WO2017068999A1

WO2017068999A1 - Polycarbonate-imide resin and paste including same

Info

Publication number: WO2017068999A1
Application number: PCT/JP2016/079912
Authority: WO
Inventors: 翔子内山; 知裕青山
Original assignee: 東洋紡株式会社
Priority date: 2015-10-19
Filing date: 2016-10-07
Publication date: 2017-04-27
Also published as: CN107922615B; TWI697514B; KR20180072591A; KR102233604B1; TW201730240A; CN107922615A

Abstract

[Problem] To provide a polycarbonate-imide resin paste which is applicable as a solder resist layer, surface-protective layer, or adhesive layer that satisfies all of (1) solubility in nitrogen-free solvents, (2) low warpage, and (3) flex resistance. [Solution] A polycarbonate-imide resin (A) characterized by comprising a constituent component represented by specific structural formula (1), a constituent component represented by specific structural formula (2), and a constituent component represented by specific structural formula (3), the amounts of the constituent component represented by specific structural formula (1), the constituent component represented by specific structural formula (2), and the constituent component represented by specific structural formula (3) being 10 mol% or greater, greater than 30 mol% but less than 70 mol%, and greater than 50 mol%, respectively, when the amount of all the constituent components is 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 substrate applications, a polycarbonate imide resin paste having excellent heat resistance and flexibility and suitable for a coating method such as a printing press, a dispenser or a spin coater, and a solder resist layer obtained by curing the paste, The present invention relates to an electronic component having a surface protective layer or an adhesive layer.

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

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

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

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

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

Moreover, the composition which improved the moldability of the resin composition by mixing a fixed amount of polycarbonate resin with a polyimide resin and imparting flexibility is disclosed (Patent Document 3) and (Patent Document 4). . Furthermore, the thermoplastic resin composition which improved the moldability by mixing a polyimide resin, an epoxy resin, and a polycarbonate resin is disclosed (Patent Document 5).

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

However, they are listed as resins suitable for melt-kneading and melt-extrusion, and have excellent heat resistance and mechanical strength, but are not soluble in non-nitrogen solvents and have low warpage and flexibility. It is hard to say that it has.

As can be seen from these examples, the conventional techniques so far have (1) non-nitrogen solvent solubility, (2) low warpage, and (3) a solder resist layer, a surface protective layer, or an adhesive layer simultaneously satisfying bending resistance. As a result, no polyimide resin paste applicable was obtained.

The present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is (1) a non-nitrogen solvent solubility, (2) low warpage, and (3) a polycarbonate imide resin excellent in heat resistance, chemical resistance, and electrical properties, An object of the present invention is to provide a polycarbonate imide resin paste to be used and an electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the paste.

When the component represented by the general formula (1), the component represented by the general formula (2), and the component represented by the formula (3) are contained and the total components are 200 mol%, the general formula (1 ) Is 10 mol% or more, the component represented by the general formula (2) is more than 30 mol% and less than 70 mol%, and the component represented by the formula (3) is 50 mol%. Polycarbonate imide resin (A) characterized by exceeding mol%.

(In the general formula (1), A is a linear 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 represents a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

(A) Alkylene glycol bisanhydro trimellitate, (b) acid dianhydride having a polycarbonate skeleton represented by general formula (4), and (c) o-tolidine diisocyanate (TODI) as essential copolymerization components And (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), wherein (a) the alkylene glycol bisanhydro trimellitate is 10 mol% or more when the total acid component is 100 mol%. Is a polycarbonate imide resin characterized in that (c) o-tolidine diisocyanate (TODI) exceeds 50 mol% when the total amine component is more than 30 mol% and less than 70 mol% and the total amine component is 100 mol% (A).

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

A polycarbonate imide resin paste comprising the polycarbonate imide resin (A), an epoxy resin (B) having two or more epoxy groups per molecule, and a filler (C).

The polycarbonate imide resin paste preferably has a fluctuation degree of 1.2 or more, and is preferably for COF® (Chip® On® Film).

An electronic component having a solder resist layer, a surface protective layer or an adhesive layer obtained by curing the polycarbonate imide resin paste.

According to the present invention, conventionally (1) non-nitrogen solvent solubility (2) low warpage (3) polycarbonate imide resin excellent in bending resistance, paste using the same, and the above An electronic component having a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the paste can be provided.

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

<Polycarbonateimide resin (A) component>
The polycarbonate imide resin (A) of the present invention will be described. The polycarbonate imide resin (A) contains a constituent represented by the general formula (1), a constituent represented by the general formula (2), and a constituent represented by the formula (3), and the total constituent is 200 mol%. The component represented by the general formula (1) is 10 mol% or more, the component represented by the general formula (2) is more than 30 mol% and less than 70 mol%, and the formula (3 Is a polycarbonate imide resin characterized by exceeding 50 mol%.

