TWI650338B - Curable composition, cured film using the composition, and coated film - Google Patents

Abstract

An object of the present invention is to provide a thermosetting resin composition which can sufficiently suppress warpage while maintaining high electrical insulation reliability under high temperature and high humidity when forming a protective film for a flexible wiring board. A thermosetting resin composition excellent in flexibility.

The curable composition of the present invention contains (component A) a compound having a specific structural unit and having at least one bond of a quinone bond and a guanamine bond, and having a functional group reactive with a hardener, (ingredient) B) Hardener and (Component C) organic solvent. (Component A) is a polycarboxylic acid derivative containing (a raw material a) having a trivalent or/or tetravalent group having an acid anhydride group, (raw material b) a polyol represented by the following formula (2), and (a raw material c) It is preferred to use a polyisocyanate as an essential component to react the compound obtained.

Description

Curable composition, cured film using the composition, and coated film

The present invention relates to a thermosetting resin composition, a method of forming a protective film for a flexible wiring board, a flexible wiring board, an electronic component, and a method of manufacturing the flexible wiring board.

In recent years, in order to reduce the size, thickness, and speed of electronic components, resin compositions (for example, sealing agents, solder resists, etc.) used in electronic components are required to have superior heat resistance. Electrical properties and moisture resistance. For this reason, in terms of the resin constituting the resin composition, it has been replaced with a polyimine resin, a polyamide amide resin, and a polyamide resin in place of the epoxy resin. However, these resins have a rigid resin structure and a lack of flexibility in the cured film. Therefore, when it is used for a film substrate, the base material after hardening tends to have large warpage, and also has problems such as poor bendability.

In order to improve warpage and flexibility, the above-mentioned resin has been reviewed and modified to be flexible and low in elastic modulus, and various modified polyamidoximine resins have been proposed (for example, reference) Patent Documents 1, 2 and 3).

Further, Patent Document 4 discloses a thermosetting resin group which is intended to improve low warpage, flexibility, solder heat resistance, and tin plating resistance. Adult. The thermosetting resin composition of Patent Document 4 has excellent performance in maintaining electrical insulation properties of high electrical characteristics under high temperature and high humidity.

However, in recent years, with the miniaturization of the wiring, when the display panel in which the flexible wiring board is connected is mounted on the casing in another place, the wiring is broken during transportation, and the protection function for the wiring is broken. A protective film (hereinafter referred to as "bending resistance") is expected.

Further, Patent Document 5 discloses a thermosetting resin composition comprising a polyamidoximine-modified polyurethane, a curing agent, and an organic solvent, which has low warpage, flexibility, and resistance. Bending performance. Further, here, low warpage, flexibility, and electrical insulating properties under high temperature and high humidity were measured.

However, even such a thermosetting resin composition is not an electric insulating protective film having a higher bending resistance than a commercially suitable bending resistance.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 62-106960

[Patent Document 2] Japanese Patent Laid-Open No. Hei 8-12763

[Patent Document 3] Japanese Patent Laid-Open No. Hei 7-196998

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2006-117922

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2015-147940

However, in the resin composition for forming the protective film of the flexible wiring board, and the conventional resin composition having improved warpage and flexibility, water molecules are easily infiltrated under high temperature and high humidity, and high electrical characteristics are maintained. Its difficulty. In order to impart high electrical characteristics, it is considered to be effective to introduce a rigid component into a resin structure and to have a high glass transition temperature. However, according to this method, the base material after curing tends to be greatly warped, and problems such as poor bendability may occur.

Further, the thermosetting resin composition described in Patent Document 4 is considered to have a certain degree of improvement in terms of low warpage, flexibility, solder heat resistance, and tin plating resistance, but it is difficult Gives protection to the breakage of the wiring.

Further, the thermosetting resin composition described in Patent Document 5 has a certain degree of bending resistance, but it is not sufficient.

Therefore, the present invention provides a protective film for forming a flexible wiring board, which can sufficiently control warpage while maintaining high electrical insulation reliability under high temperature and high humidity, and is excellent in bending resistance. The thermosetting resin composition is the main purpose.

In order to solve the above-mentioned problems, the inventors of the present invention have found that a specific structure is required, and at the same time, a compound having at least one bond having a ruthenium bond and a guanamine bond is required. When the curable composition is printed on a flexible wiring board, the cured curable composition is cured, and the warp of the flexible wiring board is small, and the cured film containing the cured composition of the curable composition is provided. In the case of the flexible wiring board covered by the protective film, the flexible wiring board covered by the protective film has a large effect of suppressing the breakage of the wiring, and thus the present invention has been completed.

That is, the present invention relates to the following matters.

[1] A curable composition comprising (Component A) A compound having a structural unit represented by the following formula (1) and having at least one bond of a ruthenium bond and a guanamine bond, and having a functional group reactive with a hardener, (Component B) Hardener, and (Component C) organic solvent.

(In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbons, and R ² each independently represents a phenyl group or a pendant phenyl group having a substituent.

[2] The curable composition according to [1], wherein the aforementioned The functional group reactive with the curing agent is at least one selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a guanamine group, and an amine group.

[3] The curable composition according to [1] or [2], wherein (Component A) contains: (raw material a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (Starting Material b) The following compound obtained by reacting the polyol represented by the formula (2) and (the starting material c) with a polyisocyanate as an essential component.

(In the formula (2), (n+1) of R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n of R ² each independently represent a phenylene group or have The substituent is a phenyl group, and n represents an integer from 1 to 60).

Further, (Component A) in the curable composition specified in [3] is a polycarboxylic acid derivative having a trivalent or/or tetravalent acid anhydride group (raw material a), and (raw material b) 2) The polyol (the raw material c) polyisocyanate shown as a raw material, and a plurality of compounds corresponding to (raw material a), (raw material b), and (raw material c) are mutually reactive. Further, if the blending ratio or reaction conditions of various monomers are changed, the obtained polymer also changes. Therefore, the structure of the obtained component A is extremely ambiguous, and it is difficult to specify it with a specific structure, which is well known. Technical knowledge of the industry's industry. Moreover, if the structure cannot be specified, the characteristics cannot be specified. That is to say, the polymeric composition specified in [3] cannot be specified by its structure or characteristics, but can be specified by the process (manufacturing method), and the application should be directly specified by its structure or characteristics. It may be possible, or it may be considered that there is a non-practical situation.

[3] The curable composition according to [1] or [2], wherein (Component A) contains at least a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) (Starting Material b) A reaction product obtained by the following polyhydric alcohol represented by the formula (2) and (raw material c) polyisocyanate.

(In the formula (2), (n+1) of R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n of R ² each independently represent a phenylene group or have The substituent is a phenyl group, and n represents an integer from 1 to 60).

[4] The curable composition according to any one of [1] to [3] wherein (Component A) further has a urethane bond.

[5] The curable composition according to any one of [1] to [4] wherein (component A) is an acid value of 10 to 50 mgKOH/g.

[6] The curable composition according to any one of [1], wherein (Component B) contains a compound having two or more epoxy groups per molecule.

[7] The curable composition according to any one of [1], wherein (Component C) is formed from an ether solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solvent. At least one organic solvent selected from the group.

[8] The curable composition according to any one of [1] to [7] further comprising (component D) at least one type of fine particles selected from the group consisting of inorganic fine particles and organic fine particles.

[9] The curable composition according to any one of [1] to [8], wherein the total amount of the component (A) and the component (B) is 100 parts by mass, and 1 to 55 parts by mass is contained. Ingredient (B).

[10] The curable composition according to any one of [1] to [9], wherein the total amount of the component (A), the component (B), the component (C), and the component (D) is included (excluding In the case of the component (D), when the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass, the component (C) is contained in an amount of 25 to 75 parts by mass.

[11] A cured product of the curable composition according to any one of [1] to [10].

[12] A coating film for a flexible wiring board, characterized in that a part or all of a surface on which a wiring is formed of a flexible wiring board formed by wiring on a flexible substrate, such as [ The curable composition according to any one of [1] to [10], which is cured and obtained.

[13] A flexible wiring board characterized by being a part or all of a surface of a flexible wiring board on which a wiring is formed on a flexible substrate, as described in [12]. The coating is covered.

[14] The flexible wiring board according to [13], wherein the wiring is tin-plated copper wiring.

[15] A method of producing a flexible wiring board covered with a coating film, comprising the following (step 1) and (step 3) and the necessity (step 2):

(step 1)

The step of forming a printed film on the pattern by printing the curable composition according to any one of [1] to [10] on at least a part of the wiring pattern portion of the flexible wiring board.

(Step 2)

The step of evaporating a part or a whole amount of the solvent in the printed film by subjecting the printed film obtained in the step 1 to an atmosphere of 40 to 100 ° C.

(Step 3)

The step of hardening and forming a coating film by heating the printing film obtained in the step 1 or the printing film obtained in the step 2 at 100 to 170 °C.

[16] An electronic component characterized by having the cured film described in [11].

In addition, the expression "(n+1) R ^{1 's} each independently" described in the present specification means that (n+1) R ^{1 's} have the same structure, and some have the same structure. The other parts are different structures, all of them are different structures, etc. It doesn't matter. Further, described in the present specification, "n number of R ² each independently represent a" performance, etc., similarly means that the n is a whole even if R ² in the same configuration, the same configuration part and the other part into different Construction, all of them are different structures, etc. It doesn't matter.

By curing the curable composition of the present invention, a protective film having low warpage, flexibility, and long-term insulation reliability can be obtained, and a flexible wiring board covered by the cured film can be provided. A protective film with a large suppression effect of wiring breakage.

