KR102233604B1 - Polycarbonate imide resin and paste using the same - Google Patents

Abstract

To provide a polycarbonate-imide resin paste that satisfies (1) non-nitrogen solvent solubility, (2) low warpage, and (3) flex resistance at the same time, applicable as a solder resist layer, a surface protective layer, or an adhesive layer.
[Solution] Constituents represented by specific structural formula (1), constituents represented by specific structural formula (2), and constituents represented by specific structural formula (3), and the total constituents are 200 mol% , 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%, and the constituent component represented by the specific structural formula (3) is Polycarbonate imide resin (A), characterized in that more than 50 mol%.

Description

Polycarbonate imide resin and paste using the same

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

In general, polyimide resins are widely used as insulating materials for electric and electronic devices because they are excellent in heat resistance, insulation, and chemical resistance. In particular, it is widely used as a raw material for COF substrates, and is applied to wiring board materials for electronic devices and substrate materials for mounting that require flexibility and small space. For example, device mounting boards for display devices used in liquid crystal displays, plasma displays, organic EL displays, etc., relay cables between boards such as smartphones, tablet devices, digital cameras, portable game machines, operation switch boards, or these boards It is widely used for coverlay materials (protective layers of circuits) and the like. In particular, in printed wiring boards, solder resists are widely used as a permanent protective film for circuits. Solder resist is a film formed on the entire surface of circuit conductors excluding soldering parts, and when wiring electronic components to a printed wiring board, it prevents solder from adhering to unnecessary parts and prevents the circuit from being directly exposed to air. It is used as a protective film.

By the way, since the solder resist layer, the surface protective layer, or the adhesive layer, which is a constituent element of the COF substrate, is often applied and printed in a solution form, a formulation made of a solvent-soluble ring-closed polyimide resin has been proposed as the material. However, conventionally, a high-boiling nitrogen-based solvent such as N-methyl-2-pyrrolidone is used as a solvent for varnishing a polyimide-based resin, so when drying/curing, curing at a high temperature of 200°C or higher for a long time There is a problem in that a process is required, and thermal deterioration of an electronic component occurs.

In addition, since polyimide-based resins are generally hard with a high modulus of elasticity, when laminated on a substrate such as a film or copper foil, warpage or the like occurs due to a difference in elastic modulus, and thus there is a problem in the subsequent process. In addition, the cured film has a problem in that the flexibility is insufficient and the flexibility is inferior.

In addition, as a polyimide-based resin soluble in a non-nitrogen-based solvent and having low warpage and flexibility in which the resin is made flexible and low elastic modulus, for example, (Patent Document 1), (Patent Document 2), etc., a polysiloxane-modified polyimide resin is used. It is disclosed.

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

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

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

However, these are mentioned as examples of resins suitable for melt kneading and melt extrusion, and although they are excellent in heat resistance and mechanical strength, it is difficult to say that they are not soluble in non-nitrogen solvents and have low warpage and flexibility.

As can be seen from such an example, in the prior art until now, as a solder resist layer, a surface protective layer, or an adhesive layer that satisfies (1) non-nitrogen solvent solubility, (2) low warpage, and (3) bending resistance at the same time. An applicable polyimide resin paste has not been obtained.

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

Constituents represented by general formula (1), constituents represented by general formula (2), and constituents represented by formula (3) are contained, and when the total constituents are 200 mol%, general formula (1) ) The component represented by the formula (2) is more than 10 mol%, 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 more than 50 mol% Polycarbonate imide resin (A), characterized in that.

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

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

Polycarbonate imide resin paste, characterized in that it contains 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 thixotropic degree of 1.2 or more, and is preferably used for COF.

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

According to the present invention, a polycarbonate imide resin having excellent solubility in a non-nitrogen solvent, (2) low warpage, and (3) excellent bending resistance, and a paste using the same, and the paste obtained by curing the paste. 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.

<Polycarbonate imide resin (A) component>

The polycarbonate-imide resin (A) of the present invention will be described. The polycarbonate-imide resin (A) contains a component represented by the general formula (1), a component represented by the general formula (2), and a component represented by the formula (3), and contains 200 moles of the total component. When it is set as %, the constituent component represented by general formula (1) is 10 mol% or more, and the constituent component represented by general formula (2) is more than 30 mol% and less than 70 mol%, and further expressed by formula (3) It is a polycarbonate-imide resin characterized in that the constituent component exceeds 50 mol%.

(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 each independently represents a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

<Constituents represented by general formula (1)>

When the polycarbonate-imide resin (A) of the present invention contains the constituent components represented by the general formula (1), the effect of improving the solubility of the non-nitrogen solvent and the heat resistance can be expected. In the general formula (1), A is a straight-chain alkylene group having 1 or more and 20 or less carbon atoms which may have a substituent, and a preferable carbon number is 2 or more and 10 or less. When it has a substituent, it is preferable that a substituent is a C1-C3 alkyl group.

The content of the constituent components 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%. It is preferably 20 mol% or more, and more preferably 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, and it is still more preferable that it is 70 mol% or less. If it is less than 10 mol%, the solubility and heat resistance of a non-nitrogen solvent may not be obtained, and if it is more than 90 mol%, a sufficient amount of the constituent component represented by the general formula (2) or the constituent component represented by the formula (3) described later It may not be able to contain as. Therefore, there are cases where low warpability and flex resistance (mechanical properties) deteriorate.

<Constituents represented by general formula (2)>

Since the constituent component represented by the general formula (2) has flexibility, it is possible to impart low warpage, non-nitrogen solvent solubility, and the like to the polycarbonate-imide resin (A) of the present invention.

In General Formula (2), a plurality of R each independently represents a divalent organic group having 1 or more carbon atoms. Preferred carbon number is 5 or more, more preferably 10 or more, 20 or less are preferable, and 18 or less are more preferable. Moreover, although it does not specifically limit as a divalent organic group, A linear alkylene group which may have a substituent is preferable, and it is preferable that the said carbon number includes carbon of a substituent as well. Moreover, n is an integer of 1 or more, an integer of 2 or more is preferable, an integer of 3 or more is more preferable, an integer of 10 or less is preferable, and an integer of 8 or less is more preferable.

