KR20180072591A - Polycarbonate imide resin and paste using the same - Google Patents

Abstract

(1) a polycarbonate imide resin paste which can be applied as a solder resist layer, a surface protective layer or an adhesive layer simultaneously satisfying both (2) solubility in non-glycolic solvent, (2) low bending property and (3) flexibility.
[MEANS FOR SOLVING PROBLEMS] A semiconductor device comprising a component represented by a specific structural formula (1), a component represented by a specific structural formula (2), and a component represented by a specific structural formula (3) , The constituent component represented by the specific structural formula (1) is 10 mol% or more, the constituent component represented by the specific structural formula (2) is more than 30 mol% and less than 70 mol% (A) of the polycarbonate imide resin (A).

Description

Polycarbonate imide resin and paste using the same

The present invention relates to a polycarbonate imide resin and a paste using the polycarbonate imide resin. In particular, a polycarbonate imide resin paste which has excellent heat resistance and flexibility and is suitable for a coating method such as a printing machine, a dispenser or a spin coater, which is useful for COF (Chip On Film) substrate, and a solder resist layer , A surface protection layer or an adhesive layer.

In general, polyimide-based resins are widely used as insulating materials for electrical and electronic devices because they are excellent in heat resistance, insulation, chemical resistance, and the like. In particular, it is used as a raw material for a COF substrate, and is applied to wiring board materials and mounting board materials that require 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, or the like, a relay cable between boards such as a smart phone, a tablet device terminal, a digital camera, (Protective layer of a circuit) of a semiconductor device. Particularly, in a printed wiring board, a solder resist is widely used as a permanent protective film of a circuit. The solder resist is a film formed on the entire surface excluding the portion to be soldered of the circuit conductor, so that it is possible to prevent the solder from adhering to the unnecessary portion when the electronic component is wired on the printed wiring board, And is used as a protective film.

However, since a solder resist layer, a surface protective layer or an adhesive layer which is a constituent element of a COF substrate is often applied and printed in the form of a solution, a combination of a solvent-free closed-ring polyimide resin as a material thereof has been proposed. However, conventionally, as a solvent for varnishing a polyimide resin, a high boiling point nitrogen solvent such as N-methyl-2-pyrrolidone is used. Therefore, during drying / curing, There is a problem that thermal degradation (thermal deterioration) of the electronic component occurs.

In addition, since the polyimide resin is generally hard with a high elastic modulus, when the laminate is laminated on a substrate such as a film or a copper foil, warpage or the like occurs due to a difference in elastic modulus. Further, the cured film has a problem of insufficient flexibility and inferior flexibility.

Examples of the polyimide-based resin having flexibility and softness that are soluble in a non-nitrogen-based solvent and made flexible and have a low elastic modulus include polyimide-modified polyimide-based resins (Patent Document 1) Lt; / RTI >

These polysiloxane-modified polyimide-based resins use diamines having expensive dimethylsiloxane bonds as starting materials for lowering the elastic modulus, resulting in poor economical efficiency. In addition, there is a problem that adhesion, solvent resistance, and chemical resistance are lowered as the amount of polysiloxane copolymerization increases.

Also disclosed is a composition in which a certain amount of a polycarbonate resin is mixed with a polyimide resin to impart flexibility to improve moldability of the resin composition (Patent Document 3) (Patent Document 4). Also disclosed is a thermoplastic resin composition in which molding processability is improved by mixing a polyimide resin with an epoxy resin and a polycarbonate resin (Patent Document 5).

Japanese Patent Application Laid-Open No. 7-304950 Japanese Patent Laid-Open No. 8-333455 Japanese Unexamined Patent Application Publication No. 5-320492 Japanese Unexamined Patent Application Publication No. 6-136267 Japanese Patent Application Laid-Open No. 62-7758

However, they are examples of resins suitable for melt-kneading and melt-extrusion, and are excellent in heat resistance and mechanical strength, but they are not soluble in non-nitrogen-based solvents, and can not be said to have low flexural strength and flexibility.

As can be seen from this example, in the prior art to date, the solder resist layer, the surface protective layer, or the adhesive layer which satisfies both (1) solubility in non-nitrogen based solvent, (2) low bending property, Applicable polyimide resin paste is not obtained.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art. That is, an object of the present invention is to provide a polycarbonate imide resin which is excellent in (1) solubility in a non-glycolide solvent, (2) low bending property, (3) excellent flexibility and heat resistance, chemical resistance and electrical properties, and a poly And an electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste.

A resin composition comprising a constituent component represented by the general formula (1), a constituent component represented by the general formula (2) and a constituent component represented by the formula (3) ) Is 10 mol% or more, the constituent component represented by the general formula (2) is more than 30 mol% but less than 70 mol%, and the constituent component represented by the formula (3) is more than 50 mol% (A). ≪ / RTI >

(In the general formula (1), A is a straight chain alkylene group which may have a substituent having 1 to 10 carbon atoms.)

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

(b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4) and (c) o-tolylidine diisocyanate (TODI) as essential comonomers, in the presence of an alkylene glycol bisanhydrotrimellitate (B) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), wherein the total amount of the acid dianhydride is 100 mol%, and the amount of the alkylene glycol bisanhydrotrimellitate is 10 mol% Is more than 30 mol% but less than 70 mol%, and (c) o-tolylidine diisocyanate (TODI) is more than 50 mol% when the total amine component is taken as 100 mol% A).

(In the general formula (4), a plurality of R's each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

Wherein the polycarbonate imide resin (A), the epoxy resin (B) having two or more epoxy groups per molecule, and the filler (C) are contained.

The polycarbonate imide resin paste preferably has a shrinkage degree of 1.2 or more, and is also preferably used for COF.

And a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the polycarbonate imide resin paste.

According to the present invention, a polycarbonate imide resin excellent in solubility in a non-nitrogen-based solvent, (2) low bending property, (3) flexibility in bending property) and a paste using the polycarbonate imide resin, An electronic component having a solder resist layer, a surface protective layer, or an adhesive layer can be provided.

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

<Component (A) of polycarbonate imide resin>

The polycarbonate imide resin (A) of the present invention will be explained. The polycarbonate imide resin (A) contains a constituent component represented by the general formula (1), a constituent component represented by the general formula (2), and a constituent component represented by the formula (3) (1) is not less than 10 mol%, the constituent component represented by the general formula (2) is not less than 30 mol% but less than 70 mol%, and the constituent component represented by the formula (3) Is more than 50% by mol. &Lt; / RTI &gt;

(In the general formula (1), A is a straight chain alkylene group which may have a substituent having 1 to 20 carbon atoms.)