Moreover, the present invention can provide a protective film made of a cured product of the curable composition, and a flexible wiring board covered by the protective film, which can sufficiently suppress high reliability of insulation. A flexible wiring board that is warped and also has excellent bendability.

[Formation of the Invention]

Hereinafter, the embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The curable composition of the present invention is characterized in that it contains a component having a structural unit represented by the following formula (1) and having at least one bond of a quinone bond and a guanamine bond. A compound having a functional group reactive with a hardener, (Component B) a hardener, and (Component C) an organic solvent.

(In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbons, and R ² each independently represents a phenyl group or a pendant phenyl group having a substituent.

(Component A) which is an essential component of the curable composition of the present invention has a structural unit represented by the formula (1) and has a quinone bond and a guanamine bond (-C(=O)-NH -) at least one bonded compound.

(Component A) may further have a urethane bond (-O-C(=O)-NH-). Further, (Component A) has a functional group reactive with a hardener. Preferred functional groups which can react with the curing agent include at least one functional group of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a guanamine group, and an amine group. When the isocyanate group is present, the isocyanate group is preferably protected by a blocking agent. Further, in other groups, the blocking agent can be protected, and the blocking body is detached and the reactant is regarded as a functional group. The wave line is tied to the end of the bond, indicating the bond with the other Bonding part.

In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms. In other words, the above-mentioned organic residue derived from a diol is a divalent group obtained by removing two hydroxyl groups from a diol.

Examples of the carbon diol having 3 to 36 are 1,3-propane diol, 1,2-propane diol, 1,4-butane diol, and 2-methyl-1,3-propane. Glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-decane Glycol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dimer ( C36) chain diol such as diol, diethylene glycol or triethylene glycol, 1,2-cyclopentane dimethanol, 1,3-cyclopentane dimethanol and bis(hydroxymethyl)tricyclic ring [5.2.1.0] 5-membered cyclic diol such as decane, and 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- 6-membered cyclic diol such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 2,2-bis(4-hydroxycyclohexyl)-propane A diol having an alicyclic structure or the like.

Preferred examples of R ¹ are a hydrocarbon group having a carbon number of 3 to 18 and a chain structure, and more preferably a hydrocarbon group having a carbon number of 4 to 9 and a chain structure, and particularly preferred examples, a carbon number of 4 a hydrocarbon group of ~6 and a chain structure. That is, preferred diol aspects of the organic residue capable of deriving R ¹ include, for example, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl -1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-decanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, more preferred diols, for example Such as 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, particularly preferred The alcohol may, for example, be 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol or 3-methyl. -1,5-pentanediol, the most preferred diol, is 1,6-hexanediol, 3-methyl-1,5-pentanediol.

Further, in the formula (1), R ² each independently represents a phenyl group or a pendant phenyl group having a substituent. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. Examples of the substituent of the phenyl group having a substituent include an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include 3-methyl-1,2-phenylene and 4-methyl-1. , 2-phenylene, 4-methyl-1,3-phenylene, 2-methyl-1,4-phenylene, 3-ethyl-1,2-phenylene, 4-ethyl a 1,1-phenylene group, a 4-ethyl-1,3-phenylene group, a 2-ethyl-1,4-phenylene group, or the like, as a substituent, a pendant phenyl group having an alkyl group. Further, in view of the phenyl group having a substituent, 3-bromo-1,2-phenylene, 4-bromo-1,2-phenylene, 4-bromo-1,3-phenylene, 2 -Bromo-1,4-phenylene, 3-chloro-1,2-phenylene, 4-chloro-1,2-phenylene, 4-chloro-1,3-phenylene, 2-chloro a phenyl group having a halogen such as a 1,4-phenylene group.

Among these, preferred are 1,2-phenylene, 1,3-phenylene, 1,4-phenylene and a substituted alkyl group having an alkyl group as a substituent, more preferably 1, 2-phenylene, 1,3-phenylene, 1,4-phenylene, particularly preferably 1,2-phenyl, 1,3-phenyl.

Further, an optimum combination of R ¹ and R ² , when R ² is a 1,2-phenylene group, R ¹ is 1,6-hexanediol or 3-methyl-1,5-pentane An organic residue derived from a diol, wherein R ² is a 1,3-phenylene group, and R ¹ is an organic residue derived from a diol of 3-methyl-1,5-pentane.

Next, the method of synthesizing (component A) will be described.

(Component A) can be synthesized, for example, by the following method.

(Method 1) (Polymer b) The polyol represented by the following formula (2)

(In the formula (2), (n+1) of R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n of R ² each independently represent a phenylene group or have The substituent phenyl group, n independently represents an integer from 1 to 60).

Reacting with (raw material c) polyisocyanate to obtain a compound having a urethane bond and having an isocyanate group at the terminal, and a polyisocyanate containing the obtained compound having a urethane bond and having an isocyanate group at the terminal. It is reacted with a polyvalent carboxylic acid derivative having a trivalent and/or tetravalent group having an acid anhydride group (bottom) as (raw material a).

(Method 2) The (raw material c) polyisocyanate is reacted with a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) to obtain at least one bond having a quinone bond and a guanamine bond. The polyisocyanate is combined, and (the raw material b) is reacted therein with the polyol represented by the formula (2).

(Method 3) The (raw material c) polyisocyanate is reacted with a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) to obtain at least one bond having a quinone bond and a guanamine bond. A compound having an acid anhydride group and/or a carboxyl group at the end, and wherein (the raw material b) is reacted with the polyol represented by the formula (2).

(Method 1) The first method is to react (the raw material b) with the polyol represented by the formula (2) and the (raw material c) polyisocyanate to synthesize a urethane bond and have an isocyanate group at the terminal. The compound (hereinafter referred to as "(A ^1-1 ) compound").

^1, and are each the same as R ² (1) of the formula R ^1, R ² of formula R (2) in the.

n in the formula (2) represents an integer of 1 to 60. The preferred n aspect is an integer from 1 to 45, particularly preferably an integer from 1 to 30. The average value of n is preferably 3 to 11, more preferably 5 to 10.

The number average molecular weight of the diol of formula (2) is from 500 to 5,000 For better, 750~4000 are better, and 1000~3000 are especially good.

The polyisocyanate which can react with the polyol of the raw material b (that is, (the raw material c)) is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyisocyanate include 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1 , 3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, norbornene diisocyanate, disulfide of isophorone diisocyanate, etc. Cyclic aliphatic polyisocyanate; diphenylmethane-2,4'-diisocyanate, 3,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,3'-dimethyl Diphenylmethane-2,4'-diisocyanate, 4,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,3'-dimethyldiphenylmethane-2,4 '-Diisocyanate, 5,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 5,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 6,2 '-Dimethyldiphenylmethane-2,4'-diisocyanate, 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'-diethyldiphenyl Methane-2,4'-diisocyanate, 3,3'-diethyldiphenylmethane-2,4'-diisocyanate, 4,2'-diethyldiphenylmethane-2,4'-di Isocyanate, 4,3'-diethyl Phenylmethane-2,4'-diisocyanate, 5,2'-diethyldiphenylmethane-2,4'-diisocyanate, 5,3'-diethyldiphenylmethane-2,4' -diisocyanate, 6,2'-diethyldiphenylmethane-2,4'-diisocyanate, 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2' -dimethoxydiphenylmethane-2,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, 4,2'-dimethoxy Phenylmethane-2,4'-diisocyanate, 4,3'-dimethyl Oxydiphenylmethane-2,4'-diisocyanate, 5,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 5,3'-dimethoxydiphenylmethane -2,4'-diisocyanate, 6,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 6,3'-dimethoxydiphenylmethane-2,4'- Diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4 '-Diisocyanate, benzophenone-4,4'-diisocyanate, diphenylphosphonium-4,4'-diisocyanate, 2,4-trichloroethylene diisocyanate, 2,6-trichloroethylene diisocyanate , m-dimethyl phenyl diisocyanate, p-dimethyl phenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-[2,2 bis(4-phenoxyphenyl)propane] Polyisocyanate having an aromatic ring such as diisocyanate; diurea of hexamethylene diisocyanate, triisocyanuric acid triisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethyl hexa Chain aliphatic polyisocyanate such as methylene diisocyanate and 2,2,4-trimethylhexane methylene diisocyanate a heteropolyisocyanate having a heterocyclic isocyanate of isophorone diisocyanate or a heterocyanurate of hexamethylene diisocyanate, etc., which may be used alone or in combination 2 More than one kind.

Considering the reaction of a synthesized tricarboxylic acid derivative having a urethane bond and having an isocyanate group at the terminal and then reacting (the starting material a) having an acid anhydride group with a trivalent and/or tetravalent polycarboxylic acid derivative Of these, preferably a polyisocyanate having an aromatic ring, more preferably diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenyl Methane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, etc. The polyisocyanate of the aromatic ring is preferably diphenylmethane-4,4'-diisocyanate.

Further, in order to avoid a change in the polyisocyanate, the isocyanate group can be stabilized by a blocking agent. Examples of the terminal blocking agent include alcohols, phenols, and hydrazines represented by hydroxy acrylate, methanol, and 2-butanone oxime, and are not particularly limited.

The reaction of the polyol of the raw material b and the polyisocyanate of the raw material c is carried out in the presence of an organic solvent, preferably in the presence of a non-nitrogen-containing polar solvent, by heating and reacting the mixture.

The non-nitrogen-containing polar solvent may, for example, be an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether. a sulfur-containing solvent such as dimethyl hydrazine, diethyl hydrazine, dimethyl hydrazine or cyclobutyl hydrazine; an ester solvent such as γ-butyrolactone and celecoxib; cyclohexanone and methyl A ketone solvent such as ethyl ketone; and an aromatic hydrocarbon solvent such as toluene or xylene. These may be used alone or in combination of two or more.