The content of the constituent component represented by the general formula (2) in the polycarbonate imide resin (A) needs to exceed 30 mol%, preferably 35 mol% when the total constituent components are 200 mol%. % Or more, more preferably 40 mol% or more. Moreover, it needs 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 solubility in a non-nitrogen solvent may decrease. Therefore, there is a possibility that the resin will precipitate within one month at 5°C to 30°C. On the other hand, when it is 70 mol% or more, bending resistance (mechanical property) and heat resistance may fall.

As the constituent component of the polycarbonate imide resin (A), the total amount of the constituent component represented by the general formula (1) and the constituent component represented by the general formula (2) is preferably 60 mol% or more, and 65 mol% or more. More preferably, it is more preferably 70 mol% or more, particularly preferably 75 mol% or more, and most preferably 80 mol% or more. When it is too small, the low warpage property and solubility in a non-nitrogen solvent may fall.

<Constituent components represented by formula (3)>

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

The content of the constituent component represented by formula (3) in the polycarbonate imide resin (A) needs to exceed 50 mol%, preferably 60 mol% when the total constituent components are 200 mol%. Or more, more preferably 70 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. When it is 50 mol% or less, the bending resistance may not be fully expressed.

The polycarbonate-imide resin (A) of the present invention contains a predetermined amount of the constituents of the general formulas (1), (2), and (3). Therefore, the polycarbonate-imide resin (A) includes (a) an alkylene glycol bisanehydrotrimelitate, (b) an acid dianhydride having a polycarbonate skeleton represented by the general formula (4), and (c) o- It is preferable to use tolididine diisocyanate as an essential copolymerization component, and when the total acid component is 100 mol%, (a) alkylene glycolbisanhydrotrimelitate is 10 mol% or more, and (b) general formula (4) When the acid dianhydride having a polycarbonate skeleton represented by) 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 desirable.

(In the general formula (4), a plurality of R 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 bisanehydrotrimellitate>

As the component (a) constituting the polycarbonateimide resin (A) used in the present invention, it is necessary to be (a) alkylene glycol bisanehydrotrimellitate (hereinafter, also simply referred to as component (a)). By using alkylene glycol bisanehydrotrimelitate, an effect of excellent solubility in non-nitrogen solvents and heat resistance can be expected.

Although it does not specifically limit as a specific example of alkylene glycol bis anhydrotrimelitate, methylene glycol bis anhydrotrimellitate, ethylene glycol bis anhydrotrimellitate (TMEG), propylene glycol bis anhydrotrimellitate, 1, 4-butanediolbisanhydrotrimelitate, hexamethylene glycolbisanhydrotrimelitate, polyethyleneglycolbisanhydrotrimelitate, or polypropylene glycolbisanhydrotrimelitate, etc., and these may be used alone or in two The above can be used together. From the viewpoint of availability, ethylene glycol bisanehydrotrimelitate (TMEG) is particularly preferred.

The copolymerization amount of the component (a) is required to be 10 mol% or more when the total acid component to be reacted is 100 mol%. It is preferably 20 mol% or more, and more preferably 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, and it is especially preferable that it is 70 mol% or less. If it is less than 10 mol%, the non-nitrogen solvent solubility and heat resistance may not be obtained, and if it is more than 90 mol%, the components (b) and (c) described below may not be copolymerized in a sufficient amount. For this reason, low warpability and flexural resistance (mechanical properties) may decrease.

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

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

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

In General Formula (4), a plurality of R each independently represents a divalent organic group having 1 or more carbon atoms. Preferred carbon number is 5 or more, more preferably 10 or more, 20 or less are preferable, and 18 or less are more preferable. Moreover, although it does not specifically limit as a divalent organic group, A linear or an alkylene group which may have a substituent is preferable, and it is preferable that the said carbon number includes carbon of a substituent as well. Moreover, n is an integer of 1 or more, an integer of 2 or more is preferable, an integer of 3 or more is more preferable, an integer of 10 or less is preferable, and an integer of 8 or less is more preferable.

The polycarbonate diol for synthesizing the component (b) used in the present invention may be a polycarbonate diol (copolymerized polycarbonate diol) having a plurality of types of alkylene groups in its skeleton, and as a commercial product, for example, Kurarepolyol C -1015N, Kurarepolyol C-1065N (Kuraray Co., Ltd. carbonate diol: 2-methyl-1,8-octanediol/1,9-nonanediol, number average molecular weight of about 1,000), Kurarepolyol C-2015N , Kurarepolyol C-2065N (Kuraray Co., Ltd. carbonate diol: 2-methyl-1,8-octanediol/1,9-nonanediol, number average molecular weight of about 2,000), Kurarepolyol C-1050, Kura Repolyol C-1090 (Kuraray Co., Ltd. carbonate diol: 3-methyl-1,5-pentanediol/1,6-hexanediol, number average molecular weight of about 1,000), Kurarepolyol C-2050, Kurarepolyol C-2090 (Kuraray Co., Ltd. carbonate diol: 3-methyl-1,5-pentanediol/1,6-hexanediol, number average molecular weight of about 2,000), DURANOL (registered trademark)-T5650E (Asahi Gasei Chemical Polycarbonate diol manufactured by Z Co., Ltd.: 1,5-pentanediol/1,6-hexanediol, number average molecular weight of about 500), DURANOL (registered trademark)-T5651 (polycarbonate diol manufactured by Asahi Chemicals Co., Ltd.) : 1,5-pentanediol/1,6-hexanediol, number average molecular weight of about 1,000), DURANOL (registered trademark)-T5652 (polycarbonate diol manufactured by Asahi Chemicals Co., Ltd.: 1,5-pentanediol/ 1,6-hexanediol, number average molecular weight of about 2,000), etc. are mentioned.

The method for producing the component (b) is not particularly limited, but can be synthesized from a chloride of trimellitic anhydride and the above-described diol compound by a known reaction method. More specifically, first, a diol compound and a deoxidizing agent 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 performed at -20 to 50°C, but from the viewpoint of reaction selectivity, more preferably at 20 to 40°C. As the reaction ratio of the chloride of trimellitic anhydride and the diol compound, it is preferable to react by using 2 mol or more of the chloride of trimellitic anhydride 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 and fractionated, and the solvent is concentrated to obtain an acid dianhydride having a polycarbonate skeleton represented by the target general formula (4) (hereinafter, also referred to as a polycarbonate skeleton-containing tetracarboxylic dianhydride). .) can be obtained.