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

<Constituent Component Shown by General Formula (1)>
The polycarbonate imide resin (A) of the present invention can be expected to have an effect of improving non-nitrogen solvent solubility and heat resistance by containing the constituent represented by the general formula (1). In the general formula (1), A is a linear alkylene group having 1 to 20 carbon atoms which may have a substituent, and preferably 2 to 10 carbon atoms. When it has a substituent, the substituent is preferably an alkyl group having 1 to 3 carbon atoms.

The content of the component of the general formula (1) in the polycarbonate imide resin (A) needs to be 10 mol% or more when all the components are 200 mol%. Preferably it is 20 mol% or more, More preferably, it is 30 mol% or more. Moreover, it is preferable that it is 90 mol% or less, It is more preferable that it is 80 mol% or less, It is further more preferable that it is 70 mol% or less. If it is less than 10 mol%, non-nitrogen solvent solubility and heat resistance may not be obtained. If it is more than 90 mol%, the component represented by the general formula (2) described later and the structure represented by the formula (3) will be described. The component may not be contained in a sufficient amount. Therefore, low warpage and bending resistance (mechanical properties) may be deteriorated.

<Constituent Component Shown by General Formula (2)>
Since the structural component represented by the general formula (2) has flexibility, the polycarbonate imide resin (A) of the present invention can be imparted with low warpage and non-nitrogen solvent solubility.

In the general formula (2), a plurality of R's each independently represents a divalent organic group having 1 or more carbon atoms. The carbon number is preferably 5 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less. Further, the divalent organic group is not particularly limited, but a linear alkylene group which may have a substituent is preferable, and the number of carbon atoms preferably includes the carbon of the substituent. 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 content of the component represented by the general formula (2) in the polycarbonate imide resin (A) needs to be more than 30 mol%, preferably 35 mol% when all the components are 200 mol%. It is above, More preferably, it is 40 mol% or more. Moreover, it is required that it is less than 70 mol%, Preferably it is 65 mol% or less, More preferably, it is 60 mol% or less. If it is 30 mol% or less, warping may occur when laminated, and solubility in non-nitrogen solvents may be reduced. For this reason, the resin may be deposited within one month at 5 to 30 ° C. On the other hand, if it is 70 mol% or more, the bending resistance (mechanical properties) and heat resistance may decrease.

As a component of the polycarbonate imide resin (A), the total amount of the component represented by the general formula (1) and the component represented by the general formula (2) is preferably 60 mol% or more, and 65 mol. % Is more preferable, 70 mol% or more is further preferable, 75 mol% or more is particularly preferable, and 80 mol% or more is most preferable. If the amount is too small, low warpage and solubility in non-nitrogen solvents may decrease.

<Constituent Component Shown by Formula (3)>
The polycarbonate imide resin (A) of the present invention can exhibit excellent bending resistance by containing the constituent represented by the formula (3).

The content of the component represented by the formula (3) in the polycarbonate imide resin (A) needs to be more than 50 mol%, preferably 60 mol% or more when all the components are 200 mol%. More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, Especially preferably, it is 90 mol% or more, Most preferably, it is 100 mol%. If it 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 components of the general formula (1), general formula (2) and formula (3). Therefore, the polycarbonate imide resin (A) comprises (a) an alkylene glycol bisanhydro trimellitate, (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), and (c) o-tolidine diisocyanate. Is an essential copolymer component, and when the total acid component is 100 mol%, (a) the alkylene glycol bisanhydro trimellitate is 10 mol% or more, and (b) the general formula (4) When the acid dianhydride having a polycarbonate skeleton represented by the formula is more than 30 mol% and less than 70 mol% and the total amine component is 100 mol%, (c) o-tolidine diisocyanate exceeds 50 mol% It is preferable.

<(A) Alkylene glycol bisanhydro trimellitate>
The component (a) constituting the polycarbonate imide resin (A) used in the present invention needs to be (a) alkylene glycol bisanhydro trimellitate (hereinafter also simply referred to as component (a)). . By using alkylene glycol bisanhydro trimellitate, excellent effects of non-nitrogen solvent solubility and heat resistance can be expected.

Specific examples of the alkylene glycol bisanhydro trimellitate are not particularly limited, but include methylene glycol bis anhydro trimellitate, ethylene glycol bis anhydro trimellitate (TMEG), propylene glycol bis anhydro trimellitate, 1 , 4-butanediol bisanhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis anhydro trimellitate, etc. Two or more kinds can be used in combination. Among these, ethylene glycol bisanhydro trimellitate (TMEG) is preferable from the viewpoint of availability.