Among the above solvents, it is preferred to use a solvent which is selected to be soluble in the resin to be produced.

Further, it is preferred to use a solvent which is directly used as a thermosetting resin composition after synthesis. Among the above solvents, cyclohexanone, γ-butyrolactone, and diethylene glycol diethyl ether are particularly preferable because they are considered to be volatile and can be efficiently and uniformly reacted.

The amount of the solvent to be used is preferably from 80 to 500 parts by mass based on 100 parts by mass of the total amount of the raw materials of the synthetic (A ¹ -1) compound. When the amount is 100 parts by mass based on 100 parts by mass of the total amount of the raw material of the compound (A ^1-1 ), the viscosity at the time of synthesis is not too high, and it is difficult to be stirred. It is better to synthesize the situation and the reaction rate is not extremely lowered.

The reaction temperature is preferably 60 to 210 ° C, 70 to 190 ° C is better, and 80 to 180 ° C is particularly good. If the temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, the colloid tends to be easily formed during the reaction. The reaction time can be appropriately selected depending on the capacity of the reaction vessel and the reaction conditions employed.

If necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium or cobalt or a semi-metal compound.

The blending ratio of the polyol of the raw material b to the polyisocyanate of the raw material c is appropriately adjusted depending on the number average molecular weight of the (A ¹ -1) compound to be formed. However, the terminal of the (A ¹ -1) compound produced is an isocyanate group, and it is necessary that the number of hydroxyl groups of the (raw material b) < (raw material c) is the number of isocyanato groups.

When the (A ^1-1 ) compound having an isocyanate group is synthesized, the ratio of the number of isocyanate groups to the number of hydroxyl groups (the number of isocyanate groups / the number of hydroxyl groups) is preferably adjusted to 1.01 or more, and it is preferably adjusted to 2.0 or less. good.

The number average molecular weight of the (A ^1-1 ) compound having an isocyanate group at the end is preferably from 500 to 30,000, more preferably from 1,000 to 25,000, and particularly preferably from 1,500 to 20,000.

The (A ¹ -1) compound having an isocyanate group at the terminal is reacted with a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) to form a urethane bond. A compound with a guanamine bond and/or a quinone bond. Further, when the raw material a is a trivalent polycarboxylic acid derivative having an acid anhydride group, it may have one group of acid anhydrides and one carboxyl group. Further, when the raw material a is a tetravalent polycarboxylic acid derivative having an acid anhydride group, it may have two groups of acid anhydrides or one group of acid anhydride groups and two carboxyl groups. The above carboxyl group may also form an ester bond with an alcohol to form a derivative. The polycarboxylic acid derivative herein means a polycarboxylic acid having an acid anhydride group, or a derivative thereof such as a carboxylic acid ester.

The trivalent polycarboxylic acid derivative having an acid anhydride group is not particularly limited, and examples thereof include the compounds represented by the following general formula (3) or (4).

(In the formula (3), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group).

(In the formula (4), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y ¹ represents -CH ₂ -, -CO-, -SO ₂ -, or -O-).

The above R ³ and R ⁴ are preferably a hydrogen atom, and in the case of Y1, -CO- or -O- is preferred.

Among them, in view of the trivalent polycarboxylic acid derivative having an acid anhydride group, anhydrous trimellitic acid is particularly preferable from the viewpoint of cost and the like.

The tetracarboxylic polycarboxylic acid derivative having an acid anhydride group is not particularly limited, and examples thereof include a tetracarboxylic dianhydride represented by the following general formula (5). These may be used alone or in combination of two or more.

(In the formula (5), Y ² represents a tetravalent organic group).

The tetracarboxylic dianhydride represented by the formula (5) is not particularly limited, and examples thereof include pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride. 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'- Diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2-bis (3, 4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, Bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5 , 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylate Acid dianhydride, bis(3,4-dicarboxyphenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)diphenyl phthalane dianhydride, 1,4-double (3,4 -Dicarboxyphenyldimethylmethylalkyl phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p -Phenylbis(trimellitic acid monoester anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decalin-1,4,5,8-tetra Carboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2 , 3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, double (external cut- Bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride) fluorene, bicyclo-(2,2,2)-octyl(7)-ene-2,3,5,6-tetracarboxylic acid Anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4- (3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4-double (2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic acid), 5-(2, 5-tertiary oxytetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,3,3a ,4,5,9b-hexahydro-5(tetrahydro-2,5-di-oxy-3-yl)naphtho[1,2-c]furan-1,3-dione, ethylene glycol Bis(trimellitic anhydride) (also known as "ethylene glycol double dehydrogenated trimellitate" or "TMEG").

Preferred is tetracarboxylic dianhydride ethylene glycol bis(trimellitic anhydride) (TMEG), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), pyromellitic acid II Anhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA).

These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In the method 1, the (A ¹ -1) compound and the polyisocyanate (hereinafter referred to as (A ¹ -2) compound) other than the (A ¹ -1) compound may be simultaneously reacted with the above (raw material a) to obtain A compound having a urethane bond, a guanamine bond and/or a quinone bond. The (A ¹ -2) compound is not particularly limited as long as it is a polyisocyanate other than the (A ¹ -1) compound, and examples thereof include the above (raw material c). These may be used alone or in combination of two or more. The ^ratio of the total number of the acid anhydride group and the carboxyl group of the starting material a to the total number of the isocyanato groups in the A ¹ -1 and the total number of the isocyanato groups in the A ¹ -2 is not particularly limited. It is preferably in the range of 0.9:1.0 to 1.1:1.0, more preferably in the range of 0.95:1.0 to 1.05:1.0.

In the present embodiment, an amine compound may be used in combination with the above polyisocyanate. The amine compound is a compound which converts the isocyanate group in the above polyisocyanate into an amine group. Conversion of an isocyanate group to an amine group can be carried out by a known method.

The amount of the (A ¹ -2) compound is preferably from 50 to 100% by mass based on the aromatic polyisocyanate. When the aromatic polyisocyanate is considered to have a balance of solubility, mechanical properties, cost, and the like, it is particularly preferable to use diphenylmethane-4,4'-diisocyanate.

(Method 2) The synthesis method firstly reacts (raw material c) polyisocyanate with a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) to synthesize a quinone bond and a guanamine At least one bonded polyisocyanate of a bond (hereinafter referred to as "(A ² -1) compound").

The blending ratio of the polyisocyanate of (the raw material c) and the trivalent and/or tetravalent polycarboxylic acid derivative having the acid anhydride group (the raw material a) can be reacted to the desired (A ² -1) compound. The number average molecular weight is appropriately adjusted. However, since the terminal of the (A ² -1) compound to be produced is an isocyanate group, the number of acid anhydride groups (the raw material a) and the total number of carboxyl groups plus the total number of isocyanate groups (the raw material c) are necessary. . Here, the number of carboxyl groups, and a compound represented by the formula -COOR ³ (4) as the compound of formula (3) in the formula of the -COOR ^4, R ³ and also R ⁴ comprises a carboxyl group of a hydrogen atom The number.

Further, (raw material a) and (raw material c) used in the synthesis method of (method 2) can be used in the same manner as (material a) and (raw material c) used in the synthesis method of (method 1).

When the (A ² -1) compound having an isocyanate group is synthesized at the end, the ratio of the number of isocyanate groups to the number of acid anhydride groups and the total number of carboxyl groups (the number of isocyanato groups / the number of acid anhydride groups and the number of carboxyl groups) The total number of additions is preferably adjusted to 1.01 or more, and it is better to adjust to 2.0 or less.

The number average molecular weight of the (A ² -1) compound having an isocyanate group at the end is preferably from 500 to 15,000, more preferably from 800 to 10,000, and particularly preferably from 1,000 to 5,000.

Next, a compound of the formula (A ² -1) having an isocyanate group at the end is reacted with a polyol represented by the formula (2) to form a urethane bond, and a guanamine bond and/or Or a compound of a quinone imine bond.

Further, when the (A ² -1) compound having an isocyanate group at the terminal is reacted with the polyol (formula b) represented by the formula (2), it may be, for example, 2,2-dimethylolpropionic acid or A polyol having a carboxyl group of 2,2-dimethylolbutanoic acid is used together.

The total number of isocyanato groups in A ² -1, the number of hydroxyl groups in the starting material b, and the polyvalent group having a carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid The ratio of the number of hydroxyl groups in the alcohol to the total number of hydroxyl groups in the alcohol is not particularly limited. When the guanamine group is present in A ² -1, it is preferably in the range of 0.9:1.0 to 1.1:1.0, more preferably 0.95. : 1.0~1.05: 1.0 range. Further, when A ² -1 does not have a guanamine group and does not use a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid, it is 0.9. A range of 1.0 to 0.95:1.0 or a range of 1.0:0.95 to 1.0:0.9 is preferred.

Further, (raw material b) used in the synthesis method of (method 2) can be the same as (material b) described in the above (method 1). Furthermore, also Further, a polyol may be further added, and a urethane bond may be formed by reacting a terminal isocyanate group with an additional polyol.

(Method 3) The synthesis method firstly reacts (raw material c) polyisocyanate with a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group (raw material a) to synthesize a quinone bond and a guanamine A compound having at least one type of bond and having an acid anhydride group and/or a carboxyl group at the terminal (hereinafter referred to as "(A ³ -1) compound").