When the total acid component is 100 mol%, the copolymerization amount of the component (b) needs to exceed 30 mol%, preferably 35 mol% or more, and more preferably 40 mol% or more. Further, it needs 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, the elastic modulus may not sufficiently decrease, and when laminated, warpage may occur or solubility in a non-nitrogen solvent may decrease. Therefore, there is a possibility that the resin will precipitate within one month at 5°C to 30°C. On the other hand, if it is 70 mol% or more, since the above-described component (a) or the later-described component (c) cannot be contained in a sufficient amount, the bending resistance (mechanical properties) and heat resistance may be deteriorated.

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, further preferably 70 mol% or more, , 75 mol% or more is particularly preferred, and 80 mol% or more is most preferred. When it is too small, the low warpage property and the solubility in a non-nitrogen-based solvent may decrease.

<Other acid components>

As the other acid component, a trivalent or tetravalent polycarboxylic acid derivative having an acid anhydride group can be used. Although it does not specifically limit as an aromatic polycarboxylic acid derivative, For example, trimellitic anhydride (TMA), pyromellitic dianhydride, 3,3'-4,4'-benzophenonetetracarboxylic dianhydride, 3, 3'-4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 ,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride Water, 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]propanedianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis[4- (2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, or 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride And water.

The aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, but, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic acid Dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohexa-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-1- En-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexa-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2),3,4 -Tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane-2,3 ,5,6-tetracarboxylic 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 hexahydrotrimellitic anhydride.

These trivalent and/or tetravalent polycarboxylic acid derivatives having an acid anhydride group may be used alone or in combination of two or more. When the acid component is 100 mol%, 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. It is more preferable, and it is especially preferable that it is 25 mol% or less, and it is most preferable that it is 20 mol% or less.

In addition, aliphatic, alicyclic, and aromatic dicarboxylic acids may be further copolymerized as necessary within a range that does not impair the desired performance. As the aliphatic dicarboxylic acid, for example, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosandioic acid, 2-methylsuccinic acid, 2-methyladip Acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9 As an alicyclic dicarboxylic acid, such as, 12-dimethyleichoic acid diacid, fumaric acid, maleic acid, dimer acid, hydrogenated dimer acid, etc., 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples of aromatic dicarboxylic acids such as carboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid, etc. include isophthalic acid, terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, Oxydianbenzoic acid, stilbene dicarboxylic acid, etc. are mentioned. These dicarboxylic acids may be used alone or in combination of two or more. In consideration of heat resistance, adhesion, solubility, cost, and the like, sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferable.

<(c) o-tolidine diisocyanate>

The component (c) constituting the polycarbonateimide resin (A) of the present invention contains o-tolidine diisocyanate (hereinafter, also referred to as TODI) as an essential component. Excellent bending resistance can be expressed by using o-tolidine diisocyanate.

(c) The amount of o-tolidine diisocyanate copolymerization, when the total amine component is 100 mol%, needs to exceed 50 mol%, preferably 60 mol% or more, more preferably 70 mol% or more , 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 elastic modulus value becomes low, and the bending resistance may not be fully expressed.

<Other isocyanate compounds>

In the polycarbonate-imide resin (A) of the present invention, an isocyanate compound may be further copolymerized as necessary within a range that does not impair the desired performance. It does not specifically limit if it is an isocyanate compound, An aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is mentioned. Preferably, aromatic polyisocyanates are used. Although not particularly limited, specifically as an aromatic polyisocyanate, for example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4, 2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2 '- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane- 2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4, 4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m -Xylylenediisocyanate, p-xylylenediisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2bis(4-phenoxyphenyl)propane]diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4' -Diisocyanate, etc. are mentioned. In consideration of heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4'-diisocyanate (MDI), tolylene-2,4-diisocyanate (TDI), m-xylylene diisocyanate are preferable. , Tolylene-2,4-diisocyanate (TDI) is more preferable. These can be used alone or in combination of two or more.

When the amine component used in the polycarbonateimide resin (A) of the present invention is 100 mol%, it is preferable that any one of the isocyanate compounds is 100 mol%. When a diamine compound corresponding to the isocyanate is used instead of the isocyanate, a polyamic acid is used as a precursor of the polycarbonate polyimide resin. When passing through polyamic acid, after applying a polyamic acid-containing paste to a substrate such as a COF (Chip On Film), it is necessary to imidize it at a high temperature of about 200°C or higher, and there is a possibility of thermal deterioration of the COF. In addition, there are cases where there are restrictions in terms of equipment. In the present invention, since only the isocyanate compound containing TODI is used as the amine component, it can be treated at a lower temperature than the polyamic acid-containing paste, and it is preferable because there is no such problem as described above.

In addition to the component (b), another flexible component may be copolymerized as necessary within a range that does not impair the target performance. For example, aliphatic/aromatic polyester diols (manufactured by Toyobo Co., Ltd., brand name VYLON (registered trademark) 220), aliphatic/aromatic polycarbonate diols (manufactured by Daisel Chemical Co., Ltd., brand name PLACCEL (registered trademark)- CD220, manufactured by Kuraray, brand names C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, etc., manufactured by Asahi Gasei Chemicals Co., Ltd. Duranol (registered trademark) T-4671, T-4672, T-5650E, T-5650J, T-5651, T5652, etc.), polycaprolactone diols (manufactured by Daicel Chemical Industry Co., Ltd., brand name PLACCEL (registered trademark)) -220, etc.), polysiloxane derivatives such as carboxy-modified acrylonitrile butadiene rubber (manufactured by Ubegosan Co., Ltd., brand name HyproCTBN1300×13, etc.), polydimethylsiloxane diol, polymethylphenylsiloxane diol, and carboxy-modified polydimethylsiloxane I can.

