen-based solvent such as N-methyl-2-pyrrolidone has been conventionally used as a solvent for varnishing a polyimide-based resin, a high-temperature and high-temperature A curing step is required, and there is a problem that the electronic components are thermally degraded.

Furthermore, since polyimide resins are generally high in elasticity and hard, when laminated on a substrate such as a film or a copper foil, there is a problem in a post-process because warpage or the like is generated due to a difference in elasticity. Further, there is a problem that the cured film lacks flexibility and is inferior in flexibility.

Examples of a polyimide resin which is soluble in a non-nitrogen-based solvent and has low warpage and flexibility 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 resins use an expensive diamine having a dimethylsiloxane bond as a starting material for lowering the modulus of elasticity, and are inferior in economical efficiency. In addition, there is a problem that the adhesion, solvent resistance, and chemical resistance decrease as the polysiloxane copolymerization amount increases.

Further, a composition in which a certain amount of a polycarbonate resin is mixed with a polyimide resin to impart flexibility, thereby improving the moldability of the resin composition is disclosed (Patent Document 3), (Patent Document 4). . Further, a thermoplastic resin composition having improved 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. Hard to say.

JP-A-7-304950 JP-A-8-333455 JP-A-5-320492 JP-A-6-136267 JP-A-62-2758

As can be seen from such an example, in the conventional techniques so far, (1) non-nitrogen-based solvent solubility (2) low warpage (3) flex resistance (4) solder resist layer that simultaneously satisfies high temperature and humidity resistance; A polyimide resin paste applicable as a surface protective layer or an adhesive layer has not been obtained.

The present invention has been made on the background of the problems of the related art. That is, the object of the present invention is (1) non-nitrogen-based solvent solubility (2) low-temperature drying / curability (3) low warpage (4) bending resistance (5) printing characteristics, and (6) high temperature resistance. An object of the present invention is to provide an electronic component having a polycarbonate imide resin having excellent wettability and heat resistance, a polycarbonate imide resin paste using the same, and a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the paste. is there.

When the composition contains the components represented by the general formula (1) and the components represented by the general formula (2), and all the components are 200 mol%, the components represented by the general formula (1) and the general formula ( The polycarbonate imide resin (A), wherein the total of the components represented by 2) is 45 mol% or more.

(In the general formula (1), a plurality of R ₁ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and q independently represents an integer of 1 to 4.)

(In the general formula (2), a plurality of R ₂ each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

It is preferable that the polycarbonate imide resin (A) further contains a component represented by the general formula (3).

(In the general formula (3), a plurality of R ₃ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, r each independently represents an integer of 1 to 4, and p is 0 or 1. is there.)

In the polycarbonate imide resin (A), the component represented by the general formula (1) is 5 to 45 mol%, the component represented by the general formula (2) is 5 to 45 mol%, and the general formula ( It is preferable that the component represented by 3) is at least 50 mol%.

(A) an acid dianhydride having a fluorene structure represented by the general formula (4); (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5); Assuming that the total acid component is 100 mol%, (a) an acid dianhydride having a fluorene structure represented by the general formula (4) and (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5) The polycarbonate imide resin (A), wherein the total amount of the components is 45 mol% or more.

(In the general formula (4), a plurality of R ₄ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and s independently represents an integer of 1 to 4.)

(In the general formula (5), a plurality of R ₅ each independently represent a divalent organic group having 1 or more carbon atoms, and m is an integer of 1 or more.)

The isocyanate component (c) is preferably a diisocyanate represented by the general formula (6).

(In the general formula (6), a plurality of R ₆ each independently represent hydrogen or an alkyl group having 1 to 3 carbons, t each independently represents an integer of 1 to 4, and p is 0 or 1. is there.)

In the polycarbonate imide resin (A), the acid dianhydride having a fluorene structure represented by the general formula (4) is 5 to 45 mol%, and the acid dianhydride having a polycarbonate skeleton represented by the general formula (5) is used. The content of the diisocyanate represented by the general formula (6) is preferably at least 50 mol% when the total isocyanate component is 100 mol%.

ポリカーボネート A polycarbonate imide resin paste containing the polycarbonate imide resin (A), the epoxy resin (B) and the filler (C).

According to the present invention, (1) solubility in non-nitrogen solvents (2) low-temperature drying / curing properties (3) low warpage (4) bending resistance (5) printing characteristics, which have been difficult to satisfy simultaneously at the same time, and (6) It has a polycarbonate imide resin excellent in high temperature and humidity resistance and heat resistance, a polycarbonate imide resin paste using the same, and a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste. Electronic components can be provided.

Hereinafter, the polycarbonate imide resin (A) and the polycarbonate imide resin paste of the present invention will be described in detail.

<Polycarbonate imide resin (A)>
The polycarbonate imide resin (A) of the present invention will be described. The polycarbonate imide resin (A) includes a component represented by the general formula (1) (hereinafter, also referred to as a component of the general formula (1)) and a component represented by the general formula (2) (hereinafter, the general formula ( When the total amount of the components is 200 mol%, the total of the components represented by the general formula (1) and the components represented by the general formula (2) is 45 mol. % Or more.

<Components represented by general formula (1)>
By containing the constituent component (cardo structure) represented by the general formula (1), effects of improving solubility in a non-nitrogen solvent, heat resistance, and an elastic modulus of a coating film can be expected. The cardo structure means a hinge structure in which four aromatic rings are bonded to carbon atoms, and has a variety of features such as high heat resistance and transparency because it contains a large number of aromatic rings.

In the general formula (1), a plurality of R ₁ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ₁ is preferably hydrogen or a methyl group, more preferably a methyl group. q independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1. The position of R ₁ is preferably 3-position with respect to the addition position of the fluorene ring, and more preferably, both R ₁ are 3-position. Further, the position of the ester group is preferably 4-position with respect to the addition position of the fluorene ring, and more preferably both of the two ester groups are 4-position. Specifically, a component represented by the formula (7) is particularly preferable.

含有 The content of the components of the general formula (1) is preferably 5 mol% or more when all the components are 200 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the solubility in a non-nitrogen solvent or the heat resistance may not be obtained. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If it is too large, it may not be possible to contain a sufficient amount of the components represented by the general formula (2) described later and other acid components. Therefore, heat resistance and bending resistance (mechanical properties) may be reduced.

<Components represented by general formula (2)>
Since the component represented by the general formula (2) has flexibility, the polycarbonateimide resin (A) of the present invention can be imparted with low warpage, non-nitrogen-based solvent solubility, and the like.

In the general formula (2), a plurality of R ₂ each independently represent a divalent organic group having 1 or more carbon atoms. The number of carbon atoms is preferably 5 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less. The divalent organic group is not particularly limited, but is preferably a linear alkylene group which may have a substituent, and the carbon number preferably includes the carbon of the substituent. Further, n is an integer of 1 or more, preferably an integer of 2 or more, more preferably an integer of 3 or more, preferably an integer of 10 or less, and more preferably an integer of 8 or less.

含有 The content of the components of the general formula (2) is preferably 5 mol% or more when all the components are 200 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, warpage may occur when the layers are laminated, or the solubility in a non-nitrogen-based solvent may decrease. Therefore, at 5 ° C. to 30 ° C., the resin may be precipitated within one month. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If the amount is too large, the heat resistance may decrease. Further, the component represented by the general formula (1) and other acid components may not be contained in a sufficient amount. Therefore, low warpage and bending resistance (mechanical properties) may be reduced.