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

<(B) Acid dianhydride having a polycarbonate skeleton represented by the general formula (4)>
The acid dianhydride (hereinafter also referred to simply as the component (b)) having the polycarbonate skeleton represented by the general formula (4) constituting the polycarbonate imide resin (A) of the present invention is a polycarbonate polyimide resin ( It is copolymerized as a flexible component that imparts low warpage and non-nitrogen solvent solubility to A).

The component (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 represents a divalent organic group having 1 or more carbon atoms. The carbon number 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 straight chain or an alkylene group which may have a substituent, and the carbon number preferably includes the carbon of the substituent. 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 polycarbonate diol for synthesizing the component (b) used in the present invention may be a polycarbonate diol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate diol). Polyol C-1015N, Kuraray polyol C-1065N (Kuraray Co., Ltd. carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight about 1,000), Kuraray polyol C- 2015N, Kuraray polyol C-2065N (Kuraray Co., Ltd. carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight of about 2,000), Kuraray polyol C-1050, Kuraray Polyol C-1090 (Kuraray Co., Ltd.) Bonate diol: 3-methyl-1,5-pentanediol / 1,6-hexanediol, number average molecular weight of 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 of about 2,000), DURANOL (registered trademark) -T5650E (Asahi Kasei Chemicals Co., Ltd. polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 500), DURANOL (registered trademark) -T5651 (Asahi Kasei Chemicals Corporation polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 1,000), DURANOL (registered trademark)- 5652: and the like (produced by Asahi Kasei Chemicals Co., Ltd. Polycarbonate diol 1,5-pentanediol / 1,6-hexanediol, about 2,000 number average molecular weight).

(B) Although it does not specifically limit as a method to manufacture a component, It can synthesize | combine by the well-known reaction method from the chloride of trimellitic anhydride and the above-mentioned diol compound. More specifically, first, a diol compound and a deoxidizing agent are put into a chloride solution of trimellitic anhydride dissolved in a solvent and stirred for 0.5 to 24 hours. The reaction temperature is −20 to 50 ° C., and more preferably 20 to 40 ° C. from the viewpoint of reaction selectivity. As a reaction ratio between the trimellitic anhydride chloride and the diol compound, it is preferable to perform the reaction by using 2 mol or more of trimellitic anhydride chloride with respect to 1 mol of the diol compound. The concentration of the solute in the reaction is preferably 5 to 80% by weight, more preferably 40 to 60% by weight. After completion of the reaction, the precipitated hydrochloride is filtered off and the solvent is concentrated to obtain an acid dianhydride having a polycarbonate skeleton represented by the general formula (4) (hereinafter also referred to as a polycarbonate skeleton-containing tetracarboxylic dianhydride). Say).

When the total acid component is 100 mol%, the amount of copolymerization of component (b) needs to be more than 30 mol%, preferably 35 mol% or more, more preferably 40 mol% or more. is there. Moreover, it is required that it is less than 70 mol%, Preferably it is 65 mol% or less, More preferably, it is 60 mol% or less. When it is 30 mol% or less, the elastic modulus may not be sufficiently lowered, and when laminated, warpage may occur or solubility in a non-nitrogen solvent may be lowered. Therefore, the resin may be deposited within 5 months at 5 ° C to 30 ° C. On the other hand, if it is 70 mol% or more, the above-mentioned component (a) and the component (c) described later cannot be contained in a sufficient amount, so that the bending resistance (mechanical properties) and heat resistance may be lowered. is there.

As the acid component of the polycarbonate imide resin (A), the total amount of the component (a) and the component (b) is preferably 60 mol% or more, more preferably 65 mol% or more, and 70 mol%. More preferably, it is more preferably 75 mol% or more, and most preferably 80 mol% or more. If the amount is too small, low warpage and solubility in non-nitrogen solvents may decrease.

<Other acid components>
As another 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 limited. For example, trimellitic anhydride (TMA), pyromellitic dianhydride, 3,3′-4,4′-benzophenone tetracarboxylic dianhydride, 3,3′-4,4′-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride , M-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis (2,3- or 3,4- Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (2,3- or 3,4) -Dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl ] Propane dianhydride 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 dianhydride, pentane-1,2,4,5-tetracarboxylic acid. Acid dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-1 -Ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3, 4-tetracarboxylic dianhydride 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2, 3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2,2,1] heptane-2,3,5,6-tetra Carboxylic 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 dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, or hexa hydro trimellitic anhydride, and the like.