The blending ratio of the polyisocyanate of (the raw material c) and the trivalent and/or tetravalent polycarboxylic acid derivative having the acid anhydride group (the raw material a) can be reacted to the desired (A ³ -1) compound. The number average molecular weight is appropriately adjusted. However, since the terminal of the (A ³ -1) compound to be produced is an acid anhydride group and/or a carboxyl group, the total number of acid anhydride groups (the raw material a) and the number of carboxyl groups plus the total number> (raw material c) isocyanic acid The base is necessary. Here, the compound represented by the formula -COOR ^3, and (4) the number of compounds of formula as also shown in (3) of the carboxyl group in the -COOR ^4, comprising R ³ and R ⁴ is a hydrogen atom of a carboxyl group .

Further, (raw material a) and (raw material c) used in the synthesis method of (method 3) can be used in the same manner as (material a) and (raw material c) used in the synthesis method of (method 1).

When the (A ³ -1) compound having an acid anhydride group and/or a carboxyl group at the end is synthesized, the ratio of the number of acid anhydride groups to the total number of carboxyl groups and the number of isocyanate groups (the number of acid anhydride groups and the number of carboxyl groups are added together) The total number/isocyanate number is preferably adjusted to 1.01 or more, and it is preferably adjusted to 2.0 or less.

The number average molecular weight of the (A ³ -1) compound having an acid anhydride group and/or a carboxyl group at the terminal is preferably from 500 to 15,000, more preferably from 800 to 10,000, and particularly preferably from 1,000 to 5,000.

Next, a (A ³ -1) compound having an acid anhydride group and/or a carboxyl group at the terminal is reacted with a polyol represented by the formula (2) with (a raw material b) to synthesize a bond having a guanamine bond and/or a ruthenium bond. Compound. The ratio of the total number of the acid anhydride groups in A ³ -1 to the number of hydroxyl groups in the raw material b is not particularly limited, and is preferably in the range of 0.9:1.0 to 1.1:1.0, more preferably 0.95:1.0 to 1.05:1.0. range.

Further, (raw material b) used in the synthesis method of (method 3) can be the same as (material b) described in the above (method 1).

From the viewpoint of improvement of chemical resistance and electrical properties, control of functional groups such as acid value, etc., a method of obtaining a compound having an isocyanate group at the end by the initial reaction (that is, (method 1) and (method 1) Method 2)) is preferred.

The reaction of these (Method 1) to (Method 3) can be carried out by heating in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent.

The non-nitrogen-containing polar solvent may, for example, be an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether. a sulfur-containing solvent such as dimethyl hydrazine, diethyl hydrazine, dimethyl hydrazine or cyclobutyl hydrazine; an ester solvent such as γ-butyrolactone and celecoxib; cyclohexanone and methyl A ketone solvent such as ethyl ketone; and an aromatic hydrocarbon solvent such as toluene or xylene are selected. These may be used alone or in combination of two or more.

Among the above solvents, it is preferred to use a solvent which is selected to be soluble in the resin to be produced. Also, it is suitable for use as soon as it is suitable for synthesis. The solvent of the thermosetting composition is preferred. Among the above solvents, in order to carry out the reaction more efficiently and uniformly, it is preferred to use γ-butyrolactone or a mixed solvent containing γ-butyrolactone.

In order to synthesize (component A), the amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) based on the total amount of (component A). If the amount used is from 0.8 to 5.0, the viscosity during the synthesis is not too high and the reaction rate is not lowered.

The reaction temperature is preferably 60 to 210 ° C, 70 to 190 ° C is better, and 80 to 180 ° C is particularly good. If the temperature is less than 60 ° C, the reaction time tends to be too long, and if it exceeds 210 ° C, the colloid tends to be easily formed during the reaction. The reaction time can be appropriately selected depending on the capacity of the reaction vessel and the reaction conditions employed.

If necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium or cobalt, or a semi-metal compound.

Further, in the present specification, the number average molecular weight means a value measured by colloidal permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.

The number average molecular weight, the mass average molecular weight, and the degree of dispersion are as defined below.

(a) number average molecular weight (Mn)

Mn=Σ(N _i M _i )/ΣN _i =ΣX _i M _i

(X _i = molar fraction of the molecule of molecular weight M _i = N _i /ΣN _i )

(b) mass average molecular weight (Mw)

Mw=Σ(N _i M _i ² )/ΣN _i M _i =ΣW _i M _i

(W _i = mass fraction of molecules with molecular weight M _i = N _i M _i /ΣN _i M _i )

(c) Molecular weight distribution (dispersion)

Dispersion = Mw / Mn

Further, in the present specification, the measurement conditions of GPC are as follows, without particular limitation.

Device name: HPLC unit HSS-2000 manufactured by Japan Seiko Co., Ltd.

Column: Shodex (registered trademark) column LF-804×3 (inline)

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus, manufactured by JASCO Corporation

Temperature: 40.0 ° C

Sample quantity: sample loop 100μL

Sample concentration: adjusted to about 0.1% by mass.

The acid value of (Component A) is preferably from 10 to 50 mgKOH/g. More preferably, it is 10 to 35 mgKOH/g, particularly preferably 15 to 30 mgKOH/g. When the acid value of the component (A) is 10 to 50 mgKOH/g, the warpage is not excessively large and the curing is sufficient. Therefore, it is preferable to suppress the decrease in weather resistance, flexibility, and the like.

Further, the acid value of (Component A) can be determined by the following method. First, the scale contains about 1 g of the solution of (Component A). Then, on the other hand, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added, and it melt|dissolved uniformly. A suitable amount of phenolphthalein as an indicator was added to the obtained solution, and titration was carried out using a 0.1 N KOH solution (alcoholic property). Then, from the titration result, the following formula (α): A=10×Vf×56.1/(Wp×I)‧‧‧‧‧(α)

To calculate the acid price. In the formula (α), A represents an acid value (mgKOH/g), Vf represents a titer (mL) of a 0.1 N KOH solution, Wp represents a mass (g) of a solution containing (Component A), and I represents a component (component) A) The proportion of non-volatile matter of the solution (% by mass).

The number average molecular weight of the component A thus obtained is preferably from 5,000 to 50,000, more preferably from 6,000 to 40,000, and particularly preferably from 7,000 to 25,000. When the number average molecular weight is from 5,000 to 50,000, the deterioration of weather resistance or chemical resistance can be suppressed, and the solubility to a non-nitrogen-containing polar solvent can be maintained, which is preferable.

Next, (component B) which is an essential component of the curable composition of the present invention will be described.

The curable composition of the present embodiment further contains a curing agent which can cure the above (Component A). The hardener is a compound having two or more functional groups reactive with the functional group of the component (A) in one molecule. When the component (A) has a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a phosphonium group or an amine group, the hardener of the component (B) has a plurality of reacting groups capable of reacting with the functional groups. An epoxy group, an isocyanate group, a hydroxyl group or a carboxyl group is preferred.

When the epoxy group-containing compound used as the curing agent contains at least one compound having an epoxy group in one molecule and at least one of them is a compound having two or more epoxy groups in one molecule, There are no special restrictions.

Specific examples of the epoxy group-containing compound used as the curing agent include a phenol novolac type epoxy resin and o-cresol. A novolac type epoxy resin, such as phenol, cresol, xylenol, resorcinol, benzenediol, phenol and/or α-naphthol, β-naphthol, dihydroxynaphthalene, etc. An epoxidized novolak type epoxy resin or bisphenol which is obtained by condensation or co-condensation of a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde or salicylaldehyde under an acidic catalyst A, bisphenol F, bisphenol S, alkyl substituted or unsubstituted diphenol, distyryl phenol, etc. (bisphenol A epoxy compound, bisphenol F epoxy compound) Epoxy propyl ether of alcohols such as bisphenol S type epoxy compound, biphenyl type epoxy compound, stilbene type epoxy compound), butanediol, polyethylene glycol, polypropylene glycol and the like a epoxidized propyl ester type epoxy resin such as phthalic acid, isophthalic acid or tetrahydrophthalic acid, aniline, bis(4-aminophenyl)methane or isomeric cyanuric acid. Epoxy propyl or methyl epoxy epoxide, p-amino phenol, which is bonded to an active hydrogen atom of a nitrogen atom, substituted with a propylene group An epoxy epoxide or methyl epoxy epoxide type epoxy resin in which an active hydrogen bonded to a nitrogen atom and an active hydrogen of a phenolic hydroxyl group are substituted with a propylene group, etc. a vinylcyclohexene diepoxide obtained by epoxidation of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3) , 4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc., alicyclic epoxy resin, para-dimethylbenzene Glycidyl ether of base and/or meta-methyl phenyl modified phenol resin, glycidyl ether of terpene modified phenol resin, epoxy propyl ether of dicyclopentadiene modified phenol resin , epoxy propyl ether of cyclopentadiene modified phenol resin, glycidyl ether of polycyclic aromatic ring modified phenol resin, epoxy propyl ether of phenol resin containing naphthalene ring, halogenated benzene a phenol novolak type epoxy resin, a hydroquinone type epoxy resin, a trimethylolpropane type epoxy resin, a linear aliphatic epoxy resin obtained by oxidizing an olefin bond by peracid such as peracetic acid, or a diphenyl group An epoxide of an aralkyl type phenol resin such as a methane type epoxy resin, a phenol aralkyl resin, a naphthol aralkyl resin, an epoxy resin containing a sulfur atom, a tricyclic ring [5, 2, 1, 02, 6] Di-epoxypropyl ether of decane dimethanol, 1,3-bis(1-adamantyl)-4,6-bis(glycidyl ether)benzene, 1-[2',4'-double (glycidyl ether) phenyl]adamantane, 1,3-bis(4'-glycidyl ether phenyl)adamantane and 1,3-bis[2',4'-bis(glycidyl ether) An epoxy resin having an adamantane structure such as phenyl]adamantane. These may be used alone or in combination of two or more.