As a component of the polycarbonate imide resin (A), it is necessary that the total amount of the component represented by the general formula (1) and the component represented by the general formula (2) is 45 mol% or more, It is preferably at least 50 mol%, more preferably at least 55 mol%, even more preferably at least 60 mol%. If the amount is too small, low warpage and solubility in a non-nitrogen solvent may be reduced. Further, it is preferably at most 90 mol%, more preferably at most 80 mol%.

<Components represented by general formula (3)>
The polycarbonate imide resin (A) of the present invention preferably further contains a component represented by the general formula (3) (hereinafter, also referred to as a component of the general formula (3)). By including the component represented by the general formula (3), excellent flex resistance can be exhibited.

In the general formula (3), each of a plurality of R ₃ independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ₃ is preferably hydrogen or a methyl group, and more preferably a methyl group. r independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1. The position of R ₃ is preferably 3-position with respect to — (CH ₂ ) p—, and more preferably, both R ₃ are 3-position. Further, the position of the binding site is preferably at position 4 with respect to-(CH ₂ ) p-, and more preferably both of the two binding sites are at position 4. p is 0 or 1, preferably 0 (biphenyl form).

Specific examples of the components of the general formula (3) include 4,4′-biphenyl diisocyanate residue, 4,3′-biphenyl diisocyanate residue, 4,2′-biphenyl diisocyanate residue, and 3,3′-biphenyl Diisocyanate residue, 3,2'-biphenyl diisocyanate residue, 2,2'-biphenyl diisocyanate residue, 3- or 2-methyl-4,4'-biphenyl diisocyanate residue, 3- or 2- or 2'- Or 4'- or 5'- or 6'-methyl-4,3'-biphenyl diisocyanate residue, 3- or 2- or 3'- or 4'- or 5'- or 6'-methyl-4,2 '-Biphenyl diisocyanate residue, 3- or 2-ethyl-4,4'-biphenyl diisocyanate residue, 3- or 2- or 2'- or 4'- or 5'- 6'-ethyl-4,3'-biphenyl diisocyanate residue, 3- or 2- or 3'- or 4'- or 5'- or 6'-ethyl-4,2'-biphenyl diisocyanate residue, 3, 3'- or 3,2'-dimethyl-4,4'-biphenyl diisocyanate residue, 3,2'- or 3,4'- or 3,5'- or 3,6'- or 2,2'- Or 2,4'- or 2,5'- or 2,6'-dimethyl-4,3'-biphenyl diisocyanate residue, 3,3'- or 3,4'- or 3,5'- or 3, 6'- or 2,3'- or 2,4'- or 2,5'- or 2,6'-dimethyl-4,2'-biphenyl diisocyanate residue, 3,3'- or 3,2'- Diethyl-4,4'-biphenyl diisocyanate residue, 3,2'- or 3,4'- or 3,5 -Or 3,6'- or 2,2'- or 2,4'- or 2,5'- or 2,6'-diethyl-4,3'-biphenyl diisocyanate residue, 3,3'- or 3 , 4'- or 3,5'- or 3,6'- or 2,3'- or 2,4'- or 2,5'- or 2,6'-diethyl-4,2'-biphenyl diisocyanate residue Group, diphenylmethane-4,4'-diisocyanate residue, diphenylmethane-4,3'-diisocyanate residue, diphenylmethane-4,2'-diisocyanate residue, diphenylmethane-3,3'-diisocyanate residue, diphenylmethane-3, 2'-diisocyanate residue, diphenylmethane-2,2'-diisocyanate residue, 3- or 2-methyldiphenylmethane-4,4'-diisocyanate residue, 3- or 2- or Is 2'- or 4'- or 5'- or 6'-methyldiphenylmethane-4,3'-diisocyanate residue, 3- or 2- or 3'- or 4'- or 5'- or 6'-methyl Diphenylmethane-4,2'-diisocyanate residue, 3,2'- or 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate residue, 3,2'- or 3,4'- or 3,5 ' -Or 3,6'- or 2,2'- or 2,4'- or 2,5'- or 2,6'-dimethyldiphenylmethane-4,3'-diisocyanate residue, 3,3'- or 3 , 4'- or 3,5'- or 3,6'- or 2,3'- or 2,4'- or 2,5'- or 2,6'-dimethyldiphenylmethane-4,2'-diisocyanate residue And the like. These may be used alone or in combination of two or more. To be able to use. Of these, a 3,3'-dimethyl-4,4'-biphenyl diisocyanate residue (o-tolidine diisocyanate residue) is preferred.

The content of the components represented by the general formula (3) is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% when all the components are 200 mol%. Mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. If it is less than 50 mol%, the flex resistance may not be sufficiently exhibited.

The polycarbonate imide resin (A) of the present invention contains the components of the general formula (1) and the components of the general formula (2) in predetermined amounts. Therefore, the polycarbonate imide resin (A) includes (a) an acid dianhydride having a fluorene structure represented by the general formula (4), (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5), and (C) When the isocyanate component is an essential copolymer component and the total acid component is 100 mol%, (a) a fluorene structure-containing dianhydride represented by the general formula (4) and (b) a general formula (5) )) Is preferably at least 45 mol%.

<(A) Fluorene structure-containing acid dianhydride represented by general formula (4)>
The component (a) constituting the polycarbonate imide resin (A) used in the present invention needs to be (a) an acid dianhydride having a fluorene structure (hereinafter, also simply referred to as the component (a)). By using the acid dianhydride having a fluorene structure, excellent effects in solubility in non-nitrogen solvents and heat resistance can be expected.

In the general formula (4), a plurality of R ₄ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ₄ is preferably hydrogen or a methyl group, and more preferably a methyl group. s each independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1. The position of R ₄ is preferably 3-position with respect to the addition position of the fluorene ring, and more preferably both R ₄ are 3-position. Further, the position of the ester group is preferably 4-position with respect to the addition position of the fluorene ring, and more preferably both of the two ester groups are 4-position. In a specific example, the compound represented by the formula (8) is particularly preferable (hereinafter, also referred to as a compound of the formula (8)). Examples of commercially available products include, but are not limited to, TBIS (registered trademark) -MPN (manufactured by Taoka Chemical), and these can be used alone or in combination of two or more.

The copolymerization amount of the component (a) is preferably 5 mol% or more when the total acid component to be reacted is 100 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the solubility in a non-nitrogen solvent or the heat resistance may not be obtained. Moreover, it is preferable that it is 45 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 35 mol% or less. If the amount is too large, it may not be possible to copolymerize a sufficient amount of other acid components described later (b). Therefore, low warpage and bending resistance (mechanical properties) may be reduced.

<(B) Acid dianhydride having polycarbonate skeleton represented by general formula (5)>
The (b) acid dianhydride having a polycarbonate skeleton represented by the general formula (5) (hereinafter, also simply referred to as component (b)) constituting the polycarbonate imide resin (A) of the present invention is a polycarbonate polyimide resin ( It is copolymerized as a flexible component which imparts low warpage, non-nitrogen solvent solubility, etc. to A).

The component (b) is an acid dianhydride having a polycarbonate skeleton represented by the general formula (5).

In the general formula (5), a plurality of R ₅ each independently represents a divalent organic group having 1 or more carbon atoms. The number of carbon atoms is preferably 5 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less. The divalent organic group is not particularly limited, but is preferably a linear alkylene group which may have a substituent, and the carbon number preferably includes the carbon of the substituent. Further, n is an integer of 1 or more, preferably an integer of 2 or more, more preferably an integer of 3 or more, preferably an integer of 10 or less, and more preferably an integer of 8 or less.