These trivalent and / or tetravalent polycarboxylic acid derivatives having an acid anhydride group may be used alone or in combination of two or more. 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, when the acid component is 100 mol%. Preferably, it is more preferably 30 mol% or less, particularly preferably 25 mol% or less, and most preferably 20 mol% or less.

In addition, aliphatic, alicyclic, and aromatic dicarboxylic acids may be copolymerized as necessary as long as the target performance is not impaired. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosane diacid, fumaric acid Examples of alicyclic dicarboxylic acids such as maleic acid, dimer acid, hydrogenated dimer acid and the like include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane, and the like. Examples of aromatic dicarboxylic acids such as dicarboxylic acid and 4,4′-dicyclohexyldicarboxylic acid include isophthal , Terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid and the like. These dicarboxylic acids may be used alone or in combination of two or more. In view of heat resistance, adhesion, solubility, cost, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferable.

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

(C) The amount of o-tolidine diisocyanate copolymerization needs to be more than 50 mol%, preferably 60 mol% or more, more preferably 70 mol%, when the total amine component is 100 mol%. More preferably, it is 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 elastic modulus becomes low, and the bending resistance may not be sufficiently exhibited.

<Other isocyanate compounds>
The polycarbonate imide resin (A) of the present invention may be further copolymerized with an isocyanate compound as necessary within a range not impairing the intended performance. If it is an isocyanate compound, it will not specifically limit, Aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned. Aromatic polyisocyanates are preferably used. Specific examples of aromatic polyisocyanates include, but are not limited to, diphenylmethane-2,4′-diisocyanate, 3,2′- or 3,3′- or 4,2′- or 4,3′- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3 ' -Or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4 , 4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylme -3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6 -Diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate, 3,3'- or 2 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate and the like. In view of heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4′-diisocyanate (MDI), tolylene-2,4-diisocyanate (TDI), m-xylylene diisocyanate are preferable, and tolylene- 2,4-diisocyanate (TDI) is more preferred. These can 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 one of the isocyanate compounds is 100 mol%. When a diamine compound corresponding to the isocyanate is used instead of the isocyanate, it passes through a polyamic acid as a precursor of the polycarbonate polyimide resin. When passing through a polyamic acid, it is necessary to imidize at a high temperature of about 200 ° C. or more after applying a paste containing polyamic acid to a substrate such as COF (Chip On Film), which may cause thermal degradation of COF. Yes, and there may be restrictions on equipment. In the present invention, since only an isocyanate compound containing TODI is used as an amine component, it can be treated at a lower temperature than a polyamic acid-containing paste, and there is no such problem, which is preferable.

Further, in addition to the component (b), other flexible components may be copolymerized as necessary within the range not impairing the intended performance. For example, aliphatic / aromatic polyester diols (trade name VYLON (registered trademark) 220 manufactured by Toyobo Co., Ltd.), aliphatic / aromatic polycarbonate diols (produced by Daicel Chemical Industries, Ltd., trade name PLACEL (registered trademark)) ) -CD220, manufactured by Kuraray Co., Ltd., trade names C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, etc., manufactured by Asahi Kasei Chemicals Corporation, trade names 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 PLACEL®) 220), carboxy-modified acrylonitrile butadiene rubbers (trade name HyproCTBN1300 × 13, etc., manufactured by Ube Industries, Ltd.), 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 (component (a) and component (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 the number of isocyanate groups / 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), heat resistance and flex resistance may be lowered, and 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 increased, and the separation of the plate may be deteriorated at the time of printing when the ink is formed.

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

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

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

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

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

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

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

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

The polycarbonate imide resin (A) used in the present invention preferably has a molecular weight corresponding to a logarithmic viscosity of 0.1 to 2.0 dl / g at 30 ° C. in γ-butyrolactone, more preferably 0.2 To a molecular weight corresponding to a logarithmic viscosity of 1.5 dl / g. When the logarithmic viscosity is less than 0.1 dl / g, the heat resistance may be lowered or the coating film may be brittle. In addition, the tackiness of the paste is strong and the release of the plate may worsen. On the other hand, when it exceeds 2.0 dl / g, it becomes difficult to dissolve in a solvent, and it tends to become insoluble during polymerization. In addition, the viscosity of the varnish becomes high and handling becomes difficult, and the adhesion to the substrate may be reduced.

The glass transition temperature of the polycarbonate imide resin (A) used in the present invention is preferably 20 ° C. or higher, more preferably 60 ° C. or higher. If it is less than 20 degreeC, heat resistance may be insufficient and resin may block. Although an upper limit is not specifically limited, 300 degrees C or less is preferable from a solvent solubility viewpoint.