The compound having two or more epoxy groups in the above-mentioned one molecule is preferably a compound having two or more epoxy groups in one molecule and having an aromatic ring structure and/or an alicyclic structure.

When the long-term electrical insulating property of the cured film of the present invention to be described later is emphasized, among the compounds having two or more epoxy groups and having an aromatic ring structure and/or an alicyclic structure, dicyclopentadiene is modified. a epoxidized propyl ether of a phenol resin (that is, a compound having a tricyclo[5,2,1,0 ^2,6 ]decane structure and an aromatic ring structure and having two or more epoxy groups), 1,3 - bis(1-adamantyl)-4,6-bis(glycidyl ether)benzene, 1-[2',4'-bis(glycidyl ether)phenyl]adamantane, 1,3-double Epoxy resin having an adamantane structure such as (4'-glycidyl ether phenyl) adamantane and 1,3-bis[2',4'-bis(glycidyl ether)phenyl]adamantane That is, a tricyclodecane structure and an aromatic ring structure having a tricyclo[3,3,1,1 ^3,7 ]decane structure and an aromatic ring structure and having two or more epoxy groups) The compound of two or more epoxy groups is preferable because it can provide a cured product having a low water absorption rate, and is particularly preferably a compound described in the following formula (6).

(m in the formula (6) represents a positive integer).

In addition, when the reactivity with (Component A) of the present invention is emphasized, among the compounds having two or more epoxy groups in one molecule and having an aromatic ring structure and/or an alicyclic structure, aniline is used. Epoxy propyl or methyl epoxy epoxide or p-amine in which bis(4-aminophenyl)methane is bonded to an active hydrogen atom of a nitrogen atom and substituted with an epoxy propyl group. An epoxy group such as an epoxy group or a methyl epoxypropyl group in which an active phenol bonded to a nitrogen atom and an active hydrogen bonded to a phenolic hydroxyl group are substituted with a propylene group such as an aminophenol such as a phenol. A compound having an amine group or an aromatic ring structure and having two or more epoxy groups is preferable, and a compound described in the following formula (7) is particularly preferable.

Further, as the polyisocyanate compound, a compound having a plurality of isocyanate groups used as a curing agent, for example, a diisocyanate compound, a triisocyanate, or another tetrafunctional or higher isocyanate may be mentioned. In view of the diurnal variation in the case where (Component A) is mixed with a curing agent, it is preferred to use a polyisocyanate compound in which an isocyanate group is stabilized by a blocking agent. These may be used alone or in combination of two or more.

Examples of the blocking agent include alcohol, phenol, hydrazine, and the like, and are not particularly limited. For the blocked isocyanate, for example, the product names "DURANATE17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T" manufactured by Asahi Kasei Chemicals Co., Ltd., and the product name "KARENZ MOI-BM" manufactured by Showa Denko Co., Ltd. , MOI-BP", and the trade name "BL-3175, BL-4165, Desmo Cup 11, Desmo Cup -12" manufactured by the BAYER urethane company. The blocked isocyanate is preferably selected in accordance with the heat hardening temperature of the component (component A), and is particularly preferably BL-3175 when cured at a low temperature.

The compound containing a hydroxyl group in one molecule is not particularly limited as long as it contains at least one compound having a hydroxyl group in one molecule and at least one of them has two or more hydroxyl groups in one molecule. system.

Examples of the hydroxyl group-containing compound used as the curing agent include a polyhydric alcohol, and the like, and specific examples thereof include ethylene glycol, glycerin, butanediol, and pentaerythritol.

The compound containing a carboxyl group in one molecule is not particularly limited as long as it contains at least one compound having a carboxyl group in one molecule and at least one of them has two or more carboxyl groups in one molecule.

Examples of the carboxyl group-containing compound used as the curing agent include polyvalent carboxylic acids and the like, and specific examples thereof include phthalic acid, succinic acid, trimellitic acid, adipic acid, and pyromellitic acid.

As the hardener, the epoxy group-containing compound, the polyisocyanate compound, the hydroxyl group-containing compound, and the carboxyl group-containing compound may be used singly or in combination, and may be selected in combination with the reactive group of (Component A). For example, when (Component A) has a hydroxyl group, it is preferred to use a blocked isocyanate, and when (Component A) has a carboxyl group or an amine group, it is preferred to use a compound containing an epoxy group. The curing agent is not limited to the epoxy group-containing compound, the polyisocyanate compound, the hydroxyl group-containing compound, and the carboxyl group-containing compound if it is reactive with the reactive group of (Component A).

The amount of (Component B) in the curable composition of the present invention is 1 to 55% by mass, preferably 2 to 45, based on the total amount of (Component A) and (Component B) in the curable composition. The mass% is more preferably 2.5 to 30% by mass. The amount of (Component B) in the curable composition of the present invention is from 1 to 55% by mass based on the total mass of (Component A) and (Component B) in the curable composition. From the viewpoint of solvent resistance of the cured film of the present invention to be described later, it is preferable to obtain low warpage of a flexible wiring board which is characterized by being coated with a cured film, and preferable electrical insulation reliability. Balance with the suppression effect of wiring breakage.

Moreover, the amount of (Component A) in the curable composition of the present invention is 45 to 99% by mass, preferably 55 to the total amount of (Component A) and (Component B) in the curable composition. 98% by mass, more preferably 70 to 97.5% by mass. The amount of (Component A) in the curable composition of the present invention is 45 to 99% by mass based on the total amount of (Component A) and (Component B) in the curable composition, and the present invention will be described later. It is preferable from the viewpoint of the solvent resistance of the cured film, and the balance between the low warpage of the flexible wiring board which is coated with the cured film and the effect of suppressing the breakage of the wiring can be obtained.

Next, the component (component C) which is an essential component of the curable composition of the present invention will be described.

The solvent to be dissolved (component A) and (component B) is not particularly limited as the organic solvent to be used (component C), and examples thereof include diethylene glycol dimethyl ether and diethylene glycol diethyl ether. Ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, An ether solvent such as triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether or tripropylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monomethyl ether acetate, methoxy An ester solvent such as methyl propyl propionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate or γ-butyrolactone; or a hydrocarbon solvent such as decalin; A ketone solvent such as cyclohexanone or an aromatic hydrocarbon solvent such as toluene or xylene may be used alone or in combination of two or more.

Among these, considering the balance between the screen printing property and the volatility of the organic solvent, γ-butyrolactone, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, and the like are used. Ethylene glycol monomethyl ether acetate is preferred, more preferably γ-butyrolactone, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, and most preferably γ-butane a separate solvent for the ester, two mixed solvents of γ-butyrolactone and diethylene glycol monoethyl ether acetate, two mixed solvents of γ-butyrolactone and diethylene glycol diethyl ether, and γ - a mixed solvent of butyrolactone, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether.

These preferred solvent combinations are preferred because they are excellent as solvents for screen printing inks.

Moreover, as a part of such a preferable organic solvent, the solvent for synthesis in the production of the above (Component A) can be directly used as a part of the organic solvent of the curable composition of the present invention, and on the process. Preferably.

The content of the component (component C) in the curable composition of the present invention is (component A), (component B), (component C), and (component D) described later as components of the curable composition of the present invention. The total amount (only when the curable composition of the present invention does not contain (component D), the total amount of the component (component A), (component B), and (component C) is preferably 25 to 7 mass%. More preferably, it is 35 to 65 mass%. The content of (Component C) is the total amount of (Component A), (Component B), (Component C) and the filler described later with respect to the component of the curable composition of the present invention. (When the curable composition of the present invention does not contain a filler, the total amount of the component (component A), (component B), and (component C)) is in the range of 25 to 75% by mass, and is hardenability. The viscosity of the composition is good in printing under the screen printing method, and the diffusion due to the penetration of the curable composition after screen printing does not become so large, and the result is from the desired hardenability. The portion of the composition (that is, the shape of the printing plate) shows that the printing area of the actual curable composition does not become excessive.

Further, in the curable composition, (Component C) is preferably contained in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of (Component A).

Further, the curable composition of the present invention may contain at least one type of fine particles selected from the group consisting of inorganic fine particles and organic fine particles as the component (component D), and is preferably contained.

Examples of the inorganic fine particles include cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), cerium oxide (Ta ₂ O ₅ ), zirconium dioxide (ZrO ₂ ), and tantalum nitride ( Si ₃ N ₄ ), barium titanate (BaO‧TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO‧TiO ₂ ), lead zirconate titanate (PZT), lead 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 zirconium dioxide (Y ₂ O ₃ -ZrO ₂ ), barium strontium 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 The carbon (C), the hydrotalcite, and the like may be used alone or in combination of two or more.

The organic fine particles are preferably fine particles of a heat resistant resin having a guanamine bond, an oxime bond, an ester bond or an ether bond. As such resins, from the viewpoint of heat resistance and mechanical properties, a polyimide resin or a precursor thereof, a polyamide amidoximine resin or a precursor thereof, or a polyamide resin is preferable. These may be used alone or in combination of two or more.

Among these, it is preferred that (Component D) include at least one selected from the group consisting of cerium oxide microparticles and hydrotalcite microparticles.

The cerium oxide microparticles used in the curable composition of the present invention are defined to also include microparticles which are physically coated with a powder or chemically surface-treated with an organic compound.

The cerium oxide particles to be used in the curable composition of the present invention are not particularly limited as long as they are dispersed in the curable composition of the present invention, and may be, for example, AEROSIL® supplied by AEROSIL, Japan.

The cerium oxide microparticles represented by these AEROSIL® are also used for imparting printability at the time of screen printing, and are also used as the purpose of imparting shake.