The method for producing the component (b) is not particularly limited, but can be synthesized from a chloride of trimellitic anhydride and the above-mentioned polycarbonate diol compound by a known reaction method. More specifically, first, a polycarbonate diol compound and a deoxidizing agent are charged into a chloride solution of trimellitic anhydride dissolved in a solvent, and the mixture is stirred for 0.5 to 24 hours. The reaction is carried out at a temperature of −20 to 50 ° C., and preferably at a temperature of 20 to 40 ° C. from the viewpoint of reaction selectivity. Regarding the reaction ratio between the chloride of trimellitic anhydride and the polycarbonate diol compound, the reaction is preferably performed using 2 mol or more of chloride of trimellitic anhydride with respect to 1 mol of the polycarbonate diol compound. The solute concentration in the reaction is preferably from 5 to 80% by weight, more preferably from 40 to 60% by weight. After completion of the reaction, the precipitated hydrochloride is separated by filtration and the solvent is concentrated to obtain the desired acid dianhydride having a polycarbonate skeleton represented by the general formula (5) (hereinafter also referred to as a polycarbonate skeleton-containing tetracarboxylic dianhydride). ) Can be obtained.

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

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

The polycarbonate diol that can be used in the present invention may be a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol), and as commercial products, for example, Kuraray polyol C-1015N, Kuraray polyol C- 1065N (carbonate diol manufactured by Kuraray Co., Ltd .: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 1,000), Kuraray polyol C-2015N, Kuraray polyol C-2065N (( Kuraray's carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 2,000), Kuraray polyol C-1050, Kuraray polyol C-1090 (Kuraray Co., Ltd.) Carbonate diol: 3-meth 1,5-pentanediol / 1,6-hexanediol, number average molecular weight about 1,000), Kuraray polyol C-2050, Kuraray polyol C-2090 (carbonate diol manufactured by Kuraray Co., Ltd .: 3-methyl-1) , 5-pentanediol / 1,6-hexanediol, number average molecular weight about 2,000), DURANOL (registered trademark) -T5650E (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation: 1,5-pentanediol / 1,6-) Hexanediol, number average molecular weight about 500), DURANOL (registered trademark) -T5651 (polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight about 1,000), DURANOL (registered trademark) -T5652 (Asahi Kasei Chemical Corporation) Ltd. Polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, may be mentioned about 2,000) and the number average molecular weight.

The copolymerization amount of the component (b) is preferably 5 mol% or more when the total acid component is 100 mol%. It is more preferably at least 10 mol%, further preferably at least 15 mol%, particularly preferably at least 20 mol%. If the amount is too small, the elastic modulus may not be sufficiently reduced, and warpage may occur when laminating, or the solubility in a non-nitrogen-based solvent may be reduced. Therefore, at 5 ° C. to 30 ° C., the resin may be precipitated within one month. On the other hand, it is preferably at most 45 mol%, more preferably at most 40 mol%, even more preferably at most 35 mol%. If the amount is too large, the component (a) and other acid components described below cannot be contained in a sufficient amount, so that low warpage, bending resistance (mechanical properties), and heat resistance may decrease.

As the acid component of the polycarbonate imide resin (A), the total amount of the component (a) and the component (b) needs to be 45 mol% or more, preferably 50 mol% or more, and 55 mol% or more. %, More preferably at least 60 mol%. If the amount is too small, low warpage and solubility in a non-nitrogen solvent may be reduced. Further, it is preferably at most 90 mol%, more preferably at most 80 mol%.

<Other acid components>
As the other acid component, a trivalent or tetravalent polycarboxylic acid derivative having an acid anhydride group can be used. The aromatic polycarboxylic acid derivative is not particularly restricted but includes, for example, trimellitic anhydride (TMA), pyromellitic dianhydride, 3,3′-4,4′-benzophenonetetracarboxylic dianhydride, 3 3,3'-4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, , 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- Carboxyphenyl) 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] Examples thereof include propane dianhydride and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride.

Examples of the aliphatic or alicyclic polycarboxylic acid derivative include, but are not limited to, 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-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.

３These trivalent and / or tetravalent polycarboxylic acid derivatives having an acid anhydride group may be used alone or in combination of two or more. The content of the trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group is preferably 10 mol% or more, more preferably 20 mol%, when the acid component is 100 mol%. And more preferably 30 mol% or more. Further, it is preferably at most 55 mol%, more preferably at most 50 mol%.

脂肪 Also, aliphatic, alicyclic, and aromatic dicarboxylic acids may be further copolymerized as needed as long as the desired performance is not impaired. Examples of the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, eicosantioic 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-dimethyleicosandioic acid, 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 Examples of aromatic dicarboxylic acids such as dicarboxylic acid and 4,4′-dicyclohexyldicarboxylic acid include, for example, 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. Considering heat resistance, adhesion, solubility, cost, and the like, sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferred.

<(C) isocyanate component>
The (c) isocyanate component constituting the polycarbonate imide resin (A) of the present invention is preferably a diisocyanate represented by the general formula (6). By using the diisocyanate represented by the general formula (6), excellent flex resistance can be exhibited.

In the general formula (6), a plurality of R ₆ each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ₆ is preferably hydrogen or a methyl group, more preferably a methyl group. t each independently represents an integer of 1 to 4, preferably 3 or less, more preferably 2 or less, and still more preferably 1. The position of R ₆ is preferably 3-position with respect to — (CH ₂ ) p-, and more preferably both R ₆ are 3-position. Further, the position of the binding site is preferably at position 4 with respect to-(CH ₂ ) p-, and more preferably both of the two binding sites are at position 4. p is 0 or 1, preferably 0 (biphenyl form).

Specific examples of the diisocyanate represented by the general formula (6) include 4,4'-biphenyl diisocyanate, 4,3'-biphenyl diisocyanate, 4,2'-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 3,2 '-Biphenyl diisocyanate, 2,2'-biphenyl diisocyanate, 3- or 2-methyl-4,4'-biphenyl diisocyanate, 3- or 2- or 2'- or 4'- or 5'- or 6'-methyl -4,3'-biphenyl diisocyanate, 3- or 2- or 3'- or 4'- or 5'- or 6'-methyl-4,2'-biphenyl diisocyanate, 3- or 2-ethyl-4,4 '-Biphenyl diisocyanate, 3- or 2- or 2'- or 4'- or 5'- or 6'-ethyl-4,3' Biphenyl diisocyanate, 3- or 2- or 3'- or 4'- or 5'- or 6'-ethyl-4,2'-biphenyl diisocyanate, 3,3'- or 3,2'-dimethyl-4,4 '-Biphenyl diisocyanate, 3,2'- or 3,4'- or 3,5'- or 3,6'- or 2,2'- or 2,4'- or 2,5'- or 2,6 '-Dimethyl-4,3'-biphenyl diisocyanate, 3,3'- or 3,4'- or 3,5'- or 3,6'- or 2,3'- or 2,4'- or 2, 5'- or 2,6'-dimethyl-4,2'-biphenyl diisocyanate, 3,3'- or 3,2'-diethyl-4,4'-biphenyl diisocyanate, 3,2'- or 3,4 ' -Or 3,5'- or 3,6'- or 2,2'- or 2,4'- or 2,5'- or 2,6'-diethyl-4,3'-biphenyl diisocyanate, 3,3'- or 3,4'- or 3,5'- or 3,6'- or 2,3'- Or 2,4'- or 2,5'- or 2,6'-diethyl-4,2'-biphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-4,3'-diisocyanate, diphenylmethane-4 2'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,2'-diisocyanate, diphenylmethane-2,2'-diisocyanate, 3- or 2-methyldiphenylmethane-4,4'-diisocyanate, 3- or 2- or 2'- or 4'- or 5'- or 6'-methyldiphenylmethane-4,3'-diisocyanate , 3- or 2- or 3'- or 4'- or 5'- or 6'-methyldiphenylmethane-4,2'-diisocyanate, 3,2'- or 3,3'-dimethyldiphenylmethane-4 4'-diisocyanate, 3,2'- or 3,4'- or 3,5'- or 3,6'- or 2,2'- or 2,4'- or 2,5'- or 2,6 '-Dimethyldiphenylmethane-4,3'-diisocyanate, 3,3'- or 3,4'- or 3,5'- or 3,6'- or 2,3'- or 2,4'- or 2, Examples thereof include 5′- or 2,6′-dimethyldiphenylmethane-4,2′-diisocyanate, and these can be used alone or in combination of two or more. Of these, 3,3'-dimethyl-4,4'-biphenyl diisocyanate (o-tolidine diisocyanate (TODI)) is preferred.