<Epoxy resin (B) component>
The epoxy resin of component (B) used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups per molecule. The epoxy resin (B) is not particularly limited. For example, bisphenol A type epoxy resin such as trade name jER (registered trademark) 828, 1001 manufactured by Mitsubishi Chemical Corporation, trade name ST manufactured by Toto Kasei Co., Ltd. -Hydrogenated bisphenol A type epoxy resins such as 2004 and 2007, trade name YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy such as 2004, product names YDB-400, 600 manufactured by Toto Kasei Co., Ltd. Brominated bisphenol A type epoxy resin, trade name jER (registered trademark) 152, 154, 157S70, 1032H60 manufactured by Mitsubishi Chemical Corporation, trade name EPN (registered trademark) -201 manufactured by Nippon Kayaku Co., Ltd., BREN (Registered trademark), a phenol novolac type epoxy resin such as the trade name DEN-438 manufactured by Dow Chemical Company, a product manufactured by Tohto Kasei Co., Ltd. YDCN-702, 703, trade name EOCN (registered trademark) -125S, 103S, 104S, etc. manufactured by Nippon Kayaku Co., Ltd., o-cresol novolac type epoxy resin, trade name YD-171, manufactured by Toto Kasei Co., Ltd., etc. Flexible epoxy resin, trade name Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., trade name Araldite (registered trademark) 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Denacor manufactured by Nagase Chemtech Co., Ltd. (Registered Trademark) Multifunctional epoxy resin such as EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, manufactured by Yuka Shell Epoxy Co., Ltd. Product name Epicort (registered trademark) 604, product name YH-434 manufactured by Tohto Kasei Co., Ltd., product name TETR manufactured by Mitsubishi Gas Chemical Co., Ltd. Amine type epoxy resins such as AD (registered trademark) -X, TETRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, Ciba Specialty Chemicals Co., Ltd. ) Product name Araldite (registered trademark) PT810, etc. manufactured by Daicel Chemical Industries, Ltd., trade name Celoxide (registered trademark) 2021, EHPE (registered trademark) 3150, UCC ERL4234, etc. Alicyclic epoxy resin, bisphenol S type epoxy resin such as trade name Epicron (registered trademark) EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc., and TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd. Bixylenol type epoxy resin such as glycidyl isocyanurate, trade name YX-4000 manufactured by Yuka Shell Epoxy Co., Ltd., oil Shell Epoxy Co., Ltd. trade name YL-6056 such as bisphenol type epoxy resins, etc., and may be used in combination singly, or two or more kinds.

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

The amount of the epoxy resin (B) used in the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, particularly preferably 3 to 30 parts by weight based on 100 parts by weight of the polycarbonate imide resin (A). Part by mass. When the blending amount of the epoxy resin (B) is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease, and when it exceeds 50 parts by mass, low warpage, mechanical properties, There exists a tendency for heat resistance, varnish stability, and compatibility with a polycarbonate imide resin (A) to fall. Furthermore, the cured film lacks flexibility, and the bending resistance (mechanical properties) tends to decrease.

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

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

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

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

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

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

A curing accelerator can be added to the polycarbonate imide resin paste of the present invention in order 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).

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 Kasei Kogyo Co., Ltd. 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z -AZINE, 2MA-OK, 2P4MHZ, imidazole derivatives such as aceguanamine, benzoguanamine, etc. , Diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide and other polyamines, their organic acid salts and / or epoxy adacs , Boron trifluoride amine complexes, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, triazine derivatives such as 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), DBN (1,5-diazabicyclo [4,3,0] -5-nonene), and organic acid salts thereof. U-CAT (registered trademark) SA1 (DBU-phenol salt), U-CAT (registered trademark) SA 102 (DBU-O) Thiolate), U-CAT (registered trademark) SA 831 (DBU-phenol novolac resin salt), U-CAT (registered trademark) 5002 (DBU-based tetraphenylborate salt) (both manufactured by San Apro Co., Ltd.) 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, tetraphenylphosphonium tetraphenylboroate, quaternary ammonia such as benzyltributylammonium chloride, phenyltributylammonium chloride Salts, polycarboxylic acid anhydride, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure (registered trademark) 261 (Ciba Specialty)・ Chemicals Co., Ltd.), Optoma-SP-170 (ADEKA Co., Ltd.) and other photocation polymerization catalysts, styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate, Examples thereof include an equimolar reaction product of an organic polyisocyanate such as isophorone diisocyanate and dimethylamine. You may use these individually or in combination of 2 or more types. Preferably, it is a curing accelerator having latent curability, and examples thereof include DBU, DBN organic acid salts and / or tetraphenylboronate, and a photocationic polymerization catalyst.