Further, the hydrotalcite is a layered inorganic compound which is a naturally occurring clay mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ‧4H ₂ O or the like. Further, the hydrotalcite may be a composition, such a hydrotalcite-based Mg/Al layered compound, which can be ion-exchanged with a carbonate group located between the layers to cause chloride ions (Cl ^- ) and/or sulfate ions (SO) The anion of ^4- ) is immobilized. By using this function, it can be effectively used for the purpose of capturing chloride ions (Cl ^- ) or sulfate ions (SO ^{4 -} ) which are causes of migration of copper or tin and improving the reliability of insulation.

As a commercial product of the hydrotalcite, for example, STABIACE HT-1, STABIACE HT-7, STABIACE HT-P of Suga Chemical Co., Ltd., or DHT-4A, DHT-4A2, DHT-4C of Xiehe Chemical Industry Co., Ltd., etc. .

The average particle diameter of the inorganic fine particles and/or organic fine particles is preferably from 0.01 to 10 μm, more preferably from 0.1 to 5 μm.

Further, the blending amount of (component D) is 0.1 to 60% by mass, preferably 0.3 to 55 mass, based on the total amount of (component A), (component B), (component C), and (component D). %, more preferably 0.5 to 40% by mass. The blending amount of (Component D) is in the range of 0.1 to 60% by mass based on the total amount of (Component A), (Component B), (Component C), and (Component D), and the curable composition is The printing performance of the viscosity under the screen printing method is good, and the diffusion due to the penetration of the curable composition after screen printing does not become so large, and the result is from the portion where the curable composition is to be applied. (In other words, the shape of the printing plate), it is understood that the printing area of the actual curable composition does not become excessive.

Further, in the curable composition, (Component D) is preferably contained in an amount of 1 to 30 parts by mass based on 100 parts by mass of (Component A).

In the curable composition of the present invention, in the method of dispersing organic and/or inorganic fine particles, generally, it is applied to roll rolling, mixer mixing, and the like which are carried out in the field of coatings, and is a method capable of sufficiently dispersing. can.

Further, the curable composition of the present invention may contain an antifoaming agent for the purpose of eliminating or suppressing the generation of bubbles at the time of printing, and is preferably included.

Specific examples of the antifoaming agent used in the curable composition of the present invention include, for example, BYK-077 (manufactured by BYK JAPAN Co., Ltd.), SN-DEFOAMER 470 (manufactured by SAN NOPCO Co., Ltd.), and TSA750S (Momentive Performance Materials). Copolyoxygen defoamer, such as polyoxyphthalic acid SH-203 (manufactured by Toray Dow Corning Co., Ltd.), DAPPO SN-348 (made by SAN NOPCO Co., Ltd.), DAPPO SN-354 (SAN NOPCO) Acrylic polymer-based defoamer, such as DAPPO SN-368 (made by SAN NOPCO Co., Ltd.), Disparlon 230HF (made by Kusumoto Kasei Co., Ltd.), SURFYNOL DF-110D (manufactured by Nissin Chemical Industry Co., Ltd.) An acetylene glycol-based antifoaming agent such as SURFYNOL DF-37 (manufactured by Nissin Chemical Industry Co., Ltd.) or a fluorine-containing polyoxo-based antifoaming agent such as FA-630. These may be used alone or in combination of two or more.

The content of the antifoaming agent is relative to the total amount of (Component A), (Component B), (Component C), and (Component D) (however, when the curable composition of the present invention does not contain (Component D), 100 parts by mass of (component A), (component B) and (component C) are preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, particularly preferably 0.1 to 3 parts by mass. .

Further, in the curable composition, the antifoaming agent is preferably contained in an amount of 0.2 to 10 parts by mass based on 100 parts by mass of the component (Part A).

Further, the curable composition of the present invention may contain a curing accelerator and is preferably included. The hardening accelerator is not particularly limited as long as it is a compound that promotes the reaction between an epoxy group and a carboxyl group, and examples thereof include melamine, acetonitrile, benzoguanamine, benzodiacylamine, and 2,4-diamine. -6-methyl propyl Eneoxyethyl-S-triazine, 2,4-methylpropenyloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2, a triazine compound such as 4-diamino-6-vinyl-s-triazine/isocyanato acid adduct, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2 -methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2- Methylimidazole, 1-(cyanoethylaminoethyl)-2-methylimidazole, N-[2-(2-methyl-1-imidazolyl)ethyl]urea, 1-cyanoethyl -2-undecylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyano Ethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-B Base-s-triazine, 2,4-diamino-6-[2'-B -4'-methylimidazolyl-(1')]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, N,N'-double (2-methyl-1-imidazolylethyl)urea, N,N'-bis(2-methyl-1-imidazolylethyl)hexanediamine, 2-phenyl-4-methyl-5 -hydroxymethylimidazole, 2-phenyl-4.5-dihydroxymethylimidazole, 2-methylimidazole‧isocyano cyanide adduct, 2-phenylimidazole‧isocyano cyanide adduct,2 ,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine ‧ iso-cyanuric acid adduct, 2-methyl-4-carbamidine Imidazole, 2-ethyl-4-methyl-5-methylpyridyl imidazole, 2-phenyl-4-methylcarbamimidazole, 1-benzyl-2-phenylimidazole, 1,2-di Methylimidazole, 1-(2-hydroxyethyl)imidazole, vinylimidazole, 1-methylimidazole, 1-allyl imidazole, 2-ethylimidazole, 2-butylimidazole, 2-butyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-benzyl-2-phenylimidazole Imidazole compound such as hydrogen bromide salt, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,5-diazabicyclo(4.3.0)nonene-5 and salts thereof a cyclic ruthenium compound such as 1,8-diazabicyclo (5.4.0) undecen-7 and a salt thereof, and a derivative of a cyclic ruthenium compound, triethylenediamine, benzyl An amine compound such as methylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, triphenylphosphine, diphenyl(p-tolyl)phosphine, and arson Phenyl)phosphine, ginseng (alkoxyphenyl)phosphine, ginseng (alkyl ‧ alkoxyphenyl) phosphine, cis (dialkylphenyl) phosphine, cis (trialkylphenyl) phosphine, ginseng (tetraalkylphenyl)phosphine, cis (dialkoxyphenyl)phosphine, cis (trialkoxyphenyl)phosphine, cis (tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkyl a phosphine-based compound such as an arylphosphine or an alkyldiarylphosphine, or a cyanodiazine.

These hardening accelerators may be used singly or in combination of two or more.

Among these hardening accelerators, it is preferable to use a melamine, an imidazole compound, a cyclic ruthenium compound, a derivative of a cyclic ruthenium compound, a phosphine compound, and an amine compound, in consideration of both the hardening promoting action and the electrical insulating property. It is melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and its salt, 1,8-diazabicyclo (5.4.0) undecene-7 and its salts.

The blending amount of such a hardening accelerator is not particularly limited as long as the hardening promoting effect can be attained. However, from the viewpoint of the curability of the curable composition of the present invention and the electrical insulating property or water resistance of the coating film obtained by curing the curable composition of the present invention, it is hardened with respect to the present invention. The total amount of the component (component A) and (component B) which are essential components of the present invention in the composition is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 by mass. Share. When the blending amount is in the range of 0.05 to 5 parts by mass based on 100 parts by mass of the total of (Component A) and (Component B), it can be cured in a short time and the curable composition of the present invention is cured. The electrical insulation properties or water resistance of the coating film are improved.

In addition, when it is necessary to suppress deterioration of the acid value of the resin and discoloration during heating, an antioxidant such as a phenol-based antioxidant, a phosphite-based antioxidant, or a thioether-based antioxidant can be added to the curable composition of the present invention. .

Further, in the curable composition of the present invention, in order to improve the workability at the time of coating and the film properties before and after the formation of the film, a coloring agent such as a leveling agent or a dye or a pigment, a flame retardant, and lubrication may be added. Agent.

The method for producing the curable composition of the present invention is not particularly limited as long as it is a method in which (Component A), (Component B), and (Component C) are soluble or dispersible in an organic solvent. For example, the curable composition of the present invention can be produced by producing a main agent containing at least (Component A) and a hardener containing at least (Component B), followed by blending a main agent and a hardener.

Further, in the curable composition of the present invention, after the screen printing property is good and the curable composition is printed, in order to prevent the composition from flowing, the film thickness cannot be made constant, and the shake modification index is desired to be 25 ° C. The time is 1.1 or more, more preferably 1.1 to 3.0, and particularly preferably 1.1 to 2.5. In order to make the shake modification index at 1.1 °C or higher at 25 ° C, The method of adjusting the shake modification index by using the above-mentioned inorganic fine particles or organic fine particles, the method of adjusting the shake modification index by using a polymer additive, and the like, and the method of adjusting the shake modification index by using inorganic fine particles or organic fine particles is preferred.

In addition, the "shake modification index" described in the present specification is measured using a cone and plate type viscometer (Model: DV-II+Pro, model of the spindle: CPE-52), and is 25 ° C. The ratio of the viscosity at the time of 1 rpm to the viscosity at 10 rpm of the spindle at 25 ° C is defined.

The sclerosing composition, the viscosity at 25 ° C measured by a rotary viscometer is 20 Pa. s~80Pa‧s is better, 30Pa. s~50Pa. s is better. The viscosity is less than 20Pa. s, the flow of the composition after printing becomes large, and there is a tendency for the film thickness to be thinned, if it exceeds 80 Pa. s, the transferability of the composition to the substrate is lowered, and the pores and pinholes in the printed film tend to increase.