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 blending amount of the 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 desirable to do it. If it is less than 0.8, it may become difficult to increase the molecular weight of the polycarbonate imide resin (A), and heat resistance and bending resistance may decrease, or the coating film may be weak. In addition, when it is higher than 1.2, the viscosity of the polycarbonate-imide resin (A) may increase, and the plate separation may worsen during printing in the case of ink formation.

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, heating while removing free-generated carbon dioxide gas from the reaction system It is preferable to carry out condensation.

The solvent is not particularly limited, but if it is an ether solvent, for example, diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), triethylene glycol If it is an ester solvent, such as diethyl ether (ethyl triglyme), for example, γ-butyrolactone, cellosolve acetate, etc., if a ketone solvent, for example methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, etc., If it is an aromatic hydrocarbon-based solvent, toluene, xylene, sorbeso, etc. are mentioned, for example. These may be used alone or in combination of two or more.

When preparing the polycarbonate imide resin (A), it is preferable to select and use a solvent that dissolves the resulting polycarbonate imide resin (A). After polymerization, it is more preferable to use a suitable solvent as the polycarbonate imide resin paste as it is. desirable. By doing so, troublesome operation such as solvent substitution is eliminated, and it becomes possible to manufacture inexpensively. In addition, the boiling point of the solvent is preferably 140°C or more and 230°C or less. If it is less than 140°C, the solvent may be volatilized during the polymerization reaction, and when screen printing is performed, for example, the volatilization of the solvent is rapid, and there is a possibility that plate clogging may occur. When it exceeds 230 degreeC, it may become difficult to impart low temperature drying/hardening property. Relatively highly volatile, low temperature drying/hardening can be imparted, varnish stability is excellent, and γ-butyrolactone, cyclohexanone, diglyme or triglyme is preferred in order to react efficiently 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 polycarbonateimide resin (A) to be produced, and more preferably 0.9 to 2.0 times. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and synthesis tends to become difficult due to inability to stir, and if it exceeds 5.0 times, the reaction rate tends to decrease.

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 is prolonged, and if it exceeds 200°C, decomposition of the monomer component may occur during the reaction. In addition, a three-dimensional reaction occurs and gelation is liable 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, and particularly the reaction concentration.

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

<Production of polycarbonate imide resin (A)>

As an example of the manufacturing method of the polycarbonate imide resin (A), it can obtain by condensation reaction (polyimide conversion) of (a) component, (b) component, and (c) component. Hereinafter, the method for producing the polycarbonate-imide resin of the present invention is illustrated, but the present invention is not limited thereto.

After dissolving by adding and dissolving (a) component, (b) component, (c) component, polymerization catalyst, and polymerization solvent to the reaction vessel, the mixture is stirred at 80 to 190°C, preferably 100 to 180°C for 5 hours or longer. After reacting, the target polycarbonate-imide resin (A) can be obtained by diluting and cooling to an appropriate solvent viscosity with a polymerization solvent.

The polycarbonateimide 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, more preferably 0.2 to 1.5, among γ-butyrolactone. It has a molecular weight corresponding to the logarithmic viscosity of dl/g. If the logarithmic viscosity is less than 0.1 dl/g, the heat resistance may decrease or the coating film may be weak. In addition, there is a case where the tackiness of the paste is strong and the plate separation is poor. On the other hand, when it exceeds 2.0 dl/g, it becomes difficult to dissolve in a solvent, and it is easy to be insolubilized during polymerization. In addition, the viscosity of the varnish is increased, making handling difficult, or in some cases, the adhesion to the substrate decreases.

The glass transition temperature of the polycarbonateimide resin (A) used in the present invention is preferably 20°C or higher, and more preferably 60°C or higher. If it is less than 20°C, heat resistance is insufficient, and there is a fear that the resin may be blocked. Although the upper limit is not particularly limited, from the viewpoint of solvent solubility, 300° C. or less is preferable.

<Epoxy resin (B) component>

The epoxy resin of the 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. Although it does not specifically limit as an epoxy resin (B), For example, the brand name jER (registered trademark) 828, 1001 manufactured by Mitsubishi Chemical Co., Ltd. bisphenol A type epoxy resin, etc., a brand name ST- manufactured by Totokasei Hydrogenated bisphenol A type epoxy resin such as 2004 and 2007, Bisphenol F type epoxy manufactured by Totokasei Co., Ltd., brand name YDF-170, 2004, etc., Brominated by Totokasei Co., Ltd. brand name YDB-400, 600, etc. Bisphenol A type epoxy resin, brand names manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 152, 154, 157S70, 1032H60, brand names manufactured by Nippon Kayaku Corporation EPN (registered trademark)-201, BREN (registered trademark) , Phenol novolac-type epoxy resins such as DEN-438 manufactured by Dow Chemical, brand names YDCN-702, 703 manufactured by Totokasei Co., Ltd., and EOCN (registered trademark)-125S manufactured by Nippon Kayaku Co., Ltd. , 103S, 104S, etc., o-cresol novolac type epoxy resins, Totogasei's brand name YD-171, etc., flexible epoxy resins, Yuka Shell Epoxy's brand name Epon1031S, Chiba Specialty Chemicals ( Note) Manufacturing brand name Araldite (registered trademark) 0163, manufactured by Nagase Chemtech Co., Ltd. brand name DENACOOL (registered trademark) EX-611, EX-614, EX-622, EX-512, EX-521, EX Multifunctional epoxy resins such as -421, EX-411, EX-321, etc., the brand name Epicoat (registered trademark) 604 manufactured by Yuka Shell Epoxy Co., Ltd., the brand name YH-434 manufactured by Totokasei Co., Ltd., Mitsubishi Gaska Amine-type epoxy resin such as TETRAD (registered trademark)-X, TETRAD-C manufactured by Gaku Co., Ltd., brand name GAN manufactured by Nippon Kayaku Corporation, brand name ELM-120 manufactured by Sumitomo Chemical Co., Ltd., Chiba Trade names manufactured by Specialty Chemicals Co., Ltd.Araldite (registered trademark) Heterocyclic-containing epoxy resin such as PT810, trade names manufactured by Daisel Chemicals Co., Ltd. Seroxide (registered trademark) 2021, EHPE (registered trademark) 3150, Paper such as ERL4234 manufactured by UCC Cyclic epoxy resin, trade name Epicron (registered trademark) manufactured by Dai Nippon Chemical Co., Ltd. Bisphenol S-type epoxy resin such as EXA-1514, Triglyci such as TEPIC (registered trademark) manufactured by Nissan Chemical Industry Co., Ltd. Diisocyanurate, bixylenol-type epoxy resins such as YX-4000 manufactured by Yucca Shell Epoxy Co., Ltd., bisphenol-type epoxy resins such as YL-6056 manufactured by Yucca Shell Epoxy Co., Ltd., and the like. You may use these individually or in combination of 2 or more types.