The use amount of the curing accelerator is preferably 0 to 20 parts by mass when the component (A) is 100 parts by mass. If it exceeds 20 parts by mass, the storage stability of the polycarbonate imide resin composition and the heat resistance of the coating film may be lowered.

<Polycarbonateimide 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, other blending components can be blended preferably in the above proportions. What is obtained by uniformly mixing these components with a roll mill, a mixer, a three roll or the like is preferable. The mixing method is not particularly limited as long as sufficient dispersion can be obtained. Multiple kneading with three rolls is preferred.

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

Stability (thixotropic properties) is also important. The degree of change of the polycarbonate imide resin paste is preferably 1.2 or more, more preferably 1.3 or more in the measurement method described later. The upper limit is preferably 7.0 or less, and more preferably 6.0 or less. If the degree of change is less than 1.2, the flow of paste after printing increases and the film thickness tends to be reduced. If it exceeds 7.0, the paste tends not to flow. The variation degree can be adjusted by the blending amount of the component (c) as the variation degree imparting agent.

The polycarbonate imide resin and paste of the present invention include known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and hydroquinone as necessary. , Known conventional polymerization inhibitors such as hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, etc., known conventional thickeners such as olben, benton, montmorillonite, defoamers such as silicones, fluorines and polymers Leveling agents, imidazole, thiazole, triazole, organoaluminum compounds, organotitanium compounds, organosilane compounds and other coupling agents / adhesion imparting agents, triphenyl phosphate, triphenyl 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) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus, etc. phosphorus flame retardant, polyphosphoric acid Ammonium, triazine, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) isocyanurate Nitrogen flame retardants such as acetoguanamine, guanylmelamine sulfate, melem sulfate, melam sulfate, metal salt flame retardants such as potassium diphenylsulfone-3-sulfonate, aromatic sulphonimide metal salt, alkali metal polystyrene sulphonate, water Hydrated metal flame retardants such as aluminum oxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide, silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide , Magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, carbonic acid Zinc, carbonate Known and commonly used additives such as inorganic flame retardants such as gnesium, calcium carbonate, barium carbonate, zinc stannate, flame retardants / flame retardants such as silicone powder, heat stabilizers, antioxidants and lubricants Can be used.

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

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

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

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

<Non-nitrogen solvent solubility>
When the polycarbonate imide resin (A) is polymerized, the components (a), (b), (c) and γ-butyrolactone are added to the reaction vessel, the temperature is raised, and when the internal temperature reaches 100 ° C., the raw material ( Evaluation was made based on whether (a) component, (b) component, and (c) component) were dissolved.
(Evaluation) ○: Completely dissolved △: Slightly undissolved ×: Almost insoluble

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

<Production of laminated film>
As the laminated film, a commercially available polyimide base film, trade name Viroflex (registered trademark) (manufactured by Toyobo), and trade name Esperflex (manufactured by Sumitomo Metal Mining) were used.
Polycarbonate imide resin paste is SUS on copper circuit (L / S = 50/50) obtained by subtractive method from Toyobo 2-layer CCL (trade name Viroflex (registered trademark), copper foil 18μm, base material 20μm) A predetermined pattern was printed with a mesh plate (150 mesh manufactured by Murakami Co., Ltd., emulsion thickness 30 μm) at a printing speed of 5 cm / second, and dried in an air atmosphere at 80 ° C. for 6 minutes (screen printing). Then, the laminated film which gave the coverlay (coating) which consists of a polycarbonate imide resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. When using CCL for COF manufactured by Sumitomo Metal Mining (trade name Esperflex, copper layer 8 μm, base material 12.5 μm), the copper circuit (L / S = 16/16) obtained by the subtractive method is used. A laminated film was obtained in the same manner as above.

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

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

<Flexibility (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 the cracks occurred was recorded.
(Judgment) ◎: No cracking when bent 250 times or more ○: No cracking when bending 200 times or more ×: Crack generated after less than 200 times

<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-like sample obtained by curing a polycarbonate imide resin paste at 120 ° C. for 90 minutes was measured under the following conditions.
Sample size: 10mm width x 40mm length
Tensile speed: 20 mm / min

(Production Example 1) (b) Synthesis of an acid dianhydride having a polycarbonate skeleton represented by the general formula (4) (b-1)
Trimellitic anhydride (TMA) (167 g, 0.87 mol) and thionyl chloride were charged into a reaction vessel and reacted to synthesize trimellitic anhydride chloride. Next, 183 g (0.87 mol) of trimellitic anhydride chloride and 434 g of Duranol T5651 (polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, molecular weight 1000, manufactured by Asahi Kasei Chemicals Corporation) as a diol compound (0.43 mol) was esterified in toluene at 30 ° C. to synthesize a polycarbonate skeleton-containing tetracarboxylic dianhydride.