The copolymerization amount of the diisocyanate represented by the general formula (6) is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol%, when all the isocyanate components are 100 mol%. Mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. If it is less than 50 mol%, the value of the elastic modulus is low, and the flex resistance may not be sufficiently exhibited.

<Other isocyanate components>
In the polycarbonate imide resin (A) of the present invention, if necessary, an isocyanate compound may be further copolymerized as an isocyanate component as long as the desired performance is not impaired. It is not particularly limited as long as it is an isocyanate compound, and examples thereof include an aromatic polyisocyanate, an aliphatic polyisocyanate and an alicyclic polyisocyanate. Preferably, an aromatic polyisocyanate is used. Although not particularly limited, specific examples of the aromatic polyisocyanate include, for example, 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, diphenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'- Diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylenediisocyanate, p-xylylenediisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2bis (4 -Phenoxyphenyl) propane] diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate And 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, and 3,3′-diethoxybiphenyl-4,4′-diisocyanate. In consideration of heat resistance, adhesion, solubility, cost, and the like, diphenylmethane-4,4'-diisocyanate (MDI), tolylene-2,4-diisocyanate (TDI), and m-xylylene diisocyanate are preferable. 2,4-diisocyanate (TDI) is more preferred. These can be used alone or in combination of two or more.

When the (c) isocyanate 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, a polyamic acid is used as a precursor of the polycarbonate polyimide resin. After passing through the polyamic acid, it is necessary to apply the polyamic acid-containing paste to a substrate such as COF (Chip \ On \ Film) and then imidize it at a high temperature of about 200 ° C. or more, which may cause thermal degradation of the COF. Yes, and there may be restrictions on facilities. In the present invention, since only the isocyanate compound containing the diisocyanate represented by the general formula (6) is used as the isocyanate component, it can be processed at a lower temperature than the paste containing polyamic acid, and is preferable because there is no problem as described above. .

In addition to the component (b), if necessary, other flexible components may be copolymerized 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, manufactured by Kuraray Co., Ltd., trade names C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, etc., manufactured by Asahi Kasei Chemicals Corporation, trade name Duranol® (registered trademark) T-4671, T-4672, T-5650E, T-5650J, T-5651, T5652, etc., polycaprolactone diols (manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark)- 220), carboxy-modified acrylonitrile-butadiene rubbers (HyproCTBN1300 × 13, etc., manufactured by Ube Industries, Ltd.), and polysiloxane derivatives such as polydimethylsiloxane diol, polymethylphenylsiloxane diol, and carboxy-modified polydimethylsiloxane. It is.

The polycarbonate imide resin (A) is produced from a polycarboxylic acid component having an acid anhydride group (components (a) and (b)) and an isocyanate component (component (c)) (isocyanate method).

In 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 such that the number of isocyanate groups / the number of acid anhydride groups = 0.8 to 1.2. It is preferable that If it is less than 0.8, it may be difficult to increase the molecular weight of the polycarbonate imide resin (A), and heat resistance and bending resistance may be reduced, or the coating film may be brittle. On the other hand, when it is higher than 1.2, the viscosity of the polycarbonate imide resin (A) may be high, and the separation of the plate may be deteriorated at the time of printing in the case of ink.

重合 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-based solvents, ester-based solvents, ketone-based solvents, and aromatic hydrocarbon-based solvents, for example, the isocyanate method is used to generate carbon dioxide gas that is liberated. It is preferred 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). Ester solvents such as γ-butyrolactone and cellosolve acetate; ketone solvents such as methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; and aromatic hydrocarbon solvents such as toluene, xylene and solvesso. No. 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 produced polycarbonate imide resin (A), and after polymerization, use a suitable solvent as the solvent for the polycarbonate imide resin paste as it is Is more preferable.
By doing so, complicated operations such as solvent replacement are eliminated, and it is possible to manufacture at low cost. The solvent preferably has a boiling point of 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 volatilization of the solvent may be quick and the plate may be clogged. If the temperature exceeds 230 ° C., it may be difficult to impart low-temperature drying / curing properties. Γ-butyrolactone, cyclohexanone, diglyme, or triglyme is preferable in order to have a relatively high volatility, impart low-temperature drying / curing properties, have excellent varnish stability, and efficiently perform the reaction in a homogeneous system.

The amount of the solvent used is preferably 0.5 to 7.0 times (mass ratio), more preferably 2.0 to 6.0 times, the polycarbonate imide resin (A) to be produced. If it is less than 0.5 times, the viscosity at the time of synthesis tends to be too high, and the synthesis tends to be difficult due to inability to stir. If it exceeds 7.0 times, the reaction rate tends to decrease.

In the isocyanate method, the reaction temperature is preferably from 60 to 200 ° C, more preferably from 100 to 180 ° C. If the temperature is lower than 60 ° C, the reaction time becomes too long. If the temperature is higher than 200 ° C, the monomer component may be decomposed during the reaction. In addition, a three-dimensional reaction occurs and gelation easily occurs. 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, and particularly the reaction concentration.

In 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 promote the reaction. Amines such as -7-undecene), alkali metal and alkaline earth metal compounds such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride and sodium fluoride, or titanium, cobalt and tin The reaction may be performed in the presence of a catalyst such as a metal such as zinc, aluminum, and aluminum, and a metalloid compound.

<Production of polycarbonate imide resin (A)>
An example of a method for producing the polycarbonate imide resin (A) can be obtained by subjecting the component (a) to a condensation reaction (polyimide) with the component (b) and the component (c). Hereinafter, a method for producing the polycarbonate imide resin of the present invention will be exemplified, but the present invention is not limited thereto.

After adding and dissolving the components (a), (b) and (c), the polymerization catalyst and the polymerization solvent in the reaction vessel, the mixture is dissolved at 80 to 190 ° C., preferably 100 to 180 ° C. while stirring under a nitrogen stream. 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 in γ-butyrolactone at 30 ° C. corresponding to an logarithmic viscosity of 0.1 to 2.0 dl / g, more preferably 0.2 to 2.0 dl / g. From 1.5 dl / g to a logarithmic viscosity. If the logarithmic viscosity is less than 0.1 dl / g, the heat resistance may decrease or the coating film may be brittle. In addition, the tackiness of the paste may be so strong that separation of the plate may be deteriorated. On the other hand, if it exceeds 2.0 dl / g, it is difficult to dissolve in a solvent, and it is easily insoluble during polymerization. In addition, the viscosity of the varnish may increase, making handling difficult, or the adhesion to the substrate may be reduced.