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

&Lt; Component Represented by General Formula (1)

The polycarbonate imide resin (A) of the present invention can be expected to exhibit an improvement in solubility in a non-zeolite solvent and heat resistance by containing a constituent component represented by the general formula (1). In the general formula (1), A is a straight chain alkylene group having 1 to 20 carbon atoms which may have a substituent, and the number of carbon atoms is preferably 2 or more and 10 or less. In the case of having a substituent, the substituent is preferably an alkyl group having 1 to 3 carbon atoms.

The content of the constituent component of the general formula (1) in the polycarbonate imide resin (A) is required to be 10 mol% or more when the total constituent components are 200 mol%. , Preferably at least 20 mol%, and more preferably at least 30 mol%. Further, it is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less. If it is less than 10 mol%, the solubility and heat resistance of the non-nitrogen-based solvent may not be obtained. If it is more than 90 mol%, the constituent component represented by the general formula (2) In some cases. Therefore, the low bending property and the bending resistance (mechanical property) may be lowered.

&Lt; Component represented by general formula (2)

Since the constituent component represented by the general formula (2) has flexibility, the polycarbonate imide resin (A) of the present invention can be imparted with low warpage property, solubility in non-glycolic solvent, and the like.

In the general formula (2), a plurality of R's 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, and is preferably 20 or less, and more preferably 18 or less. The divalent organic group is not particularly limited, but a straight chain alkylene group which may have a substituent is preferable, and it is preferable that the carbon number of the divalent organic group also includes substituent carbon. In addition, n is an integer of 1 or more, preferably 2 or more, more preferably 3 or more, more preferably 10 or less, and more preferably 8 or less.

The content of the constituent component represented by the general formula (2) in the polycarbonate imide resin (A) should be more than 30 mol%, preferably 35 mol% % Or more, and more preferably 40 mol% or more. Further, it is required to be less than 70 mol%, preferably 65 mol% or less, and more preferably 60 mol% or less. If it is 30 mol% or less, warpage may occur in the case of lamination, or the solubility in the non-nitrogen-based solvent may be lowered. Therefore, the resin may be precipitated within 5 to 30 占 폚 within one month. On the other hand, if it is 70 mol% or more, the bending resistance (mechanical properties) and heat resistance may be lowered.

As the constituent components of the polycarbonate imide resin (A), the total amount of the constituent components represented by the general formula (1) and the constituent components represented by the general formula (2) is preferably at least 60 mol%, more preferably at least 65 mol% , More preferably 70 mol% or more, particularly preferably 75 mol% or more, and most preferably 80 mol% or more. When the amount is too small, the low-bending property and the solubility in the non-nitrogen-based solvent may be lowered.

&Lt; Component represented by the formula (3) >

The polycarbonate imide resin (A) of the present invention can exhibit excellent flex resistance by containing the constituent component represented by the formula (3).

The content of the constituent component represented by the formula (3) in the polycarbonate imide resin (A) should be more than 50 mol%, preferably not less than 60 mol% when the total constituent component is 200 mol% , More preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. When the content is 50 mol% or less, the bending resistance may not be sufficiently exhibited.

The polycarbonate imide resin (A) of the present invention contains a predetermined amount of the constituents of the above-mentioned general formulas (1), (2) and (3). (B) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4); and (c) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4). The polycarbonate imide resin (A) (A) an alkylene glycol bisanhydrotrimellitate in an amount of 10 mol% or more, and (b) a compound represented by the general formula (4) ) Is more than 30 mol% and less than 70 mol%, and the total amine component is 100 mol%, (c) the amount of the o-tolylidine diisocyanate exceeds 50 mol% .

(In the general formula (4), a plurality of R's each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

< (a) Alkylene glycol bisanhydrotrimellitate >

The component (a) constituting the polycarbonate imide resin (A) used in the present invention is required to be (a) an alkylene glycol bisanhydrotrimellitate (hereinafter, simply referred to as component (a)). By using alkylene glycol bisanhydrotrimellitate, an effect of excellent solubility in non-glycolide solvent and heat resistance can be expected.

Specific examples of the alkylene glycol bisanhydrotrimellitate include, but are not limited to, methylene glycol bisanhydrotrimellitate, ethylene glycol bisanhydrotrimellitate (TMEG), propylene glycol bisanhydrotrimellitate, 4-butanediol bisanhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate, polyethylene glycol bisanhydrotrimellitate or polypropylene glycol bisanhydrotrimellitate, and these may be used singly or in combination of two or more species Or more can be used in combination. Among them, ethylene glycol bisanhydrotrimellitate (TMEG) is preferable from the viewpoint of availability.

The copolymerization amount of the component (a) is required to be 10 mol% or more when the total acid component of the reaction object is 100 mol%. , Preferably at least 20 mol%, and more preferably at least 30 mol%. Further, it is preferably 90 mol% or less, more preferably 80 mol% or less, particularly preferably 70 mol% or less. If it is less than 10 mol%, the solubility and heat resistance of the non-zeolite solvent may not be obtained. If it is more than 90 mol%, the components (b) and (c) described later may not be copolymerized sufficiently. Therefore, the low bending property and the bending resistance (mechanical property) may be lowered.

<(b) An acid dianhydride having a polycarbonate skeleton represented by the general formula (4)

(B) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4) (hereinafter, simply referred to as a component (b)) constituting the polycarbonate imide resin (A) of the present invention is a polycarbonate imide Is copolymerized as a flexible component which imparts low bending property, non-nitrogen-based solvent solubility, etc. to the resin (A).

(b) is an acid dianhydride having a polycarbonate skeleton represented by the general formula (4).

In the general formula (4), a plurality of R's 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, and is preferably 20 or less, and more preferably 18 or less. The divalent organic group is not particularly limited, but an alkylene group which may be a straight chain or a substituent is preferable, and it is preferable that the carbon number also includes substituent carbon. In addition, n is an integer of 1 or more, preferably 2 or more, more preferably 3 or more, more preferably 10 or less, and more preferably 8 or less.