(Production Example 2)
The component (b-1) 60.0 g (0.04 mol), trimellitic anhydride (TMA) 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (synthesized in Production Example 1) TMEG) 16.4 g (0.04 mol), diisocyanate o-tolidine diisocyanate (TODI) 26.4 g (0.1 mol), polymerization catalyst 1,8-diazabicyclo [5,4,0] -7-undecene 0.08 g was added and dissolved in 97.9 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 83.9 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-1.

(Production Example 3)
(B-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 12.3 g (synthesized in Production Example 1) 0.03 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst, Dissolved in 108.8 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 by adding 93.3 g of γ-butyrolactone, and cooled to room temperature, whereby a brown viscous solution having a non-volatile content of 35% by mass was obtained. To obtain a polycarbonate imide resin solution A-2.

(Production Example 4)
(B-1) component 90.0 g (0.06 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 8.2 g (synthesized in Production Example 1) 0.02 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst, Dissolved in 119.7 g of γ-butyrolactone. Thereafter, the mixture was reacted for 6 hours at 80 ° C. to 190 ° C. with stirring under a nitrogen stream, diluted by adding 102.6 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-3.

(Production Example 5)
Component (b-1) 60.0 g (0.04 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 16.4 g (synthesized in Production Example 1) 0.04 mol), 21.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1, 0.08 g of 8-diazabicyclo [5,4,0] -7-undecene was added and dissolved in 96.1 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 82.4 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-4.

(Production Example 6)
(B-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 12.3 g (synthesized in Production Example 1) 0.03 mol), 21.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1, 0.08 g of 8-diazabicyclo [5,4,0] -7-undecene was added and dissolved in 107.0 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 91.7 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution A-5.

(Production Example 7)
The component (b-1) 75.0 g (0.05 mol), trimellitic anhydride (TMA) 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate (synthesized in Production Example 1) TMEG) 12.3 g (0.03 mol), o-tolidine diisocyanate (TODI) 22.5 g (0.09 mol) as diisocyanate, 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst 0.06 g was added and dissolved in 83.4 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 22.8 g of γ-butyrolactone, cooled to room temperature, and then cooled to room temperature to give a brown viscous solution having a non-volatile content of 50% by mass. 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 U-CAT as a curing accelerator with respect to 100 parts by mass of the nonvolatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2 1.0 part by weight of SA1 (manufactured by San Apro Co., Ltd.), 1.1 parts by weight of BYK-054 (manufactured by Big Chemie) as an antifoaming agent, and BYK-354 (manufactured by BYK Chemie) as a leveling agent 1.2 parts by mass was added to obtain a polycarbonate imide resin composition. The composition was first kneaded roughly and then kneaded three times using a high-speed three-roll to obtain a paste having thixotropic properties in which the filler was uniformly dispersed. 4.0 parts by mass of γ-butyrolactone solution (solid content 70%) of jER157S70 (trade name of phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent amount of about 208 g / eq) with respect to 100 parts by mass of this paste. Parts (8.2 parts by mass with respect to 100 parts by mass of the polycarbonate imide resin (A-1)) were 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 232 poise and the throttling rate was 1.32. Polycarbonate imide of the present invention on a copper circuit (L / S = 50/50) obtained by a subtractive method from Toyobo's two-layer CCL (trade name Viroflex (registered trademark), copper foil 18 μm, base material 20 μm) A predetermined pattern was printed on the resin paste (1) with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., emulsion thickness 30 μm) at a printing speed of 5 cm / second, and dried in an air atmosphere at 80 ° C. for 6 minutes. Then, the COF board | substrate (evaluation sample 1) which gave the coverlay (coating) which consists of a polycarbonate imide resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. The evaluation results are shown in Table 1.

(Examples 2 to 5, 7)
A paste was prepared in the same manner as in Example 1 except that the polycarbonate imide resin (A) solution and the components (B) to (C) shown in Table 1 were used, and then evaluation samples 2 to 5 and 7 were prepared. Produced. The evaluation results are shown in Table 1.