Finally, a method of producing the cured film of the present invention, the coated film of the present invention, the flexible wiring board, and the flexible wiring board will be described.

The cured film of the present invention is a cured product obtained by curing the curable composition of the present invention. Moreover, the electronic component of the present invention has the above cured film.

Further, the coating film of the present invention is a coating film for a flexible wiring board comprising a cured product of the curable composition of the present invention, and more specifically, by coating the curable composition of the present invention One of the surfaces on which the wiring is formed on the flexible wiring board in which the wiring is formed on the flexible substrate A coating film for a flexible wiring board obtained by partially or completely hardening.

Further, in the flexible wiring board of the present invention, part or all of the surface on which the wiring is formed on the flexible wiring board in which the wiring is formed on the flexible substrate is flexible by the coating film. Wiring board.

Further, in the wiring covered by the coating film, it is preferable to use a tin-plated copper wiring wire in consideration of the oxidation resistance and economy of the wiring.

Further, the method for producing a flexible wiring board according to the present invention includes the method for producing a flexible wiring board covered by a coating film in the following steps 1' and 2'.

(Step 1 ') A step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of the wiring pattern portion of the flexible wiring board

(Step 2') The printed film obtained in the step 1', the printing film obtained in the step 1' is placed in an atmosphere of 40 to 100 ° C to thereby remove a part of the solvent of the solvent in the printing film. a printed film obtained by placing the printed film obtained in the step 1' under an atmosphere of 40 to 100 ° C and evaporating the entire amount of the solvent in the printed film, thereby removing the printed film by 100 to 170 The step of heating to harden and form a coating film.

In the curable composition of the present invention, for example, an ink for an insulating coating film for wiring can be used, and the cured product of the present invention can be used as a coating film for insulating protection. In particular, it is used as a coating film for insulation protection of wiring by covering all or a part of the wiring of a flexible wiring board such as a film-on-film (COF).

Hereinafter, the manufacturer of the flexible wiring board of the present invention will be described. The specific steps implemented by the law. For example, the coating film of the flexible wiring board can be formed by the following steps 1 and 3 and the step 2 as needed.

(step 1)

The step of forming a printed film on the pattern by printing the curable composition of the present invention on at least a part of the wiring pattern portion of the flexible wiring board.

(Step 2)

The step of evaporating a part or a whole amount of the solvent in the printed film by subjecting the printed film obtained in the step 1 to an atmosphere of 40 to 100 ° C.

(Step 3)

The step of hardening and forming a coating film by heating the printing film obtained in the step 1 or the printing film obtained in the step 2 at 100 to 170 °C.

Step 2 is carried out by placing the printing film obtained in the step 1 in an atmosphere of 40 to 100 ° C to evaporate the solvent in the printing film, taking into account the evaporation rate of the solvent and the subsequent operation (100 to 170). The operation of heating at °C to harden it) rapid migration, usually 40 to 100 ° C, preferably 60 to 100 ° C, more preferably 70 to 90 ° C. In the step 2, the printing film obtained in the step 1 is placed in an atmosphere of 40 to 100 ° C, and the time for evaporating the solvent in the printing film is not particularly limited, but is preferably 10 to 120 minutes, more preferably 20~100 points.

In addition, this is done by placing the printed film obtained in step 1 at 40~ The operation of evaporating the solvent in the printed film in an atmosphere of 100 ° C is performed in response to the need, and immediately after the operation of the step 1, the process proceeds to step 3 and is heated at 100 to 170 ° C to harden it. And the operation of forming the coating film is carried out, and the hardening reaction and the solvent removal can be simultaneously performed. The thermosetting conditions to be carried out are preferably from 105 to 160 ° C, more preferably from the viewpoint of preventing diffusion of the plating layer and obtaining low warpage and flexibility as a protective film. It is 110~150 °C. The heat hardening time by heating is not particularly limited, and is preferably from 10 to 150 minutes, more preferably from 15 to 120 minutes.

According to the above method, a flexible wiring board obtained by partially or completely covering one surface of the flexible wiring board on which the wiring is formed on the flexible substrate is formed The person covered by the film.

Further, the curable composition of the present invention can be blended with any of the above-mentioned optional components as needed, and can be uniformly mixed, and the film-forming material can be used for coating inks, solder resist inks for semiconductor elements or various electronic parts, In addition to the interlayer insulating film, a coating material, a coating agent, an adhesive, or the like can be used.

[Examples]

The present invention will be further illustrated by the following examples, which are not to be construed as being limited to the following examples.

<Measurement of acid value>

The solution containing (Component A) used in the present invention is obtained by the following method to determine the acid value, and the acid value of (Component A) is determined using the formula (α). However, among the solvents used in the above solution, those having an acid value of "0" are used.

First, the scale contains about 1 g of the solution of (Component A). Then, on the other hand, 30 g of a mixed solvent of isopropyl alcohol / toluene = 1/2 (mass ratio) was added, and it melt|dissolved uniformly. A suitable amount of phenolphthalein as an indicator was added to the obtained solution, and titration was carried out using a 0.1 N KOH solution (alcoholic property). Then, from the titration result, the following formula (α): A = 10 × Vf × 56.1 / (Wp × I) ‧ ‧ ‧ ‧ (α)

To calculate the acid price. In the formula (α), A represents an acid value (mgKOH/g), Vf represents a titer (mL) of a 0.1 N KOH solution, Wp represents a mass (g) of a solution containing (Component A), and I represents a component (component) The proportion (% by mass) of the component (A) of the solution of A).

<Measurement of hydroxyl value>

The hydroxyl value was measured in accordance with JIS K0070.

<Measurement of number average molecular weight>

The number average molecular weight is a polystyrene-equivalent number average molecular weight measured by GPC, and the measurement conditions of GPC are as follows.

Device name: HPLC unit HSS-2000 manufactured by Japan Seiko Co., Ltd.

Column: Shodex (registered trademark) column LF-804×3 (inline)

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus, manufactured by JASCO Corporation

Temperature: 40.0 ° C

Sample quantity: sample loop 100μL

Sample concentration: adjusted to about 0.1% by mass.

<Measurement of Shake Modification Index>

The shake modification index of the curable composition was measured by the following method.

Using a curable composition of about 0.8 g, a cone-and-plate viscometer (model of Brookfield Co., Ltd.; model of DV-II+Pro spindle; CPE-52) was used at a temperature of 25.0 ° C and a number of revolutions of 10 rpm. Viscosity after 7 minutes. Thereafter, the viscosity after 7 minutes from the start of the measurement was measured under the conditions of a temperature of 25.0 ° C and a number of revolutions of 1 rpm.

In addition, the shake modification index is obtained by the following calculation.

The method of obtaining the shake modification index: Shake modification index = [1 rpm viscosity] ÷ [10 rpm viscosity]

<Synthesis of Polyester Polyol> (Refer to Synthesis Example 1) <Polyester diol (α)>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor with a distillation device, 983.5 g (6.74 mol) of anhydrous phthalic acid and 879.2 g (7.44 mol) of 1,6-hexanediol were added to the inside of the reaction vessel. The temperature was raised to 140 ° C using an oil bath and stirring was continued for 4 hours. After that, continue to stir while adding After adding 1.74 g of mono-n-butyltin oxide, the internal temperature of the reaction vessel was slowly raised, followed by a vacuum pump, and the pressure in the reaction vessel was gradually reduced by a small amount, and the water was removed to the outside of the reaction vessel by distillation under reduced pressure. Finally, the internal temperature is raised to 220 ° C, and the pressure is reduced to 133.32 Pa. After 15 hours, it was confirmed that the water was completely distilled off and the reaction was completed. The obtained polyester polyol (hereinafter referred to as polyester diol (α)) has the structure of the above formula (2), and n = 1 to 20. As a result of measuring the hydroxyl value thereof, the hydroxyl value was 53.1 mg-KOH/g.

<Synthesis of (Component A)> (Synthesis Example 1) <A-1 solution>

3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. 270.7 parts by mass of 964.4 parts by mass of γ-butyrolactone as a solvent was stirred and dissolved at 120 °C. To this, 142.6 parts by mass of 4,4'-diphenylmethane diisocyanate (MDI) as a diisocyanate compound was added and stirred, and 1,8-diazabicyclo ring as a catalyst was added thereto [5.4.0] 0.1 parts by mass of -7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a terminal acid group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was obtained.

Next, the obtained acid anhydride group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C, and stirred, and 908.7 parts by mass of the polyester diol (α) and γ-butyrolactone were added. 1018.7 parts by mass and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. After cooling down to the room A solution of a compound having a quinone imine bond and a hydroxyl group (hereinafter referred to as "compound (A-1)") having a solid content concentration of 40% by mass was obtained. The compound (A-1) had a number average molecular weight of 15,000, a degree of dispersion of 4.0, and an acid value of a solid content of 25 mgKOH/g.

(Synthesis Example 2) <A-2 solution>

3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. 270.7 parts by mass of 964.4 parts by mass of γ-butyrolactone as a solvent was stirred and dissolved at 120 °C. To this, 142.6 parts by mass of 4,4'-diphenylmethane diisocyanate (MDI) as a diisocyanate compound was added and stirred, and 1,8-diazabicyclo ring as a catalyst was added thereto [5.4.0] 0.1 parts by mass of -7-undecene (DBU) was reacted at 120 ° C for 3 hours under a nitrogen stream. Thereafter, by cooling to room temperature, a terminal acid group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was obtained.