The polycarbonate diol used for synthesizing the component (b) used in the present invention may be a polycarbonate diol (copolymerized polycarbonate diol) having a plurality of alkylene groups in its skeleton, and commercially available products include, for example, 1,10-hexanediol, 1,9-nonanediol, number average molecular weight of about 1,000), and a curepolyol C-2015N (trade name, manufactured by Kuraray Co., 1,8-octanediol / 1,9-nonanediol, number average molecular weight: about 2,000), a curepolyol C-1050, a curepolyol C-2065N (a carbonate diol manufactured by Kuraray Co., 1,6-hexanediol, number average molecular weight of about 1,000), Kuraraypolyol C-2050 (manufactured by Kuraray Co., Ltd., carbonate diol: 3-methyl-1,5-pentanediol / C-2090 (carbonate diol manufactured by Kuraray Co., Ltd., 3-methyl-1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 2,000), DURANOL (registered trademark) -T5650E (Number average molecular weight: about 500), DURANOL (registered trademark) -T5651 (manufactured by Asahi Kasei Chemicals Co., Ltd.) 1,6-hexanediol, number average molecular weight of about 1,000), DURANOL (registered trademark) -T5652 (manufactured by Asahi Chemical Industry Co., Ltd., polycarbonate diol: 1,5 - pentanediol / 1,6-hexanediol, number average molecular weight: about 2,000).

The method for producing the component (b) is not particularly limited, but can be synthesized by a reaction method known from the chloride of trimellitic anhydride and the diol compound described above. More specifically, first, a diol compound and a deoxidizer are added to 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 캜, but it is more preferably 20 to 40 캜 from the viewpoint of the reaction selectivity. As the reaction ratio of the chloride of trimellitic anhydride to the diol compound, it is preferable to use 2 moles or more of a chloride of trimellitic anhydride relative to 1 mole of the diol compound. The concentration of the solute 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 an acid dianhydride having a polycarbonate skeleton represented by the general formula (4) (hereinafter also referred to as polycarbonate skeleton-containing tetracarboxylic acid dianhydride .) Can be obtained.

The copolymerization amount of the component (b) should exceed 30 mol%, preferably 35 mol% or more, and more preferably 40 mol% or more when the total acid component is 100 mol%. Further, it is required to be less than 70 mol%, preferably 65 mol% or less, and more preferably 60 mol% or less. When the content is less than 30 mol%, the modulus of elasticity may not be sufficiently lowered, and when it is laminated, warpage may occur or the solubility in a non-nitric solvent may decrease. Therefore, the resin may be precipitated within 5 to 30 占 폚 within one month. On the other hand, if it is at least 70 mol%, the above-mentioned component (a) or the component (c) described later can not be contained in a sufficient amount, so that the bending resistance (mechanical properties) and heat resistance may decrease.

As the acid component of the polycarbonate imide resin (A), the total amount of the components (a) and (b) is preferably 60 mol% or more, more preferably 65 mol% or more, still more preferably 70 mol% , Particularly preferably 75 mol% or more, and most preferably 80 mol% or more. If it is too small, the low-bending property and the solubility in the non-nitrogen-based solvent may be lowered.

<Other acid components>

As other acid components, trivalent or tetravalent polycarboxylic acid derivatives having an acid anhydride group can be used. Examples of the aromatic polycarboxylic acid derivative include, but are not limited to, trimellitic acid anhydride (TMA), pyromellitic acid dianhydride, 3,3'-4,4'-benzophenonetetracarboxylic acid dianhydride, 3'-4,4'-biphenyltetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2 , 3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Water, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro 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, and the like, or 1,3-bis (3,4-dicarboxyphenyl) 1,1,3,3-tetramethyldisiloxane dianhydride.

The aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, and examples thereof include butane-1,2,3,4-tetracarboxylic acid dianhydride, pentane-1,2,4,5-tetracarboxylic acid Cyclohexa-1-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-ethylcyclohexa-1-ene, cyclohexanetetracarboxylic acid dianhydride, hexahydropyromellitic dianhydride, Ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic acid dianhydride, Ethyl-cyclohex-1-en-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2) -Tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic acid dianhydride, 1,3-dipropylcyclohexane-1- (2,3) Tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2,2,1] heptane-2,3 , 5,6- Tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3) - (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2,2,1] heptane- 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 acid dianhydride or hexahydrotrimellitic anhydride.

The trivalent and / or tetravalent polycarboxylic acid derivatives having these acid anhydride groups may be used singly or in combination of two or more kinds. The trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group is preferably 40 mol% or less, more preferably 35 mol% or less, and 30 mol% or less, based on 100 mol% , Particularly preferably 25 mol% or less, and most preferably 20 mol% or less.

In addition, aliphatic, alicyclic, and aromatic dicarboxylic acids may be further copolymerized as needed within the scope of not impairing the intended performance. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, dodecanedioic acid, 3-methylpentanedicarboxylic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9 Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, dicyclohexyl dicarboxylic acid, Benzoic acid, oxydianic acid, stilbene dicarboxylic acid, and the like. These dicarboxylic acids may be used singly or in combination of two or more kinds. Considering heat resistance, adhesion, solubility, cost, and the like, sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimeric acid and isophthalic acid are preferable.

< (c) o-Tollydine diisocyanate >

The component (c) constituting the polycarbonate imide resin (A) of the present invention contains o-tolylidine diisocyanate (hereinafter also referred to as TODI) as an essential component. By using o-tolylidine diisocyanate, excellent flex resistance can be exhibited.

The amount of (c) o-tolylidine diisocyanate copolymerization should be more than 50 mol%, preferably not less than 60 mol%, more preferably not less than 70 mol%, based on 100 mol% , More preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. If it is 50 mol% or less, the value of the modulus of elasticity is lowered, and the flexural resistance may not be sufficiently manifested.

&Lt; Other isocyanate compounds >

The polycarbonate imide resin (A) of the present invention may further be copolymerized with an isocyanate compound as necessary insofar as the desired performance is not impaired. Isocyanate compound is not particularly limited and examples thereof include aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate. Preferably, an aromatic polyisocyanate is used. Specific examples of the aromatic polyisocyanate 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 4,3'- 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- Diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether- Diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m - xylylene di Diisocyanate, 4,4'- [2,2bis (4-phenoxyphenyl) propane] diisocyanate, 3,3'- or 2,2'-diisocyanate, p-xylylene diisocyanate, Diisobiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate And the like. (MDI), tolylene-2,4-diisocyanate (TDI) and m-xylylene diisocyanate are preferable from the viewpoints of heat resistance, adhesion, solubility and cost, , And tolylene-2,4-diisocyanate (TDI) are more preferable. These may be used alone or in combination of two or more.