Among these epoxy resins, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin having more than two epoxy groups per molecule, and an o-cresol novolak type epoxy resin are preferable. In addition, the amine-type epoxy resin is non-halogen-based, and is preferable from the viewpoint of improving compatibility with the polycarbonateimide resin (A), solvent resistance, chemical resistance, and moisture resistance.

The amount of the epoxy resin (B) used in the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, particularly preferably 3 parts by mass per 100 parts by mass of the polycarbonate imide resin (A). It is -30 parts by mass. When the blending amount of the epoxy resin (B) is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease, and when it exceeds 50 parts by mass, low warpage, mechanical properties, heat resistance, varnish stability and poly The compatibility with the carbonate imide resin (A) tends to decrease. In addition, the cured film has insufficient flexibility, and there is a tendency for the bending resistance (mechanical properties) to decrease.

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

The method of adding 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). It may be added to the carbonate 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 is dispersed in the above-described polycarbonate-imide resin (A) to form a paste and can impart thixotropy (thixotropy) to the paste. That is, it is preferably an inorganic or organic filler capable of imparting thixotropy to the polycarbonate-imide resin paste of the present invention. Examples of such inorganic fillers include silica (SiO ₂ , brand name AEROSIL (registered trademark) manufactured by Nippon Aerosil Co., Ltd.), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), and tantalum oxide (Ta ₂ O ₅ ). , Zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO TiO ₂ ), lead zirconate titanate (PZT), zircon titanate scattering Tan lead (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 (C), organic smectite (Trade names manufactured by Corp. Chemical Co., Ltd., Lucentite (registered trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN), etc. can be used, and these may be used alone or in combination of two or more. Does not matter. From the viewpoint of imparting color tone, transparency, mechanical properties, and thixotropic properties of the resulting paste, it is preferable to use silica or leucentite.

As the inorganic filler used in the present invention, the average particle diameter is preferably 50 µm or less and the maximum particle diameter is 100 µm or less, more preferably 20 µm or less, and most preferably 10 µm or less. The average particle diameter (median diameter) referred to herein is a value obtained on a volume basis using a laser diffraction/scattering particle size distribution measuring device. 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 decrease. 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 may be dispersed in the above polycarbonate-imide resin solution to form a paste, and may impart thixotropy to the paste. Polyimide resin particles, benzoguanamine resin particles, and epoxy resins Particles, etc. are mentioned.

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

To the polycarbonate-imide resin paste of the present invention, a curing accelerator may be added to further improve 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 is capable of accelerating the curing reaction of the polycarbonate imide resin (A) and the epoxy resin (B).

Specific examples of such a curing accelerator include, for example, manufactured by Shikoku Chemicals Co., Ltd., 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, Imidazole derivatives such as 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, guanamines such as acetoguanamine and benzoguanamine Polyamines, such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, and organic acid salts thereof And/or an epoxy adduct, an amine complex of boron trifluoride, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-tri Triazine derivatives such as azine, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6- Tris(dimethylaminophenol), tetramethylguanidine, DBU(1,8-diazabicyclo[5,4,0]-7-undecene), DBN(1,5-diazabicyclo[4,3,0] -5-nonene), and other organic acid salts thereof, U-CAT (registered trademark) SA1 (DBU-phenol salt), U-CAT (registered trademark) SA 102 (DBU-octylate), U-CAT (Registered trademark) SA 831 (DBU-phenol novolac resin salt), U-CAT (registered trademark) 5002 (DBU-based tetraphenyl borate salt) (all manufactured by San Apro Co., Ltd.) and/or tetraphenylboroate, Organic phosphines such as polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) Quaternary phosphonium salts such as phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylboroate, benzyltrimethylammonium chloride, quaternary ammonium salts such as phenyltributylammonium chloride, the polycarboxyl Acid anhydride, dipe Niliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyryllium hexafluorophosphate, Irgacure (registered trademark) 261 (Chiba Specialty Chemicals) Co., Ltd.), photocationic polymerization catalysts such as Optomer SP-170 (manufactured by ADEKA Co., Ltd.), styrene-maleic anhydride resin, an equimolar reaction product of phenyl isocyanate and dimethylamine, or tolylene diisocyanate, isophorone diisocyanate An equimolar reaction product of an organic polyisocyanate, such as dimethylamine, etc. are mentioned. These may be used alone or in combination of two or more. Preferably, it is a curing accelerator having latent curing properties, and examples thereof include organic acid salts of DBU and DBN and/or tetraphenylboroate, photocationic polymerization catalysts, and the like.

The amount of the curing accelerator used is preferably 0 to 20 parts by mass when the component (A) is 100 parts by mass. When it 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 aforementioned polycarbonate-imide resin (A) component, epoxy resin (B) component, and filler (C) component. Further, if necessary, other blending components can be preferably blended in the above-described ratio. It is preferable to obtain by uniformly mixing each of these components with a roll mill, mixer, three rolls, or the like. The mixing method is not particularly limited as long as it is a method capable of obtaining sufficient dispersion. A plurality of kneading times by three rolls is preferable.

The polycarbonate-imide resin paste of the present invention preferably has a viscosity in the range of 50 dPa·s to 1000 dPa·s at 25°C in a Brookfield viscometer (hereinafter, also referred to as a B-type viscometer), and 100 dPa·s to The range of 800 dPa·s is more preferable. If the viscosity is less than 50 dPa·s, the outflow of the paste after printing increases, and the film thickness tends to become thinner. When the viscosity exceeds 1000 dPa·s, during printing, the transferability of the paste to the substrate decreases, resulting in blurring, and voids and pinholes in the printing film tend to increase.