ガラス The glass transition temperature of the polycarbonate imide resin (A) used in the present invention is preferably 60 ° C or higher, more preferably 100 ° C or higher. If the temperature is lower than 60 ° 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>
In the present invention, an epoxy resin can be blended as the component (B) with the polycarbonate imide resin (A). The epoxy resin (B) used in the present invention is not particularly limited as long as it has two or more epoxy groups per molecule. The epoxy resin (B) is not particularly limited. For example, bisphenol A type epoxy resin such as jER (registered trademark) 828,1001 (trade name, manufactured by Mitsubishi Chemical Corporation) and ST (trade name, manufactured by Toto Kasei Co., Ltd.) -Hydrogenated bisphenol A epoxy resin such as 2004, 2007, etc .; Bisphenol F type epoxy such as YDF-170, 2004, manufactured by Toto Kasei Co., Ltd .; YDB-400, 600, etc. manufactured by Toto Kasei Co., Ltd. Brominated bisphenol A type epoxy resin, trade names jER (registered trademark) 152, 154, 157S70, 1032H60, manufactured by Mitsubishi Chemical Corporation, EPN (registered trademark) -201, BREN manufactured by Nippon Kayaku Co., Ltd. (Registered trademark), a phenol novolak type epoxy resin such as DEN-438 (trade name, manufactured by Dow Chemical Company), a product manufactured by Toto Kasei Co., Ltd. O-Cresol novolak type epoxy resin such as YDCN-702, 703, trade name EOCN (registered trademark) -125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd., trade name YD-171 manufactured by Toto Kasei Co., Ltd. Flexible epoxy resin, Epon1031S (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite (registered trademark) 0163 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Denacol (trade name, manufactured by Nagase Chemtech Co., Ltd.) (Registered trademark) polyfunctional epoxy resins such as EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, trade name of DIC Corporation Dicyclopentadiene type epoxy resins such as HP-7200, HP-7200H, HP-7200HH, Yuka Shell Epoxy Co., Ltd. (Trade name) Epikote (registered trademark) 604, trade name YH-434 (trade name, manufactured by Toto Kasei Co., Ltd.), TETRAD (registered trademark) -X, TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Nippon Kayaku ( Includes amine type epoxy resins such as GAN (trade name) manufactured by Sumitomo Chemical Co., Ltd., and ELM-120 (trade name) manufactured by Sumitomo Chemical Co., Ltd .; and heterocyclic rings such as Araldite (registered trademark) PT810 (trade name) manufactured by Ciba Specialty Chemicals Epoxy resins, alicyclic epoxy resins such as Celloxide (registered trademark) 2021, EHPE (registered trademark) 3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.), ERL4234 (trade name, manufactured by UCC), manufactured by Dainippon Ink and Chemicals, Inc. Bisphenol S type epoxy resin such as EPICLON (registered trademark) EXA-1514 and TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd. Glycidyl isocyanurate, a bixylenol-type epoxy resin such as YX-4000 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), and a bisphenol-type epoxy resin such as YL-6056 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.). 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 novolak type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin Resins are preferred. Further, the amine type epoxy resin is a 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 60 parts by mass, more preferably 2 to 50 parts by mass, particularly preferably 3 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate imide resin (A). Parts by weight. If the amount of the epoxy resin (B) is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease. If it exceeds 60 parts by mass, low warpage, mechanical properties and The compatibility with the polycarbonate imide resin (A) tends to decrease.

エポキシ 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 method for adding the epoxy resin (B) is not particularly limited, and the epoxy resin (B) to be added may be dissolved in the same solvent as the solvent contained in the polycarbonate imide resin (A) in advance, and then added. Further, it may be directly added to the polycarbonate imide resin (A).

<Filler (C) component>
In the present invention, a filler can be blended as the component (C) with the polycarbonate imide resin (A). The filler (C) (hereinafter, also simply referred to as component (C)) used in the present invention 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 impart thixotropic properties (thixotropic) 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 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 ), and 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 (brand name manufactured by Corp Chemical Co., Ltd. Tight (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN) and the like may be used, and these may be used alone or in combination of two or more. It is preferable to use silica or lucentite from the viewpoint of imparting the color tone, transparency, mechanical properties, and thixotropic properties of the obtained paste.

無機 As the inorganic filler used in the present invention, those having an average particle diameter of 50 μm or less and a maximum particle diameter of 100 μm or less are preferable, the average particle diameter is 20 μm or less, and the average particle diameter is 10 μm or less is most preferable. The average particle diameter (median diameter) here is a value obtained on a volume basis using a laser diffraction / scattering type particle size distribution analyzer. If the average particle size exceeds 50 μm, it becomes difficult to obtain a paste having sufficient thixotropic properties, and the flexibility of the coating film may be reduced. If 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 may be any 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.

使用 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, particularly preferably 3 to 12 parts by mass. If the amount of the inorganic or organic filler is less than 1 part by mass, 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>
In order to further improve properties such as adhesion, chemical resistance, and heat resistance, a curing accelerator can be added to the polycarbonate imide resin paste of the present invention. The curing accelerator used in the present invention is not particularly limited as long as it can promote the curing reaction of the above-mentioned polycarbonate imide resin (A) and epoxy resin (B).

Specific examples of such a curing accelerator include, for example, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, manufactured by Shikoku Chemical Industry Co., Ltd. Guanamines such as imidazole derivatives such as 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z -AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, acetoguanamine and benzoguanamine , Diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polyamines such as polybasic hydrazide, and their organic acid salts and / or epoxy adducts G, boron trifluoride amine complex, 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), and their organic acid salts U-CAT® SA1 (DBU-phenol salt), U-CAT® SA # 102 (DBU-O U-CAT (registered trademark) SA # 831 (DBU-phenol novolak resin salt), U-CAT (registered trademark) 5002 (DBU-based tetraphenylborate salt) (all manufactured by San Apro Corporation) and / or Or organic phosphines such as tetraphenylboroate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexa Quaternary phosphonium salts such as decyltributylphosphonium chloride and tetraphenylphosphonium tetraphenylboroate, and quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride Salts, the aforementioned polycarboxylic anhydrides, diphenyliodonium tetrafluoroboronate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure® 261 (Ciba Specialty) A cationic photopolymerization catalyst such as Chemicals Co., Ltd., Optoma-SP-170 (ADEKA Co., Ltd.), styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate, An equimolar reaction product of an organic polyisocyanate such as isophorone diisocyanate and dimethylamine is exemplified. These may be used alone or in combination of two or more. Preferred is a curing accelerator having latent curing properties, and examples thereof include organic salts of DBU and DBN and / or tetraphenylboroate, and a cationic photopolymerization catalyst.

使用 The amount of the curing accelerator used is preferably 0 to 20 parts by mass when the component (A) is 100 parts by mass. If the amount exceeds 20 parts by mass, the storage stability of the polycarbonate imide 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-described polycarbonate imide resin (A) component, epoxy resin (B) component, and filler (C) component. Further, if necessary, a curing accelerator and other compounding components can be preferably added in the above ratio. What is obtained by uniformly mixing these components with a roll mill, a mixer, a three-roll mill or the like is preferable. The mixing method is not particularly limited as long as a sufficient dispersion can be obtained. Plural kneading with three rolls is preferred.

The polycarbonate imide resin paste of the present invention preferably has a Brookfield viscometer (hereinafter also referred to as a B-type viscometer) having a viscosity at 25 ° C. of 50 dPa · s to 1000 dPa · s, and 100 dPa · s to 800 dPa · s. Is more preferable. If the viscosity is less than 50 dPa · s, the flow of the paste after printing tends to be large and the film thickness tends to be thin. If the viscosity exceeds 1000 dPa · s, during printing, the transferability of the paste to the substrate tends to decrease, causing blurring and increasing the number of voids and pinholes in the printed film.