When the amine component used in the polycarbonate imide resin (A) of the present invention is 100 mol%, it is preferable that any of the above isocyanate compounds is 100 mol%. If a diamine compound corresponding to the isocyanate is used in place of the isocyanate, a polyamic acid is used as a precursor of the polycarbonate polyimide resin. When polyamic acid is used, it is necessary to apply the polyamic acid-containing paste to a substrate such as COF (Chip On Film) and then to imidize it at a high temperature of about 200 DEG C or higher. In addition, there are restrictions on the facilities. In the present invention, since only the isocyanate compound containing TODI is used for the amine component, the paste can be treated at a lower temperature than the polyamic acid-containing paste.

In addition to the component (b), other flexible components may be copolymerized as needed within a range that does not impair the desired performance. For example, aliphatic / aromatic polyester diols (VYLON (registered trademark) 220 manufactured by Toyobo Co., Ltd.), aliphatic / aromatic polycarbonate diols (PLACCEL (registered trademark) manufactured by Daicel Chemical Industries, (Trade name) manufactured by Asahi Kasei Chemicals Co., Ltd., such as CD220, C-1015N, C-1050, C-1065N, C-1090, C-2015N, C- (Trade name: PLACCEL (registered trademark) manufactured by Dai-ichi Kogaku Kogyo K.K., a trade name, manufactured by Dai-ichi Kogaku Kogyo K.K.), T- -220, etc.), carboxy-modified acrylonitrile butadiene rubbers (trade name: HyproCTBN1300x13 manufactured by Ube Kosan Co., Ltd.), polysiloxane derivatives such as polydimethylsiloxane diol, polymethylphenylsiloxane diol and carboxy modified polydimethylsiloxane .

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

In the isocyanate method, the blending amount of the component (a), the component (b) and the component (c) is such that the ratio of the number of the acid anhydride groups to the number of the isocyanate groups is from 0.8 to 1.2 in the number of isocyanate groups / . If it is less than 0.8, it may be difficult to increase the molecular weight of the polycarbonate imide resin (A), and the heat resistance and bending resistance may be reduced or the coating film may be fragile. If it is higher than 1.2, the viscosity of the polycarbonate imide resin (A) may be increased, and the plate separation may be deteriorated at the time of printing in the case of making 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-based 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 generated in the isocyanate process is removed And condensation.

Examples of the solvent include, but are not limited to, ethers such as diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), triethylene glycol Butyrolactone, and acetic acid cellosolve are used as the ester solvent, and methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone and the like are used as the ketone solvent, Examples of the aromatic hydrocarbon solvent include toluene, xylene, and sorbic acid. 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 which dissolves the polycarbonate imide resin (A) to be produced. It is more preferable to use a solvent suitable for the polycarbonate imide resin paste after polymerization desirable. By doing so, troublesome operations such as solvent replacement and the like are eliminated, and production can be made at a 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 占 폚, the solvent may volatilize during the polymerization reaction. In addition, when screen printing is performed, for example, the volatilization of the solvent may be accelerated and clogging may occur. If it exceeds 230 ° C, it may be difficult to impart low temperature drying / curability. It is preferable to use γ-butyrolactone, cyclohexanone, diglyme or triglyme in order to impart relatively high volatility, low-temperature drying / curability, excellent varnish stability and efficient reaction in a homogeneous system Do.

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

In the isocyanate method, the reaction temperature is preferably from 60 to 200 캜, and more preferably from 100 to 180 캜. If the temperature is lower than 60 ° C, the reaction time becomes longer. If the temperature exceeds 200 ° C, the monomer component may be decomposed during the reaction. Further, a three-dimensional reaction occurs and gelation tends to occur. The reaction temperature may be set in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and in particular, the reaction concentration.

In the isocyanate method, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo [2,2,2] octane), DBU (1,8-di Aminocarbocyclo [5,4,0] -7-undecene), alkali metal, alkaline earth metal compounds such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride, Titanium, cobalt, tin, zinc, aluminum or the like, or a semi-metal compound.

&Lt; Preparation of polycarbonate imide resin (A) >

An example of the production method of the polycarbonate imide resin (A) can be obtained by condensation reaction (polyimide) of the component (a), 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 the components (a), (b), (c), the polymerization catalyst and the polymerization solvent are added and dissolved in the reaction vessel, the mixture is stirred at 80 to 190 캜, preferably 100 to 180 캜, for 5 hours or more After the reaction, the desired polycarbonate imide resin (A) can be obtained by diluting with a polymerization solvent to a suitable solvent viscosity and cooling.

The polycarbonate imide resin (A) used in the present invention preferably has a molecular weight corresponding to the logarithmic viscosity of 0.1 to 2.0 dl / g at 30 占 폚 in? -Butyrolactone, more preferably 0.2 to 1.5 dl / g. &lt; / RTI &gt; When the logarithmic viscosity is less than 0.1 dl / g, the heat resistance may decrease or the coating film may be fragile. Further, the tackiness of the paste is high, and the plate separation may be deteriorated. On the other hand, when it exceeds 2.0 dl / g, it is difficult to dissolve in a solvent, and it tends to be insolubilized during polymerization. In addition, the viscosity of the varnish may increase, which may make handling difficult, or the adhesion with the substrate may be deteriorated.

The glass transition temperature of the polycarbonate imide resin (A) used in the present invention is preferably 20 占 폚 or higher, and more preferably 60 占 폚 or higher. If the temperature is lower than 20 占 폚, heat resistance is insufficient and the resin may be blocked. The upper limit is not particularly limited, but 300 占 폚 or lower is preferable from the viewpoint of solvent solubility.