Thixotropy is also important. The thixotropy of the polycarbonate-imide resin paste is preferably 1.2 or more, and more preferably 1.3 or more in the measurement method described later. 7.0 or less are preferable and, as for the upper limit, 6.0 or less are more preferable. When the thixotropic degree is less than 1.2, the outflow of the paste after printing increases, and the film thickness tends to become thinner. If it exceeds 7.0, there is a tendency that the paste does not flow. The thixotropic degree can be adjusted by the blending amount of the component (c) as the thixotropic degree imparting agent.

In the polycarbonateimide resin and paste of the present invention, if necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and hydro Known and commonly used polymerization inhibitors such as quinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, etc. Defoamers, leveling agents, imidazole-based, thiazole-based, triazole-based, organic aluminum compounds, organic titanium compounds, organic silane compounds and other coupling agents/adhesion imparting agents, triphenyl phosphate, tricredyl phosphate, tricsilenyl phosphate, Triethyl phosphate, credyldiphenyl phosphate, xylenyldiphenyl phosphate, credylbis (2,6-xylenyl) phosphate, 2-ethylhexyl phosphate, dimethylmethyl phosphate, resorcinolbis (diphenol A bis(di Cresyl) phosphate, diethyl-N,N-bis (2-hydroxyethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, phosphorus-based flame retardants such as red phosphorus, ammonium polyphosphate, triazine, melamine cyanurate, Succinoguanamine, ethylenedimelamine, triguanamine, cyanurate triazinyl salt, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanyl melamine sulfate, melem sulfate, melam sulfate Nitrogen-based flame retardants such as diphenyl sulfone-3-sulfonate potassium, aromatic sulfonimide metal salts, polystyrene sulfonic acid alkali metal salts and other metal salt-based flame retardants, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, Hydrated metal-based flame retardants such as zirconium hydroxide and 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 Inorganic flame retardants such as, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, and zinc stannate, silicon wave Known and commonly used additives such as flame retardants/flame retardant aids such as wood, heat stabilizers, antioxidants, and lubricants can be used.

<Cured coating>

The polycarbonate-imide resin paste of the present invention can be cured as follows, for example, as a solder resist to obtain a cured product. That is, on a COF (Chip On Film) substrate formed by plating copper on a resin substrate such as a polyimide film, 5 to 80 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. The polycarbonate-imide resin paste of the present invention is applied to a thickness of, and the coating film is pre-dried at 60 to 120°C, followed by main drying at 120 to 200°C. Drying may be carried out in air or in an inert atmosphere. Here, as a method of plating copper on a resin base material, electroless plating may be sufficient, and a method of sputtering copper on a resin base material may be sufficient.

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 the COF substrate. As described above, the polycarbonate-imide resin paste of the present invention can be used as a film forming material, not only useful for overcoat inks for semiconductor devices and various electronic components, solder resist inks, but also as paints, coatings, adhesives, and the like. Here, the solder resist layer is a film formed on the entire surface of the circuit conductor excluding the portion to be soldered. When wiring electronic components to a printed wiring board, solder is prevented from being adhered to unnecessary portions, and the circuit is directly exposed to air. It is used as a protective film to prevent it from being formed. The surface protective layer is used to mechanically and chemically protect an electronic member from a processing process or a use environment by bonding to the surface of a circuit member. The adhesive layer is mainly used when bonding a metal layer and a film layer to perform bonding processing.

Example

Examples are given below in order to explain the present invention more specifically, but the present invention is not limited to the examples at all. In addition, the measured values described in Examples were 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 Uberode type viscometer, and calculated by the following equation.

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

In the above formula, V1 represents the solvent viscosity measured by an Uberode type viscometer, and V1 and V2 represent the polymer solution and solvent (N-methyl-2-pyrrolidone) passing through the capillary of the viscosity tube. It was calculated from time. In addition, V3 is the polymer concentration (g/dl).

<Non-nitrogen solvent solubility>

During polymerization of the polycarbonate-imide resin (A), the (a) component, (b) component, (c) component, and γ-butyrolactone were added to the reaction vessel to increase the temperature, and when the internal temperature reached 100°C, the raw material ( It evaluated by whether or not (a) component, (b) component, and (c) component) were dissolved.

(Evaluation) ○: Completely dissolved

△: Slightly dissolved residue

×: almost insoluble

<Preparation of polycarbonate imide resin paste>

A filler (C) was added to the polycarbonate imide resin (A), and diluted with γ-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 kneading was repeated 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>

For the laminated film, a commercially available base film made of polyimide, a brand name Viroflex (registered trademark) (manufactured by Toyobo), and a brand name Espaplex (manufactured by Sumitomo Ginjokugosan) were used.

Polycarbonate imide on a copper circuit (L/S = 50/50) obtained by a subtractive method with a two-layer CCL manufactured by Toyobo (trade name Viroflex (registered trademark), copper foil 18 µm, base material 20 µm) The resin paste was printed with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., an emulsion thickness of 30 µm), a predetermined pattern was printed at a printing speed of 5 cm/sec, and dried at 80° C. for 6 minutes in an air atmosphere (screen printing). Thereafter, by heating and curing at 120° C. for 90 minutes, a laminated film having a coverlay (film) made of a polycarbonate imide resin paste was obtained. The thickness of the film was 15 µm. In the case of using CCL for COF manufactured by Sumitomo Ginjokugosan (trade name Espaplex, copper layer 8 µm, base material 12.5 µm), a copper circuit obtained by the subtractive method (L/S = 16/16) was used as described above. A laminated film was obtained by the formula.

<Yophile degree (tick consumption)>

It was measured by the following procedure using a Brookfield BH type rotational viscometer. 90 ml of 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, after stirring 40 times over 12 to 15 seconds using a glass rod, a predetermined rotor was installed, left to stand for 5 minutes, and then the scale when rotated at 10 rpm for 3 minutes was read and the viscosity was calculated. Similarly, it was calculated by the following equation from the viscosity value measured at 25°C and 1 rpm.