The degree of thixotropic (thixotropic) is also important. The thixotropic degree of the polycarbonate imide resin paste is preferably 1.1 or more, more preferably 1.2 or more, in a measuring method described later. The upper limit is preferably equal to or less than 7.0, and more preferably equal to or less than 6.0. If the degree of fluctuation is less than 1.1, the flow 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 amount of the component (c) as the thixotropic agent.

The polycarbonate imide resin and the paste of the present invention may contain, if necessary, known and commonly used coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, and hydroquinone. , Hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, phenothiazine, etc., known and commonly used thickeners such as orben, benton, montmorillonite, etc., silicone-based, fluorine-based, polymer-based antifoaming agents , Leveling agents, coupling agents / adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based, organoaluminum compounds, organotitanium compounds, and organosilane compounds, triphenyl phosphate, and triphenyl phosphate Cresyl phosphate, trixylenyl 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 bis (dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphate, phosphoric amide, organic phosphine oxide, phosphorus-based flame retardant such as red phosphorus, polyphosphoric acid Ammonium, triazine, melamine cyanurate, succinoguanamine, ethylenedimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) isocyanurate Nitrogen flame retardants such as acetoguanamine, guanylmelamine sulfate, melem sulfate, and melam sulfate; metal salt flame retardants such as potassium diphenylsulfon-3-sulfonate; metal salts of aromatic sulfonimides; alkali metal salts of polystyrene sulfonate; water Aluminum oxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrated metal flame retardants such as 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 Zinc, carbonated Inorganic flame retardants such as gnesium, calcium carbonate, barium carbonate, and zinc stannate; flame retardants such as silicone powder; flame retardant aids; heat stabilizers; antioxidants; Can be used.

<Curing coating>
The polycarbonate imide resin paste of the present invention can be cured as follows, for example, as a solder resist, to obtain a cured product. That is, on a COF (Chip On Film) substrate formed by plating copper on a resin substrate such as a polyimide film, a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like. Then, the polycarbonate imide resin paste of the present invention is applied to a thickness of 5 to 80 μm, and the coating film is preliminarily 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.

(4) The layer of the cured product of the polycarbonate imide resin paste of the COF substrate obtained as described above becomes a solder resist layer, a surface protection layer, or an adhesive layer of the COF substrate. As described above, the polycarbonate imide resin paste of the present invention is useful as an overcoat ink for semiconductor elements and various electronic components and a solder resist ink as a film forming material, and can also be used as a paint, a coating agent, an adhesive and the like. Here, the solder resist layer is a film that is formed on the entire surface of the circuit conductor except for the part to be soldered.When wiring electronic components on a printed wiring board, it is necessary to prevent solder from adhering to unnecessary parts. It is used as a protective film to prevent and prevent the circuit from being directly exposed to air. The surface protective layer is used to be attached to the surface of the circuit member to mechanically and chemically protect the electronic member from a processing step and a use environment. The adhesive layer is mainly used for bonding a metal layer and a film layer and performing a bonding process.

実施 Examples will be given below to describe the present invention more specifically, but the present invention is not limited to the examples. The measured values described in the examples are measured by the following method.

<Logarithmic viscosity>
The polycarbonate imide resin (A) was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration became 0.5 g / dl. The solution viscosity and the solvent viscosity of the solution were measured at 30 ° C. using an Ubbelohde type viscosity 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 type viscosity tube, and V1 and V2 were determined from the time when the polymer solution and the solvent (N-methyl-2-pyrrolidone) passed through the capillary of the viscosity tube. V3 is the polymer concentration (g / dl).

<Non-nitrogen solvent solubility>
During the polymerization of the polycarbonate imide resin (A), the components (a), (b), (c) and γ-butyrolactone are added to the reaction vessel and the temperature is increased. When the internal temperature reaches 100 ° C., the raw material ( Evaluation was made based on whether or not the components (a), (b), and (c) were dissolved.
(Evaluation) ○: Completely dissolved △: Slightly undissolved ×: Almost insoluble

<Preparation of polycarbonate imide resin paste>
Filler (C) was added to polycarbonate imide resin (A), and the mixture was diluted with γ-butyrolactone to obtain a polycarbonate imide resin composition. An antifoaming 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 mill to obtain a paste in which the filler was uniformly dispersed. The epoxy resin (B) was mixed with this paste to obtain a polycarbonate imide resin paste.

<Preparation of laminated film>
As the laminated film, Viroflex (registered trademark) (manufactured by Toyobo) was used as a commercially available polyimide base film.
A polycarbonate imide resin paste is printed on a two-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, base material 20 μm) manufactured by Toyobo using a SUS mesh plate (150 mesh manufactured by NBC Meshtech, emulsion thickness 21 μm). A predetermined pattern was printed at a speed of 5 cm / sec, and dried at 80 ° C. for 6 minutes in an air atmosphere (screen printing). Thereafter, by heating and curing at 150 ° C. for 2 hours, a laminated film provided with a coverlay (coating) made of a polycarbonate imide resin paste was obtained. The thickness of the coating was 10 μm. This sample was used for evaluation of printing characteristics, low warpage, solder heat resistance, adhesion, and pencil hardness.
Furthermore, a polycarbonate imide resin paste was 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, substrate 20 μm). Was printed with a SUS mesh plate (150 mesh manufactured by NBC Meshtech Co., Ltd., emulsion thickness 21 μm) at a printing speed of 5 cm / sec, and dried at 80 ° C. for 6 minutes in an air atmosphere (screen printing). Thereafter, by heating and curing at 150 ° C. for 2 hours, a laminated film having a coverlay (coating) made of a polycarbonate imide resin paste on a copper circuit was obtained. The thickness of the coating was 10 μm. This sample was used for evaluating flex resistance.

<Low temperature drying / curability>
The polycarbonate imide-based resin paste was applied to a 100 μm-thick polypropylene film with an applicator so that the thickness after drying became 20 μm. Then, after drying at a temperature of 120 ° C. for 90 minutes, it was peeled off from the polypropylene film. 0.125 g of the peeled film was dissolved in 25 ml of N-methyl-2-pyrrolidone at 100 ° C. for 2 hours, and the solvent was filtered off with a glass filter. The remaining gel component 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 (%) = mass after dissolution of solvent / initial mass × 100
(Evaluation) ：: Gel fraction ≧ 85%
×: less than 85% gel fraction

<Thickness (thixotropic ratio)>
Using a Brookfield BH rotational viscometer, the measurement was performed according to the following procedure. 90 ml of the 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 thermostatic water bath. Next, after stirring 40 times for 12 to 15 seconds using a glass rod, a predetermined rotor is set, the mixture is allowed to stand for 5 minutes, and then read at a scale when rotated at 10 rpm for 3 minutes to calculate the viscosity. did. Similarly, it was calculated from the value of the viscosity measured at 25 ° C. and 1 rpm by the following equation.
Thixotropic degree = 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) ：: Good plate releasability and flat printing surface △: Poor plate releasability or unevenness on printing surface ×: Poor plate releasability and unevenness on printing surface Be

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

<Flex resistance (MIT test)>
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 cracks occurred was recorded.
(Judgment) ：: No crack occurred after bending 250 times or more ○: No crack occurred after bending 200 times or more ×: Crack occurred less than 200 times

<Solder heat resistance>
The obtained laminated film was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with JIS-C-6481 (1996), and observed for appearance abnormality such as peeling or swelling.
(Judgment) ○: No appearance abnormality △: Slight appearance abnormality ×: Overall appearance abnormality

<Adhesion>
According to JIS-K-5600-5-6 (1999), 100 laminated grids of 1 mm were formed on the obtained laminated film, and a peeling test was performed with Cellotape (registered trademark) to evaluate the peeled state of the grid. did.
(Judgment) ○: No peeling at 100/100 (no peeling)
Δ: 70 to 99/100 no peeling (1 to 30 peeling)
×: No peeling from 0 to 69/100 (31 to 100 peels)

<Pencil hardness>
The obtained laminated film was evaluated according to JIS-K-5600-5-4 (1999). The pencil hardness is preferably 2H or more, more preferably 3H or more.