&Lt; 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. Examples of the epoxy resin (B) include, but are not limited to, bisphenol A type epoxy resins such as trade name jER (registered trademark) 828 and 1001 manufactured by Mitsubishi Chemical Corporation, trade name ST- 2004 and 2007, bisphenol F type epoxy resins such as YDF-170 and 2004 manufactured by Tokyo Chemical Industry Co., Ltd .; and YDB-400 and 600 commercialized by Tokto Chemicals Co., Bisphenol A type epoxy resin, trade name jER (registered trademark) 152, 154, 157S70, 1032H60, manufactured by Mitsubishi Kagaku K.K., EPN (trade name) -201 manufactured by Nippon Kayaku Co., Phenol novolak type epoxy resin such as DEN-438 (trade name, manufactured by Dow Chemical Company), YDCN-702 and 703 (trade names, manufactured by TOKO KASEI Co., Ltd.) and EOCN (registered trademark) Cresol novolak type epoxy resin such as 103S and 104S, YD-171 (trade name, manufactured by Toki Chemical Co., Ltd.) Epon 1031S manufactured by Yucca Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals Inc., Denacol (registered trademark) EX manufactured by Nagase Chemtech Co., Polyfunctional epoxy resin such as EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411 and EX-321 manufactured by Yucca Epoxy Co., TETRAD (registered trademark) -X, TETRAD-C, manufactured by Mitsubishi Chemical Corporation, trade name GAN manufactured by Nippon Kayaku Co., Ltd., An amine type epoxy resin such as ELM-120 (trade name) manufactured by Sumitomo Chemical Co., Ltd., a polycondensation epoxy resin such as Araldite TM PT810 (trade name, manufactured by Ciba Specialty Chemicals) An alicyclic epoxy resin such as SEROCIDE (registered trademark) 2021, EHPE (registered trademark) 3150 manufactured by UCC, ERL4234 manufactured by UCC, Bisphenol S type epoxy resin such as Epikrone (registered trademark) EXA-1514 manufactured by Ponkagaku Kogyo Co., Ltd., triglycidyl isocyanurate such as TEPIC (registered trademark) manufactured by Nissan Kagaku Kogyo Co., Bisphenol-type epoxy resins such as YX-4000 (trade name, manufactured by Yucca Shell Epoxy Co., Ltd.), and bisphenol-type epoxy resins (such as YL-6056 manufactured by Yucca Shell Epoxy Co., Ltd.) These may be used in combination.

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 per molecule, and o-cresol novolak type epoxy resin are preferable. The amine type epoxy resin is a non-halogen type epoxy resin 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) to be used in the present invention is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, particularly preferably from 3 to 50 parts by mass based on 100 parts by mass of the polycarbonate imide resin (A) To 30 parts by mass. If the blending amount of the epoxy resin (B) is less than 1 part by mass, the solder heat resistance, solvent resistance, chemical resistance and moisture resistance tend to be lowered. When the amount exceeds 50 parts by mass, the low warpage, mechanical properties, heat resistance, The compatibility with the carbonate imide resin (A) tends to be lowered. In addition, the cured film tends to have low flexibility and bending resistance (mechanical properties) to deteriorate.

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

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

<Filler (C) Component>

The filler (C) (hereinafter, 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-described polycarbonate imide resin (A) to form a paste and give thixotropic property (thixotropic property) 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. (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), and the like. Examples of the inorganic filler include silica (SiO ₂ , trade name AEROSIL (registered trademark) manufactured by Nippon Aerosil Co., , Zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT) tannap (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)} , barium silicate (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 (Trade name: Lucentite (registered trademark) STN, Lucentite SPN, Lucene Sites SAN, and the like Lucerne tight SEN), which does not matter even be used alone in combination use of two or more. It is preferable to use silica or lucentite in terms of hue, transparency, mechanical properties, and thixotropy of the resulting paste.

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

The organic filler used in the present invention is not particularly limited as long as it can be dispersed in the above-mentioned polycarbonate imide resin solution to form a paste and can impart thixotropy to the paste. Polyimide resin particles, benzoguanamine resin particles, Particles and the like.

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

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

CN, 2ZMZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN and 2PZ-CN produced by Shikoku Chemicals Corporation, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ- Imidazole derivatives such as 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, and 2P4BHZ, guanamines such as acetoguanamine and benzoguanamine Polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide, organic acid salts thereof And / or epoxy adducts, amine complexes of boron trifluoride, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl- A triazine derivative such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) Tris (dimethyl Aminophenol), tetramethylguanidine, DBU (1,8-diazabicyclo [5,4,0] -7-undecene), DBN (1,5-diazabicyclo [ U-CAT (registered trademark) SA1 (DBU-phenol salt), U-CAT (registered trademark) SA 102 (DBU-octylate), U-CAT ) SA 831 (DBU-phenol novolac resin salt), U-CAT (registered trademark) 5002 (DBU tetraphenylborate salt) (all available from SANA PRO) and / or tetraphenylborate, , Organic phosphines such as polyvinylphenol bromide, tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) , Quaternary phosphonium salts such as hexadecyltributylphosphonium chloride and tetraphenylphosphonium tetraphenylborate, quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride, Diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, IRGACURE (registered trademark) 261 ( A cationic polymerization initiator such as a styrene-maleic anhydride resin, a condensation reaction product of phenyl isocyanate and dimethylamine, a tolylene diisocyanate, Dimethylformamide, isophorone diisocyanate, and the like, and diaminodiphenylamine. These may be used alone or in combination of two or more. Preferably, the curing accelerator has latent curing properties, and examples thereof include organic acid salts of DBU and DBN and / or tetraphenylborate, and photocationic polymerization catalysts.

The amount of the curing accelerator to be used is preferably 0 to 20 parts by mass when the amount of the component (A) is 100 parts by mass. When 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 polycarbonate imide resin (A) component, the epoxy resin (B) component and the filler (C) component described above. If necessary, other components may be blended in the above-mentioned ratio. It is preferable that these components are uniformly mixed with a roll mill, a mixer, a three-necked roll or the like. The mixing method is not particularly limited as far as it is a method capable of obtaining sufficient dispersion. A plurality of kneading by three main rolls is preferable.

The viscosity of the polycarbonate imide resin paste of the present invention in a Brookfield viscometer (hereinafter also referred to as a B-type viscometer) is preferably in the range of 50 dPa · s to 1000 dPa · s at 25 ° C., More preferably in the range of 800 dPa · s. If the viscosity is less than 50 dPa · s, the outflow of the paste after printing becomes large and the film thickness tends to be reduced. When the viscosity exceeds 1000 dPa · s, the transferability of the paste onto the base material is lowered at the time of printing, resulting in a hazy portion, and voids and pinholes in the printed film tend to increase.

Irregularities (thixotropy) are also important. The aspect ratio of the polycarbonate imide resin paste is preferably 1.2 or more, and more preferably 1.3 or more, in a later-described measuring method. The upper limit is preferably 7.0 or less, more preferably 6.0 or less. If the aspect ratio is less than 1.2, the outflow of the paste after printing becomes large and the film thickness tends to be reduced. If it exceeds 7.0, the paste tends not to flow. The degree of irregularity can be adjusted by the blending amount of the component (c) as a shrinkage imparting agent.