Thixotropy = viscosity (1 rpm)/viscosity (10 rpm)

<Evaluation of the amount of warpage>

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

(Judgment) ○: Less than 2 mm in height

△: height 2 mm or more and less than 10 mm

×: height 10 mm or more

<Bending resistance (MIT test)>

The obtained laminated film was evaluated according to JIS-C-6471 (1995). With a load of 300 g and a diameter of a core rod of 0.38 mm, the presence or absence of cracks was confirmed, and the number of bendings when cracks occurred was recorded.

(Judgment) ◎: No cracking in more than 250 bends

○: No cracking in bending more than 200 times

×: cracks occur less than 200 times

<Tensile test>

Tensile modulus and elongation at break were evaluated according to JIS-K-7161 (2014) using a tensile tester (trade name "Tensile and Compression Tester TG-2kN", manufactured by Minevea Co., Ltd.). A film-like sample obtained by curing the polycarbonate-imide resin paste at 120° C. for 90 minutes was measured under the following conditions.

Sample size: 10 mm wide x 40 mm long

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)

In a reaction vessel, 167 g (0.87 mol) of trimellitic anhydride (TMA) and thionyl chloride were added and reacted to synthesize a chloride of trimellitic anhydride. Subsequently, 183 g (0.87 mol) of a chloride of trimellitic anhydride and Duranol T5651 (manufactured by Asahi Chemicals Co., Ltd.) as a diol compound: 1,5-pentanediol/1,6-hexanediol, molecular weight 1000 ) 434 g (0.43 mol) was esterified in toluene at 30°C to synthesize a polycarbonate skeleton-containing tetracarboxylic dianhydride.

(Production Example 2)

(B-1) component 60.0 g (0.04 mol) synthesized in Preparation Example 1, trimellitic anhydride (TMA) 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate (TMEG) 16.4 g (0.04 mol) ), o-tolidine diisocyanate (TODI) 26.4 g (0.1 mol) as a diisocyanate, 1,8-diazabicyclo[5,4,0]-7-undecene 0.08 g as a polymerization catalyst, and γ-buty It dissolved in 97.9 g of lolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 83.9 g of γ-butyrolactone, and cooling to room temperature, whereby a nonvolatile content of 35% by mass is brown and viscous. A polycarbonate imide resin solution A-1 was obtained.

(Production Example 3)

Synthesized in Preparation Example 1, (b-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 12.3 g (0.03 mol), as diisocyanate o -Toridine diisocyanate (TODI) 26.4 g (0.1 mol), 1,8-diazabicyclo[5,4,0]-7-undecene 0.08 g was added as a polymerization catalyst, and γ-butyrolactone was dissolved in 108.8 g I did. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 93.3 g of γ-butyrolactone and cooling to room temperature. A polycarbonate imide resin solution A-2 was obtained.

(Production Example 4)

(B-1) component 90.0 g (0.06 mol) synthesized in Preparation Example 1, trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 8.2 g (0.02 mol), as diisocyanate o -Toridine diisocyanate (TODI) 26.4 g (0.1 mol), 1,8-diazabicyclo[5,4,0]-7-undecene 0.08 g was added as a polymerization catalyst, and γ-butyrolactone was dissolved in 119.7 g I did. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 102.6 g of γ-butyrolactone and cooling to room temperature. A polycarbonate imide resin solution A-3 was obtained.

(Production Example 5)

(B-1) component 60.0 g (0.04 mol) synthesized in Preparation Example 1, trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 16.4 g (0.04 mol), as diisocyanate o -Tolidene diisocyanate (TODI) 21.1 g (0.08 mol), 2,4-tolylene diisocyanate (TDI) 3.5 g (0.02 mol), 1,8-diazabicyclo[5,4,0]-7 as polymerization catalyst -0.08 g of undecene was added and dissolved in 96.1 g of γ-butyrolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 82.4 g of γ-butyrolactone and cooling to room temperature. A polycarbonate imide resin solution A-4 was obtained.

(Production Example 6)

Synthesized in Preparation Example 1, (b-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 12.3 g (0.03 mol), as diisocyanate o -Tolidene diisocyanate (TODI) 21.1 g (0.08 mol), 2,4-tolylene diisocyanate (TDI) 3.5 g (0.02 mol), 1,8-diazabicyclo[5,4,0]-7 as polymerization catalyst -0.08 g of undecene was added and dissolved in 107.0 g of γ-butyrolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 91.7 g of γ-butyrolactone, and cooling to room temperature, whereby a nonvolatile content of 35% by mass is brown and viscous. A polycarbonate imide resin solution A-5 was obtained.

(Production Example 7)

Synthesized in Preparation Example 1, (b-1) component 75.0 g (0.05 mol), trimellitic anhydride (TMA) 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate (TMEG) 12.3 g (0.03 mol) ), o-tolidine diisocyanate (TODI) 22.5 g (0.09 mol) as a diisocyanate, 1,8-diazabicyclo[5,4,0]-7-undecene 0.06 g as a polymerization catalyst, and γ-buty It was dissolved in 83.4 g of lolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 22.8 g of γ-butyrolactone, and cooling to room temperature, whereby 50% by mass of non-volatile content was brown and viscous. A polycarbonate imide resin solution A-6 was obtained.