<Tensile test>
The tensile modulus and elongation at break were evaluated according to JIS-K-7161 (2014) using a tensile tester (trade name “Tensile Compression Tester TG-2kN”, manufactured by Minebea Co., Ltd.). A film sample obtained by curing the polycarbonate imide resin paste at 150 ° C. for 30 minutes was measured under the following conditions.
Sample size: width 10mm x length 40mm
Tensile speed: 20 mm / min

<High temperature and high humidity resistance>
The polycarbonate imide resin paste was applied to a 25 μm-thick Kapton (registered trademark) EN film (a polyimide film manufactured by Du Pont-Toray Co., Ltd.) using an applicator so that the thickness after drying became 10 μm. Then, after drying at a temperature of 150 ° C. for 2 hours, a sample was prepared.
The obtained sample was put into a saturated pressure steam test (PCT: Pressure Cooker Test) at 121 ° C., 2 atm and 100% RH. After 265 hours, the sample was taken out and the surface condition was evaluated.
(Judgment) ：: No abnormality in appearance △: Slight abnormality in appearance ×: Swelling and falling off or dissolved in coating film

(Production Example 1) (b) Synthesis of acid dianhydride having a polycarbonate skeleton represented by general formula (5) (b-1)
In a reaction vessel, 167 g (0.87 mol) of trimellitic anhydride (TMA) and thionyl chloride were charged and reacted to synthesize chloride of trimellitic anhydride. Next, 183 g (0.87 mol) of chloride of trimellitic anhydride and 434 g (0.43 mol) of Duranol T5651 (Asahi Kasei Chemicals, Inc., molecular weight 1000) as a diol compound were esterified in toluene at 30 ° C. Thus, a tetracarboxylic dianhydride containing a polycarbonate skeleton was synthesized.

(Production Example 2)
30.0 g (0.02 mol) of the component (b-1), 9.61 g (0.05 mol) of trimellitic anhydride (TMA), an acid dianhydride containing a fluorene structure (formula (1)) synthesized in Production Example 1. (8) Compound) 20.7 g (0.03 mol), o-tolidine diisocyanate (TODI) 25.1 g (0.095 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0]-as polymerization catalyst 0.07 g of 7-undecene (DBU) was added and dissolved in 308.2 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 with 96.3 g of γ-butyrolactone, and cooled to room temperature to give a brownish brown matter having a nonvolatile content of 16% by mass. A good polycarbonate imide resin solution A-1 was obtained.

(Production Example 3)
30.0 g (0.02 mol) of the component (b-1), 9.61 g (0.05 mol) of trimellitic anhydride (TMA), an acid dianhydride containing a fluorene structure (formula (1)) synthesized in Production Example 1. (8) Compound) 20.7 g (0.03 mol), o-tolidine diisocyanate (TODI) 23.5 g (0.09 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0]-as polymerization catalyst 0.07 g of 7-undecene (DBU) was added and dissolved in 227.9 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 with 12.7 g of γ-butyrolactone, and cooled to room temperature to obtain a brownish brown matter having a nonvolatile content of 24% by mass. A good polycarbonate imide resin solution A-2 was obtained.

(Production Example 4)
30.0 g (0.02 mol) of the component (b-1), 9.61 g (0.05 mol) of trimellitic anhydride (TMA), an acid dianhydride containing a fluorene structure (formula (1)) synthesized in Production Example 1. (8) Compound) 20.7 g (0.03 mol), 20.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, 3.31 g (0.3%) of 2,4-tolylene diisocyanate (TDI). 02 mol) and 0.07 g of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were dissolved in 301.4 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 with 41.9 g of γ-butyrolactone, and cooled to room temperature to obtain a brownish solid with a nonvolatile content of 18% by mass. A good polycarbonate imide resin solution A-3 was obtained.

(Production Example 5)
45.0 g (0.03 mol) of the component (b-1), 9.61 g (0.05 mol) of trimellitic anhydride, an acid dianhydride containing a fluorene structure (formula (8)) synthesized in Production Example 1. Compound) 13.8 g (0.02 mol), o-tolidine diisocyanate (TODI) 25.9 g (0.098 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene as polymerization catalyst 0.07 g of (DBU) was added and dissolved in 390.3 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 with 28.0 g of γ-butyrolactone, and cooled to room temperature to obtain a brownish brown matter having a nonvolatile content of 17% by mass. A good polycarbonate imide resin solution A-4 was obtained.

(Production Example 6)
15.0 g (0.01 mol) of the component (b-1), 9.61 g (0.05 mol) of trimellitic anhydride, an acid dianhydride containing a fluorene structure (formula (8)) synthesized in Production Example 1 Compound) 27.6 g (0.04 mol), o-tolidine diisocyanate (TODI) 25.1 g (0.095 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene as polymerization catalyst 0.07 g of (DBU) was added and dissolved in 275.8 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 with 38.3 g of γ-butyrolactone, and cooled to room temperature to give a brownish solid with a nonvolatile content of 18% by mass. A good polycarbonate imide resin solution A-5 was obtained.

(Example 1)
With respect to 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2, 4.5 parts by mass of Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.) as a filler and BYK (registered) as an antifoaming agent (Trademark) -054 (manufactured by Big Chemie) and 2.7 parts by mass of BYK-354 (manufactured by Big Chemie) as a leveling agent to obtain a polycarbonate imide resin composition. The composition was first roughly kneaded, and then kneaded three times using a high-speed three-roll mill, whereby a paste having uniform filler dispersion and thixotropic properties was obtained. A solution of HP-7200 (trade name of dicyclopentadiene type epoxy resin manufactured by DIC Corporation, epoxy equivalent: about 278 g / eq) in γ-butyrolactone solution (solid content: 75 %) Was added to obtain a polycarbonate imide resin paste (1) of the present invention. When the viscosity was adjusted with γ-butyrolactone, the solution viscosity was 200 poise and the thixotropic degree was 1.22. The polycarbonateimide of the present invention was placed on a copper circuit (L / S = 50/50) obtained by a subtractive method from Toyobo 2-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, base material 20 μm). A predetermined pattern was printed on the resin paste (1) with a SUS mesh plate (150 mesh, NBC Meshtec Co., Ltd., emulsion thickness 21 μm) at a printing speed of 5 cm / sec, and dried in an air atmosphere at 80 ° C. for 6 minutes. Thereafter, by heating and curing at 150 ° C. for 2 hours, a COF substrate (evaluation sample 1) provided with a coverlay (coating) made of a polycarbonate imide resin paste was obtained. The thickness of the coating was 10 μm. Table 1 shows the evaluation results.

(Examples 2 to 5)
Except that the polycarbonate imide resin (A) solution and the components (B) to (C) shown in Table 1 were used, pastes were prepared in the same manner as in Example 1, and evaluation samples 2 to 5 were produced. . Table 1 shows the evaluation results.