The polycarbonate imide resin and paste of the present invention may contain a known coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, Known polymerization inhibitors such as quinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol and phenothiazine, known thickeners such as orthobenzene and montmorillonite, silicone-based, fluorine-based and high- A coupling agent / adhesion-imparting agent such as an antifoaming agent, a leveling agent, an imidazole system, a thiazole system, a triazole system, an organoaluminum compound, an organic titanium compound and an organosilane compound; Triethyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, cresylbis (2,6-crown (Dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, diphenylmethyl phosphate, Phosphorus amide, organic phosphorus flame retardants such as phosphine oxide and red phosphorus, ammonium polyphosphate, triazine, melamine cyanurate, succinoguanamine, ethylene dimelamine, tiguanamine, cyanuric acid triazinyl salt, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanyl melamine sulfate, melamine sulfate and melamine sulfate, potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, alkali polystyrene sulfonate Metal salt flame retardants such as metal salts, metal hydrides such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, A metal oxide such as 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, Inorganic flame retardants such as zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate and zinc stearate, silicon powder and the like, flame retardant additives such as heat stabilizer, antioxidant and lubricant Can be used.

<Coating film>

In the polycarbonate imide resin paste of the present invention, for example, as a solder resist, a cured product can be obtained by curing as follows. That is, it is possible to produce a chip on film (COF) substrate formed by plating copper on a resin substrate such as a polyimide film by a screen printing method, a spraying method, a roll coating method, an electrostatic coating method or a curtain coating method, , The coating film is preliminarily dried at 60 to 120 캜 and then dried at 120 to 200 캜. The drying may be performed in air or in an inert atmosphere. Here, as a method for plating copper on the resin substrate, electroless plating may be used, or copper may be sputtered on the resin substrate.

The layer of the polycarbonate-imide resin paste of the COF substrate thus obtained is a solder resist layer, a surface protective layer, or an adhesive layer of a COF substrate. As described above, the polycarbonate imide resin paste of the present invention can be used as a coating material, a coating agent, an adhesive, etc. in addition to being useful for a semiconductor element, an overcoat ink for various electronic parts, and a solder resist ink. Here, the solder resist layer is a film formed on the entire surface excluding the soldering portion of the circuit conductor, so that it is possible to prevent the solder from adhering to the unnecessary portion when wiring the electronic component to the printed wiring board, As a protective film for preventing the film from being broken. The surface protection layer is used to mechanically and chemically protect the electronic member from the processing step or the use environment by adhering to the surface of the circuit member. The adhesive layer is used when bonding is performed mainly by bonding a metal layer and a film layer.

Example

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The measurements described in the examples were measured by the following methods.

<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 viscosities and solvent viscosities of the solutions were measured at 30 占 폚 by a Uberode-type viscometer and were calculated by the following equations.

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

Where V1 represents the solvent viscosity as measured by the uberodem type viscosity tube where V1 and V2 represent the viscosity of the polymer solution and the solvent (N-methyl-2-pyrrolidone) passing through the capillary of the viscosity tube Time. V3 is the polymer concentration (g / dl).

&Lt; Solubility of non-zeolite solvent &

(A), the component (b), the component (c) and the? -Butyrolactone are added to the reaction vessel during the polymerization of the polycarbonate imide resin (A) (a), (b), and (c)) were dissolved.

(evaluation) ○: completely dissolved

Δ: slightly soluble residue

×: Almost insoluble

&Lt; Preparation of polycarbonate imide resin paste >

A filler (C) was added to the polycarbonate imide resin (A) and diluted with? -Butyrolactone to obtain a polycarbonate imide resin composition. To this solution, a curing accelerator (D), an antifoaming agent and a leveling agent were added. This solution was coarsely kneaded, and then kneaded three times by using a high speed three-roll mill to obtain a paste in which fillers were uniformly dispersed. This paste was mixed with an epoxy resin (B) to obtain a polycarbonate imide resin paste.

&Lt; Fabrication of laminated film &

As the laminated film, commercially available polyimide base film, trade name Viroflex (registered trademark) (manufactured by Toyobo Co., Ltd.) and product name Esprafex (manufactured by Sumitomo Ginzoku Kogyo Co., Ltd.) were used.

On a copper circuit (L / S = 50/50) obtained by a subtractive method with CCL (trade name: Viroflex (registered trademark), copper foil 18 탆, base 20 탆) manufactured by Toyobo Co., Ltd., polycarbonate imide The resin paste was printed with a predetermined pattern at a printing speed of 5 cm / sec in an SUS mesh plate (150 mesh, manufactured by Murakami Corporation, emulsion thickness of 30 占 퐉) at 80 占 폚 for 6 minutes (screen printing). Thereafter, the film was heated and cured at 120 DEG C for 90 minutes to obtain a laminated film in which a coverlay (coating film) made of a polycarbonate imide resin paste was applied. The thickness of the coating was 15 mu m. (L / S = 16/16) obtained by the subtractive method was used in the case of using CCL (trade name: Espraflex, copper layer 8 μm, substrate 12.5 μm) manufactured by Sumitomo Heavy Industries Co., To obtain a laminated film.

<Aspect ratio (tic consumption)>

Using Brookfield BH type rotational viscometer. 90 ml of a polycarbonate imide resin paste was put in a light-shielding bottle (100 ml) having a wide mouth, and the liquid temperature was adjusted to 25 ° C ± 0.5 ° C using a constant temperature water bath. Subsequently, the sample was agitated for 40 to 120 seconds using a glass rod, and then a predetermined rotor was provided. The sample was allowed to stand for 5 minutes and then rotated at 10 rpm for 3 minutes. The scale was read to calculate the viscosity. Likewise, the viscosity was measured at 25 ° C and 1 rpm, and the viscosity was calculated by the following formula.

Aspect Ratio = Viscosity (1 rpm) / Viscosity (10 rpm)

&Lt; Evaluation of bending amount &

The obtained laminated film was cut into 10 cm x 10 cm. The sample whose humidity was adjusted at 25 DEG C and 65% RH for 24 hours was placed on a horizontal glass plate in a convex downward direction, and the average of the heights of the four corners was evaluated.