(Example 1)

With respect to 100 parts by mass of the non-volatile content of the polycarbonate imide resin solution A-1 obtained in Production Example 2, 4.0 parts by mass of Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.) as a filler, and U-CAT SA1 (San-A) as a curing accelerator Pro (manufactured by Co., Ltd.), 1.0 parts by mass, BYK-054 (manufactured by Vicchemy, Inc.) as a defoaming agent, 1.1 parts by mass, and 1.2 parts by mass of BYK-354 (manufactured by Vicchemy, Inc.) were added as a leveling agent. A mid resin composition was obtained. This composition was first co-kneaded, and then, by repeating the kneading three times using a high-speed three roll, the filler was uniformly dispersed to obtain a thixotropic paste. To 100 parts by mass of this paste, 4.0 parts by mass of a γ-butyrolactone solution (solid content 70%) of jER157S70 (trade name of a phenol novolak type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 208 g/eq) (8.2 mass parts per 100 mass parts of polycarbonate imide resin (A-1)) was added, and the polycarbonate imide resin paste (1) of this invention was obtained. When the viscosity was adjusted with γ-butyrolactone, the solution viscosity was 232 poise and the thixotropic degree was 1.32. On the copper circuit (L/S = 50/50) obtained by the subtractive method with a two-layer CCL manufactured by Toyobo (trade name Viroflex (registered trademark), copper foil 18 µm, base material 20 µm), the polycarbonate of the present invention was The mid resin paste 1 was printed on a predetermined pattern with a SUS mesh plate (150 mesh manufactured by Murakimi Co., Ltd., an emulsion thickness of 30 µm) at a printing speed of 5 cm/sec, and dried at 80° C. for 6 minutes in an air atmosphere. Thereafter, by heating and curing at 120° C. for 90 minutes, a COF substrate (evaluation sample 1) on which a coverlay (film) made of a polycarbonate imide resin paste was applied was obtained. The thickness of the film was 15 µm. Table 1 shows the evaluation results.

(Examples 2 to 5, 7)

After preparing a paste in the same manner as in Example 1, except for using the polycarbonate-imide resin (A) solution and the components (B) to (C) described in Table 1, evaluation samples 2 to 5 and 7 were prepared. . Table 1 shows the evaluation results.

(Example 6)

After preparing a paste in the same manner as in Example 1, except that the polycarbonate-imide resin solution (A) solution and the components (B) to (C) obtained in Preparation Example 2 were used as described in Table 1, Sumitomo Ginzoku On the copper circuit (L/S = 16/16) obtained by the subtractive method with CCL for COF manufactured by Kosan (trade name Espaplex (registered trademark), copper layer 8 µm, substrate 12.5 µm), the polycarbonate imide of the present invention The system resin paste was printed with a SUS mesh plate (150 mesh manufactured by Murakami Co., Ltd., an emulsion thickness of 30 µm), a predetermined pattern was printed at a printing speed of 5 cm/sec, and dried at 80° C. for 6 minutes in an air atmosphere. Thereafter, by heating and curing at 120° C. for 90 minutes, a COF substrate (evaluation sample 6) on which a coverlay (film) made of a polycarbonate-imide resin paste was applied was obtained. The thickness of the film was 15 µm. Table 1 shows the evaluation results.

(Comparative Example 1)

(B-1) component 45.0 g (0.03 mol) synthesized in Preparation Example 1, trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 20.6 g (0.05 mol), as diisocyanate o -Toridine diisocyanate (TODI) 26.4 g (0.1 mol), 1,8-diazabicyclo[5,4,0]-7-undecene 0.08 g was added as a polymerization catalyst, and γ-butyrolactone was dissolved in 87.0 g I did. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by dilution by adding 74.6 g of γ-butyrolactone, and cooling to room temperature, whereby 35% by mass of nonvolatile content was brown and viscous. A polycarbonate imide resin solution B-1 was obtained. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. Table 1 shows the evaluation results. In this case, the amount of copolymerization of the component (b-1), which is a flexible component, is small, so that the warpage is large.

(Comparative Example 2)

(B-1) component 105.0 g (0.07 mol) synthesized in Preparation Example 1, trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 4.1 g (0.01 mol), as diisocyanate o -Tolidene diisocyanate (TODI) 21.1 g (0.08 mol), 2,4-tolylene diisocyanate (TDI) 3.5 g (0.02 mol), 1,8-diazabicyclo[5,4,0]-7 as polymerization catalyst -0.08 g of undecene was added and dissolved in 128.8 g of γ-butyrolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by dilution by adding 110.4 g of γ-butyrolactone, and cooling to room temperature. A polycarbonate imide resin solution B-2 was obtained. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. Table 1 shows the evaluation results. In this case, since the copolymerization amount of the component (b-1) as the flexible component is large, the amount of warpage is small, but the tensile modulus of the coating film is low, resulting in inferior bending resistance.

(Comparative Example 3)

Synthesized in Preparation Example 1, (b-1) component 75.0 g (0.05 mol), trimellitic anhydride 3.8 g (0.02 mol), ethylene glycol bisanehydrotrimellitate 12.3 g (0.03 mol), as diisocyanate o -Tolidene diisocyanate (TODI) 13.2 g (0.05 mol), 2,4-tolylene diisocyanate (TDI) 8.7 g (0.05 mol), 1,8-diazabicyclo[5,4,0]-7 as polymerization catalyst -0.08 g of undecene was added and dissolved in 104.3 g of γ-butyrolactone. Thereafter, the reaction was carried out at 80°C to 190°C for 6 hours while stirring in a nitrogen stream, followed by diluting by adding 89.4 g of γ-butyrolactone, and cooling to room temperature. A polycarbonate imide resin solution B-3 was obtained. After preparing a paste in the same manner as in Example 1, an evaluation sample was prepared. Table 1 shows the evaluation results. In this case, the amount of warpage was small, but the elongation at break was small, resulting in poor bending resistance.

(Comparative Example 4)

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

The polycarbonate-imide resin obtained by the present invention and a paste made of the same have excellent heat resistance, flexibility, and bending resistance as a film-forming material. For this reason, in addition to being useful in overcoat inks and solder resist inks for various electronic components such as COF substrates, it can be used in a wide range of fields of electronic devices as paints, coating agents, adhesives, and the like, and is expected to greatly contribute to the industrial world.

Claims (6)

Constituents represented by general formula (1), constituents represented by general formula (2), and constituents represented by formula (3) are contained, and when the total constituents are 200 mol%, general formula (1) ) The component represented by the formula (2) is more than 10 mol%, 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 more than 50 mol% Polycarbonate imide resin (A), characterized in that.

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

(In the general formula (4), a plurality of R 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) according to claim 1 or 2, 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 thixotropic degree is 1.2 or more. The polycarbonate-imide resin paste according to claim 3, which is used for COF (Chip On Film). An electronic component comprising a solder resist layer, a surface protective layer, or an adhesive layer obtained by curing the polycarbonate-imide resin paste according to claim 3.