(Comparative Example 1)
9.61 g (0.05 mol) of trimellitic anhydride, 34.5 g (0.05 mol) of an acid dianhydride having a fluorene structure (compound of formula (8)), and o-tolidine diisocyanate (TODI) as a diisocyanate. 1 g (0.1 mol) and 0.07 g of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) as a polymerization catalyst were added and dissolved in 156.5 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours while stirring under a nitrogen stream, diluted with 26.1 g of γ-butyrolactone, and cooled to room temperature to obtain a brownish brown matter having a nonvolatile content of 25% by mass. A good polycarbonate imide resin solution B-1 was obtained. After preparing a paste in the same manner as in Example 1, Evaluation Sample 6 was produced. Table 1 shows the evaluation results. In this case, the warpage increased because the amount of the flexible component (b-1) was not copolymerized.

(Comparative Example 2)
30.0 g (0.02 mol) of the component (b-1), 11.5 g (0.06 mol) of trimellitic anhydride, an acid dianhydride containing a fluorene structure (formula (8)) synthesized in Production Example 1 Compound) 13.8 g (0.02 mol), o-tolidine diisocyanate (TODI) 25.1 g (0.095 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene as polymerization catalyst 0.07 g of (DBU) was added and dissolved in 288.3 g of γ-butyrolactone. Thereafter, the mixture was polymerized at 80 ° C. to 190 ° C. while stirring under a nitrogen stream, but could not be evaluated due to insolubilization (almost insoluble) in the process.

(Comparative Example 3)
15.0 g (0.01 mol) of the component (b-1), 13.5 g (0.07 mol) of trimellitic anhydride, an acid dianhydride containing a fluorene structure (formula (8)) synthesized in Production Example 1 Compound) 13.8 g (0.02 mol), o-tolidine diisocyanate (TODI) 25.1 g (0.095 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene as polymerization catalyst 0.07 g of (DBU) was added and dissolved in 235.9 g of γ-butyrolactone. Thereafter, the mixture was polymerized at 80 ° C. to 190 ° C. while stirring under a nitrogen stream, but could not be evaluated due to insolubilization (almost insoluble) in the process.

(Comparative Example 4)
13.5 g (0.07 mol) of trimellitic anhydride, 20.7 g (0.03 mol) of a fluorene structure-containing dianhydride (compound of formula (8)), and o-tolidine diisocyanate (TODI) as a diisocyanate. 1 g (0.095 mol) and 0.07 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were added and dissolved in 203.6 g of γ-butyrolactone. Thereafter, the mixture was polymerized at 80 ° C. to 190 ° C. while stirring under a nitrogen stream, but could not be evaluated due to insolubilization (almost insoluble) in the process.

(Comparative Example 5)
75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 9.61 g (0.05 mol) of trimellitic anhydride, and 25.1 g of o-tolidine diisocyanate (TODI) as a diisocyanate. (0.095 mol), 0.07 g of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) was added as a polymerization catalyst, and dissolved in 405.4 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 with 56.3 g of γ-butyrolactone, and cooled to room temperature to obtain a brownish brown matter having a nonvolatile content of 18% by mass. A good polycarbonate imide resin solution B-5 was obtained. After preparing a paste in the same manner as in Example 1, Evaluation Sample 7 was produced. Table 1 shows the evaluation results. In this case, since the fluorene structure-containing acid anhydride, which is a rigid component, was not copolymerized, the coating film was flexible and elongated, and the bending resistance effect was not observed. Furthermore, heat resistance was low, and solder heat resistance and high-temperature high-humidity were reduced.

(Reference Example 1)
Example 1 was repeated except that the polycarbonate imide resin solution A-2 obtained in Production Example 3 was used and that HP-7200H (trade name of dicyclopentadiene type epoxy resin manufactured by DIC Corporation) was not blended. A paste was prepared in the same manner as described above (evaluation sample 8). Since the epoxy resin was not blended, the curing of the paste was insufficient and the solder heat resistance was reduced. Table 1 shows the evaluation results.

(Reference Example 2)
A paste was prepared in the same manner as in Example 1 except that the polycarbonate imide-based resin solution A-2 obtained in Production Example 3 was used and no filler was blended (evaluation sample 9). Since no filler was added, thixotropic properties were insufficient, and screen printing was impossible. Therefore, a laminated film sample for evaluation could not be produced.

ポリカーボネート The polycarbonate imide resin obtained by the present invention and the paste using the same have excellent non-nitrogen-based solvent solubility, low warpage, bending resistance, and high-temperature and high-humidity resistance as a film-forming material. It is useful for overcoat inks and solder resist inks for various electronic components such as COF substrates, and can be used in a wide range of electronic equipment as paints, coatings, adhesives, etc. There is expected.

Claims

When the composition contains the components represented by the general formula (1) and the components represented by the general formula (2), and all the components are 200 mol%, the components represented by the general formula (1) and the general formula ( The polycarbonate imide resin (A), wherein the total of the components represented by 2) is 45 mol% or more.

(In the general formula (1), a plurality of R 1 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and q independently represents an integer of 1 to 4.)

(In the general formula (2), a plurality of R 2 each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)
The polycarbonate imide resin (A) according to claim 1, further comprising a component represented by the general formula (3).

(In the general formula (3), a plurality of R 3 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, r each independently represents an integer of 1 to 4, and p is 0 or 1. is there.)
3. The polycarbonate imide resin (A) according to claim 1, wherein the component represented by the general formula (1) is 5 to 45 mol%, and the component represented by the general formula (2) is 5 to 45 mol%. ).
(4) The polycarbonate imide resin (A) according to claim 2 or 3, wherein the component represented by the general formula (3) is 50 mol% or more.
A polycarbonate imide resin paste containing the polycarbonate imide resin (A), the epoxy resin (B), and the filler (C) according to any one of claims 1 to 4.
(A) an acid dianhydride having a fluorene structure represented by the general formula (4); (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5); Assuming that the total acid component is 100 mol%, (a) an acid dianhydride having a fluorene structure represented by the general formula (4) and (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (5) The polycarbonate imide resin (A), wherein the total amount of the components is 45 mol% or more.

(In the general formula (4), a plurality of R 4 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and s independently represents an integer of 1 to 4.)

(In the general formula (5), a plurality of R 5 each independently represent a divalent organic group having 1 or more carbon atoms, and m is an integer of 1 or more.)
The polycarbonate imide resin (A) according to claim 6, wherein (c) the isocyanate component is a diisocyanate represented by the general formula (6).

(In the general formula (6), a plurality of R 6 each independently represent hydrogen or an alkyl group having 1 to 3 carbons, t each independently represents an integer of 1 to 4, and p is 0 or 1. is there.)
(A) The fluorene structure-containing acid dianhydride represented by the general formula (4) is 5 to 45 mol%, and (b) the acid dianhydride having a polycarbonate skeleton represented by the general formula (5) is 5 to 45 mol%. The polycarbonate imide resin (A) according to claim 6 or 7, which is mol%.
(10) The polycarbonate imide resin (A) according to any one of claims 6 to 8, wherein the diisocyanate represented by the general formula (6) is at least 50 mol%, when the total isocyanate component is 100 mol%.
A polycarbonate imide resin paste containing the polycarbonate imide resin (A) according to any one of claims 6 to 9, an epoxy resin (B), and a filler (C).
The polycarbonate imide resin paste according to claim 5 or 10, wherein the degree of thixotropic is 1.1 or more.
The polycarbonate imide resin paste according to claim 5, 10 or 11, which is used for COF.
A cured product of the polycarbonate imide resin paste according to any one of claims 5, 10 to 12.
An electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer containing the cured product according to claim 13 as a component.