(Judgment) ○: less than 2 mm in height

Δ: Height 2 mm or more and less than 10 mm

×: Height 10 mm or more

<Flexibility (MIT test)>

The obtained laminated film was evaluated in accordance with JIS-C-6471 (1995). The load was 300 g and the diameter of the mandrel was 0.38 mm. The occurrence of cracks was confirmed, and the number of times of bending at the time of cracking was recorded.

(Judgment) ◎: No crack at over 250 bends

○: No crack occurred at bending more than 200 times

C: Crack occurred in less than 200 cycles

<Tensile test>

The tensile elastic modulus and the elongation at break were evaluated in accordance with JIS-K-7161 (2014) using a tensile tester (trade name "Tensile Compression Tester TG-2kN", manufactured by Minebea Co., Ltd.). A polycarbonate imide resin paste was cured at 120 占 폚 for 90 minutes and film-like samples were obtained under the following conditions.

Sample size: width 10 mm × length 40 mm

Tensile speed: 20 mm / min

(Production Example 1) (b) Synthesis of acid dianhydride having polycarbonate skeleton represented by general formula (4) (b-1)

167 g (0.87 mol) of trimellitic anhydride (TMA) and thionyl chloride were added to the reaction vessel to synthesize a chloride of trimellitic anhydride. Then, 183 g (0.87 mol) of a chloride of trimellitic anhydride and 183 g (0.87 mol) of dichlormol T5651 (polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol manufactured by Asahi Chemical Industry Co., ) Was esterified at 30 DEG C in toluene to synthesize a polycarbonate skeleton-containing tetracarboxylic dianhydride.

(Production Example 2)

60.0 g (0.04 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride (TMA) and 16.4 g (0.04 mol) of ethylene glycol bisanhydrotrimellitate 26.4 g (0.1 mol) of o-tolylidine diisocyanate (TODI) as a diisocyanate and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were charged, Was dissolved in 97.9 g of lactone. Thereafter, the mixture was allowed to react at 80 to 190 ° C for 6 hours under stirring in a nitrogen stream, and then 83.9 g of? -Butyrolactone was added to dilute it. The mixture was cooled to room temperature to obtain a brown, viscous To obtain a polycarbonate imide resin solution A-1.

(Production Example 3)

75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 12.3 g (0.03 mol) of ethylene glycol bisanhydrotrimellitate, 26.4 g (0.1 mol) of tolylidine diisocyanate (TODI) and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were added and dissolved in 108.8 g of? -Butyrolactone Respectively. Thereafter, the mixture was reacted under stirring in a nitrogen stream at 80 to 190 ° C for 6 hours, diluted with 93.3 g of? -Butyrolactone and cooled to room temperature to obtain a brown, viscous To obtain a polycarbonate imide resin solution A-2.

(Production Example 4)

90.0 g (0.06 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 8.2 g (0.02 mol) of ethylene glycol bisanhydrotrimellitate, 26.4 g (0.1 mol) of tolylidine diisocyanate (TODI) and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were added and dissolved in 119.7 g of? -Butyrolactone Respectively. Thereafter, the mixture was allowed to react at 80 to 190 ° C for 6 hours while stirring under nitrogen flow, and then 102.6 g of? -Butyrolactone was added to dilute it. The mixture was cooled to room temperature to obtain a brown, viscous Thereby obtaining a polycarbonate imide resin solution A-3.

(Production Example 5)

60.0 g (0.04 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 16.4 g (0.04 mol) of ethylene glycol bisanhydrotrimellitate, 21.1 g (0.08 mol) of tolylidine diisocyanate (TODI), 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1,8-diazabicyclo [5.4.0] -7 -Undecene were added and dissolved in 96.1 g of? -Butyrolactone. Thereafter, the mixture was allowed to react at 80 to 190 DEG C for 6 hours under stirring in a nitrogen stream, and then 82.4 g of? -Butyrolactone was added to dilute the mixture. The mixture was cooled to room temperature to obtain a brown, viscous Thereby obtaining a polycarbonate imide resin solution A-4.

(Production Example 6)

75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 12.3 g (0.03 mol) of ethylene glycol bisanhydrotrimellitate, 21.1 g (0.08 mol) of tolylidine diisocyanate (TODI), 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1,8-diazabicyclo [5.4.0] -7 -Undecene (0.08 g), and dissolved in 107.0 g of? -Butyrolactone. Thereafter, the mixture was reacted with stirring at 80 to 190 ° C for 6 hours under a nitrogen stream, and then 91.7 g of? -Butyrolactone was added to dilute. The mixture was cooled to room temperature to obtain a brown, viscous To obtain a polycarbonate imide resin solution A-5.

(Production Example 7)

75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride (TMA) and 12.3 g (0.03 mol) of ethylene glycol bisanhydrotrimellitate 22.5 g (0.09 mole) of o-tolylidine diisocyanate (TODI) as a diisocyanate and 0.06 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were charged, Was dissolved in 83.4 g of lactone. Thereafter, the mixture was allowed to react at 80 to 190 ° C for 6 hours while stirring under a nitrogen stream, 22.8 g of? -Butyrolactone was added to dilute it, and the mixture was cooled to room temperature to obtain a brown, viscous To obtain a polycarbonate imide resin solution A-6.

(Example 1)

4.0 parts by mass of Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.) as a filler and 0.04 parts by mass of U-CAT SA1 as a curing accelerator were added to 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A- 1.1 parts by mass of BYK-054 (manufactured by Beck Chemicals Co., Ltd.) as a defoaming agent and 1.2 parts by mass of BYK-354 (manufactured by Beck Chemicals Co., Ltd.) as a leveling agent were added, To obtain a mid resin composition. This composition was first coarsely kneaded and then kneaded three times using a high speed triple roll to uniformly disperse the filler to obtain a paste having thixotropic properties. To 100 parts by mass of this paste, 4.0 parts by mass of a? -Butyrolactone solution (solid content: 70%) of jER157S70 (trade name of phenol novolak type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 208 g / eq) (8.2 parts by mass based on 100 parts by mass of the polycarbonate imide resin (A-1)) was added to obtain the polycarbonate imide resin paste (1) of the present invention. When the viscosity was adjusted with? -butyrolactone, the solution had a viscosity of 232 poise and an aspect ratio of 1.32. On the copper circuit (L / S = 50/50) obtained by the subtractive method with CCL (trade name: Viroflex (registered trademark), copper foil of 18 μm, substrate of 20 μm) manufactured by TOYO BOSE CORPORATION, polycarbonate The mid resin paste 1 was printed with a predetermined pattern at a printing speed of 5 cm / sec in an SUS mesh plate (150 mesh, manufactured by Murakami Co., Ltd., emulsion thickness 30 占 퐉) at 80 占 폚 for 6 minutes. Thereafter, the substrate was heated and cured at 120 DEG C for 90 minutes to obtain a COF substrate (evaluation sample 1) on which a coverlay (coating film) made of a polycarbonate imide resin paste was applied. The thickness of the coating was 15 mu m. The evaluation results are shown in Table 1.