(Example 6)
After preparing a paste in the same manner as in Example 1 except that the polycarbonate imide resin solution obtained in Production Example 2 (A) and the components (B) to (C) shown in Table 1 were used. On the copper circuit (L / S = 16/16) obtained by the subtractive method from CCL for COF (trade name Esperflex (registered trademark), copper layer 8 μm, base material 12.5 μm) manufactured by Sumitomo Metal Mining, The polycarbonateimide resin paste of the present invention was printed with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., emulsion thickness 30 μm) at a printing speed of 5 cm / second and dried at 80 ° C. for 6 minutes in an air atmosphere. . Then, the COF board | substrate (evaluation sample 6) which gave the coverlay (coating) which consists of a polycarbonate imide-type resin paste was obtained by heat-hardening for 90 minutes at 120 degreeC. The thickness of the coating was 15 μm. The evaluation results are shown in Table 1.

(Comparative Example 1)
The component (b-1) 45.0 g (0.03 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 20.6 g (synthesized in Production Example 1) 0.05 mol), 26.4 g (0.1 mol) of o-tolidine diisocyanate (TODI) as a diisocyanate, and 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene as a polymerization catalyst, Dissolved in 87.0 g of γ-butyrolactone. Thereafter, the mixture was reacted for 6 hours at 80 ° C. to 190 ° C. with stirring under a nitrogen stream, diluted by adding 74.6 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution B-1. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, the warpage increased because the amount of copolymerization of component (b-1), which is a flexible component, was small.

(Comparative Example 2)
Component (b-1) 105.0 g (0.07 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 4.1 g (synthesized in Production Example 1) 0.01 mol), 21.1 g (0.08 mol) of o-tolidine diisocyanate (TODI) as diisocyanate, 3.5 g (0.02 mol) of 2,4-tolylene diisocyanate (TDI), 1, 0.08 g of 8-diazabicyclo [5,4,0] -7-undecene was added and dissolved in 128.8 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, and then diluted by adding 110.4 g of γ-butyrolactone, and cooled to room temperature. To obtain a polycarbonate imide resin solution B-2. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, since the amount of copolymerization of component (b-1), which is a flexible component, was large, the amount of warpage was small, but the tensile elasticity modulus of the coating film was low, resulting in poor flex resistance.

(Comparative Example 3)
(B-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanhydro trimellitate 12.3 g (synthesized in Production Example 1) 0.03 mol), o-tolidine diisocyanate (TODI) 13.2 g (0.05 mol) as diisocyanate, 8.7 g (0.05 mol) 2,4-tolylene diisocyanate (TDI), 1, 0.08 g of 8-diazabicyclo [5,4,0] -7-undecene was added and dissolved in 104.3 g of γ-butyrolactone. Thereafter, the mixture was reacted at 80 ° C. to 190 ° C. for 6 hours with stirring in a nitrogen stream, diluted by adding 89.4 g of γ-butyrolactone, and cooled to room temperature, whereby a brown viscous solution having a nonvolatile content of 35% by mass was obtained. To obtain a polycarbonate imide resin solution B-3. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. The evaluation results are shown in Table 1. In this case, although the amount of warping was small, the elongation at break was small, resulting in poor bending resistance.

(Comparative Example 4)
75.0 g (0.05 mol) of component (b-1) synthesized in Production Example 1, 9.6 g (0.05 mol) of trimellitic anhydride, 26.4 g of o-tolidine diisocyanate (TODI) as diisocyanate (0.1 mol), 0.08 g of 1,8-diazabicyclo [5,4,0] -7-undecene was added as a polymerization catalyst and dissolved in 102.2 g of γ-butyrolactone. Thereafter, the temperature was raised to 80 ° C. to 190 ° C. with stirring in a nitrogen stream, but evaluation was not possible because it was insolubilized during the polymerization process.

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

Claims

When the component represented by the general formula (1), the component represented by the general formula (2), and the component represented by the formula (3) are contained and the total components are 200 mol%, the general formula (1 ) Is 10 mol% or more, the component represented by the general formula (2) is more than 30 mol% and less than 70 mol%, and the component represented by the formula (3) is 50 mol%. Polycarbonate imide resin (A) characterized by exceeding mol%.

(In the general formula (1), A is a linear 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 represents a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)
(A) Alkylene glycol bisanhydro trimellitate, (b) acid dianhydride having a polycarbonate skeleton represented by general formula (4), and (c) o-tolidine diisocyanate (TODI) as essential copolymerization components And (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), wherein (a) the alkylene glycol bisanhydro trimellitate is 10 mol% or more when the total acid component is 100 mol%. Is a polycarbonate imide resin characterized in that (c) o-tolidine diisocyanate (TODI) exceeds 50 mol% when the total amine component is more than 30 mol% and less than 70 mol% and the total amine component is 100 mol% (A).

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