(Examples 2 to 5 and 7)

Evaluation samples 2 to 5 and 7 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 (C) . The evaluation results are shown in Table 1.

(Example 6)

A paste was prepared in the same manner as in Example 1 except that the solution of the polycarbonate imide resin solution (A) obtained in Production Example 2 and the components (B) to (C) On the copper circuit (L / S = 16/16) obtained by the subtractive method with CCL for high acid production COF (Esfaflex (registered trademark), copper layer 8 占 퐉, substrate 12.5 占 퐉), polycarbonate imide Based resin paste was printed with a predetermined pattern at a printing speed of 5 cm / sec using an SUS mesh plate (150 mesh, manufactured by Murakami Co., Ltd., emulsion thickness 30 占 퐉) and dried at 80 占 폚 for 6 minutes in an air atmosphere. Thereafter, the substrate was heated and cured at 120 DEG C for 90 minutes to obtain a COF substrate (evaluation sample 6) on which a coverlay (coating film) made of a polycarbonate imide resin paste was applied. The thickness of the coating was 15 mu m. The evaluation results are shown in Table 1.

(Comparative Example 1)

45.0 g (0.03 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 20.6 g (0.05 mol) of ethylene glycol bisanhydrotrimellitate, 26.4 g (0.1 mol) of tolylidine diisocyanate (TODI) and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst were added and dissolved in 87.0 g of? -Butyrolactone Respectively. Thereafter, the mixture was allowed to react at 80 to 190 ° C for 6 hours under stirring in a nitrogen stream, and 74.6 g of? -Butyrolactone was added to dilute the mixture. The mixture was cooled to room temperature to obtain a brown, viscous To obtain a polycarbonate imide resin solution B-1. A paste was prepared in the same manner as in Example 1, and an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, since the copolymerization amount of the component (b-1) as the flexible component was small, the warpage was increased.

(Comparative Example 2)

105 g (0.07 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 4.1 g (0.01 mol) of ethylene glycol bisanhydrotrimellitate, 21.1 g (0.08 mol) of tolylidine diisocyanate (TODI), 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1,8-diazabicyclo [5.4.0] -7 -Undecene was added, and the solution was dissolved in 128.8 g of? -Butyrolactone. Thereafter, the mixture was allowed to react at 80 to 190 ° C for 6 hours under stirring in a nitrogen stream, diluted with 110.4 g of? -Butyrolactone and cooled to room temperature to obtain a brown, viscous Thereby obtaining a polycarbonate imide resin solution B-2. A paste was prepared in the same manner as in Example 1, and an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, since the copolymerization amount of the component (b-1) as the flexible component was large, the flexural amount was small, but the tensile elastic modulus of the coating film was low.

(Comparative Example 3)

75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 3.8 g (0.02 mol) of trimellitic anhydride, 12.3 g (0.03 mol) of ethylene glycol bisanhydrotrimellitate, 13.2 g (0.05 mol) of toluidine diisocyanate (TODI), 8.7 g (0.05 mol) of 2,4-tolylene diisocyanate (TDI), 1,8-diazabicyclo [5,4,0] -7 -Undecene were added and dissolved in 104.3 g of? -Butyrolactone. Thereafter, the mixture was reacted at 80 to 190 ° C for 6 hours under stirring in a nitrogen stream, and then 89.4 g of? -Butyrolactone was added to dilute. The mixture was cooled to room temperature to obtain a brown, viscous Thereby obtaining a polycarbonate imide resin solution B-3. A paste was prepared in the same manner as in Example 1, and an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, although the amount of warpage was small, since the elongation at break was small, the flexing resistance was poor.

(Comparative Example 4)

75.0 g (0.05 mol) of the component (b-1) synthesized in Production Example 1, 9.6 g (0.05 mol) of trimellitic anhydride, 26.4 g (0.1 mol) of o-tolylidine diisocyanate (TODI) as a diisocyanate, 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a catalyst was added and dissolved in 102.2 g of? -Butyrolactone. Thereafter, the temperature was raised to 80 占 폚 to 190 占 폚 under stirring in a nitrogen stream, but evaluation was not possible because it was insoluble in the course of polymerization.

The polycarbonate imide resin obtained by the present invention and the paste using the polycarbonate imide resin have excellent heat resistance, flexibility and flex resistance as a film-forming material. Therefore, it can be used in a wide range of fields of electronic apparatuses such as paints, coatings, adhesives, etc. in addition to being useful for overcoat inks and solder resist inks for various electronic parts, such as COF substrates.

Claims (6)

A resin composition comprising a constituent component represented by the general formula (1), a constituent component represented by the general formula (2) and a constituent component represented by the formula (3) ) Is 10 mol% or more, the constituent component represented by the general formula (2) is more than 30 mol% but less than 70 mol%, and the constituent component represented by the formula (3) is more than 50 mol% (A). &Lt; / RTI &gt;

(In the general formula (1), A is a straight chain alkylene group which may have a substituent having 1 to 10 carbon atoms.)

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

(b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), and (c) o-tolylidine diisocyanate (TODI) as essential comonomers, in the presence of an alkylene glycol bisanhydrotrimellitate (B) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), wherein the total amount of the acid dianhydride is 100 mol%, and the amount of the alkylene glycol bisanhydrotrimellitate is 10 mol% Is more than 30 mol% but less than 70 mol%, and (c) o-tolylidine diisocyanate (TODI) is more than 50 mol% when the total amine component is taken as 100 mol% A).

(In the general formula (4), a plurality of R's each independently represent a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.) A polycarbonate imide resin paste characterized by containing the polycarbonate imide resin (A) according to claim 1 or 2, the epoxy resin (B) having two or more epoxy groups per molecule, and the filler (C). The polycarbonate imide resin paste according to claim 3, wherein the aspect ratio is 1.2 or more. The polycarbonate imide resin paste according to claim 3 or 4, which is for COF (Chip On Film). An electronic part having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the polycarbonate imide resin paste according to any one of claims 3 to 5.