Next, the obtained acid anhydride-containing sulfonimide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C, and stirred, and 3-methyl-1,5-pentanediol: isobenzene was added. 908.7 parts by mass of a polyester polyol of diformic acid (trade name: KURARAY Polyol P-2030 (*), manufactured by Kuraray Co., Ltd.) and 1018.7 parts by mass of γ-butyrolactone were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a quinone imine bond and a hydroxyl group (hereinafter referred to as "compound (A-2)") having a solid content concentration of 40% by mass was obtained. Compound (A-2) The number average molecular weight was 15,000, the degree of dispersion was 4.0, and the acid value of the solid content was 25 mgKOH/g.

(※ is a polyester polyol having the structure of the above formula (2), and the average of n is 8.0 to 8.1)

(Synthesis Example 3) <A-3 solution>

3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 °C. To which COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound of a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass of (TDI) and stirred, and 0.1 parts by mass of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream. It was allowed to react at 120 ° C for 3 hours. Thereafter, by cooling to room temperature, a terminal acid group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was obtained.

Next, the obtained acid anhydride group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C, and stirred, and 908.7 parts by mass of the polyester diol (α) and γ-butyrolactone were added. 1054.8 parts by mass were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a quinone imine bond and a hydroxyl group (hereinafter referred to as "compound (A-3)") having a solid content concentration of 40% by mass was obtained. Compound The number average molecular weight of (A-3) was 15,000, the degree of dispersion was 4.0, and the acid value of the solid content was 26 mgKOH/g.

(Synthesis Example 4) <A-4 solution>

3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 °C. To which COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound of a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.3 parts by mass of (TDI) and stirred, and 0.1 parts by mass of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) as a catalyst was added thereto under a nitrogen stream. It was allowed to react at 120 ° C for 3 hours. Thereafter, by cooling to room temperature, a terminal acid group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was obtained.

Next, the obtained acid anhydride-containing sulfonimide prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C, and stirred, and 3-methyl-1,5-pentanediol: isobenzene was added. 908.7 parts by mass of a polyester polyol of diformic acid (trade name: KURARAY Polyol P-2030, manufactured by Kuraray Co., Ltd.) and 1054.8 parts by mass of γ-butyrolactone were stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution of a compound having a quinone imine bond and a hydroxyl group (hereinafter referred to as "compound (A-4)") having a solid content concentration of 40% by mass was obtained. Number average molecule of compound (A-4) The amount was 15,000, the degree of dispersion was 4.0, and the acid value of the solid fraction was 26 mgKOH/g.

(Synthesis Example 5) <A-5 solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 380.29 g (0.179 mol) of polyester diol (α) was placed, and MILLIONATE MT (Japanese polyamine) of 4,4'-diphenylmethane diisocyanate was placed. 53.65g (0.214mol) manufactured by Carbamate Industry Co., Ltd. and COSMONATE T-80 as a mixture of 2:4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 ( 24.89 g (0.143 mol) and 685.3 g of γ-butyrolactone manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and dissolved all the raw materials at 150 ° C, and allowed to react for 4 hours to form an amine group. A polyisocyanate of an acid ester linkage.

Next, the temperature of the reaction liquid was lowered to 60 ° C, and 63.71 g (0.332 mol) of anhydrous trimellitic acid was added thereto to completely dissolve it, and then MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. With 146.07 g of γ-butyrolactone, the temperature was raised to 120 ° C to dissolve all the raw materials, and the reaction was carried out for 1 hour.

Thereafter, the temperature of the reaction liquid was raised to 180 ° C, and the mixture was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction liquid was lowered to 120 ° C, and 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the solid content was 40% by mass after cooling to room temperature. A solution of a guanamine bond and a compound of a guanidine bond and a blocked isocyanate group (hereinafter referred to as "compound (A-5)").

The obtained compound (A-5) has a number average molecular weight of 10,500 and a degree of dispersion. The acid value of the solid fraction was 3.1 mg KOH/g.

(Synthesis Example 6) <A-6 solution>

A polyester polyol containing 3-methyl-1,5-pentanediol:isophthalic acid in a reaction vessel equipped with a stirring device, a thermometer, and a capacitor (trade name: KURARAY Polyol P, manufactured by KURARAY Co., Ltd.) -2030) 378.29 g (0.179 mol), and placed in a 4,4'-diphenylmethane diisocyanate, MILLIONATE MT (manufactured by Nippon Polyurethane Co., Ltd.), 53.65 g (0.214 mol), and as 2, COSMONATE T-80 (manufactured by Mitsui Chemicals, Inc.), a mixture of 4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate, having a mass ratio of 80:20, 24.89 g (0.143 mol) 685.3 g of γ-butyrolactone was dissolved at 150 ° C, and reacted for 4 hours to form a polyisocyanate having a urethane bond.

Next, the temperature of the reaction liquid was lowered to 60 ° C, and 63.71 g (0.332 mol) of anhydrous trimellitic acid was added thereto to completely dissolve it, and then MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) were added. With 146.07 g of γ-butyrolactone, the temperature was raised to 120 ° C to dissolve all the raw materials, and the reaction was carried out for 1 hour.

Thereafter, the temperature of the reaction liquid was raised to 180 ° C, and the mixture was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction liquid was lowered to 120 ° C, and 5.61 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the solid content was 40% by mass after cooling to room temperature. a compound of a guanidine bond and a sulfhydryl bond with a blocked isocyanate group (hereinafter referred to as A solution of "compound (A-6)").

The obtained compound (A-6) had a number average molecular weight of 10,500, a degree of dispersion of 3.1, and an acid value of a solid content of 19 mgKOH/g.

(Synthesis Example 7) <A-7 solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 369.85 g (0.175 mol) of polyester diol (α) and Desmodule-W (4,4'-dicyclohexylmethane diisocyanate) were placed. 91.70g (0.350mol) of a urethane ester company, 692.33g of γ-butyrolactone (made by Mitsubishi Chemical Corporation) as a solvent, dissolved all the raw materials at 150 ° C, and allowed to react for 4 hours. It is made to form a polyisocyanate having a urethane bond.

Next, the temperature of the reaction liquid was lowered to 80 ° C, and Desmodule-W 45.85 g (0.175 mol) and anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 33.60 g (0.175 mol) and γ-butyrolactone ( 119.18 g of Mitsubishi Chemical Corporation was heated to 150 ° C, and all the raw materials were dissolved and allowed to react for 3 hours.

When the temperature of the reaction liquid was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) as a diol was added, and the temperature was raised to 120 ° C to dissolve all the raw materials and react 4 hour. Then, the temperature of the reaction liquid was lowered to 80 ° C, and 9.67 g (0.105 mol) of glycerol (manufactured by Kanto Chemical Co., Ltd.) and 39.10 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) were added as a triol. The reaction was allowed to proceed after 110 °C. The reaction is carried out while confirming the presence of the isocyanate group in the reaction liquid by IR measurement. When the reaction of the isocyanate group in the reaction system is not confirmed, the reaction is terminated, and by cooling to room temperature, a compound having a hydroxyl group, a guanamine bond, and a quinone bond and a hydroxyl group having a solid content of 40% by mass is obtained. (The following is a solution of "compound (A-7)").

The obtained compound (A-7) had a number average molecular weight of 10,000, a degree of dispersion of 4.3, an acid value of a solid content of 17 mgKOH/g, and a hydroxyl value of 10 mgKOH/g.

(Comparative Synthesis Example 1) <CA-1 Solution>

3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) as a tetracarboxylic dianhydride was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer. 270.7 parts by mass and 863.2 parts by mass of γ-butyrolactone as a solvent were stirred and dissolved at 120 °C. To which COSMONATE T-80 (Mitsui Chemical Polyurethane) was added as a diisocyanate compound of a mixture of 2,4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20. 99.27 parts by mass of the company, stirred, and 0.1 parts by mass of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) as a catalyst was added thereto, and the mixture was placed under a nitrogen stream. The reaction was carried out at 120 ° C for 3 hours. Thereafter, by cooling to room temperature, a terminal acid group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was obtained.

Next, the obtained acid anhydride group-containing quinone imine prepolymer having a solid content concentration of 30% by mass was heated to 100 ° C, and stirred to add a polycarbonate diol compound as a polyol compound (trade name: DURANOL) T5650E: Asahi Kasei Chemicals Co., Ltd., Mn=500) 100.0 A polyester diol (trade name: OD-X-688 DIC (manufactured by OD-X-688 DIC), number average molecular weight: about 2,000) 460.0 parts by mass of adipic acid/neopentyl glycol/1,6-hexanediol 531.71 parts by mass with γ-butyrolactone and stirred. 2.4 parts by mass of 4-dimethylaminopyridine (DMAP) as a catalyst was added thereto, and allowed to react at 100 ° C for 8 hours. Thereafter, by cooling to room temperature, a solution having a solid content of 40% by mass of a compound having a quinone bond and a carboxyl group and a hydroxyl group (hereinafter, "compound (CA-1)")) was obtained. The compound (CA-1) had a number average molecular weight of 13,500, a degree of dispersion of 4.0, and an acid value of a solid content of 36 mgKOH/g.

(Comparative Synthesis Example 2) <CA-2 Solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, a composition unit derived from 1,4-cyclohexanedimethanol and a composition derived from 1,6-hexanediol were placed at a molar ratio of 1:1. 161.44g (0.179mol) of polycarbonate diol UM-CARB90 (1/1) (manufactured by Ube Industries, Ltd.) was placed in the unit and placed into MILLIONATE MT as 4,4'-diphenylmethane diisocyanate. 53.65g (0.214mol) manufactured by Japan Polyurethane Industry Co., Ltd. and COSMONATE T as a mixture of 2:4-trichloroethylene diisocyanate and 2,6-trichloroethylene diisocyanate in a mass ratio of 80:20 -80 (manufactured by Mitsui Chemicals, Polyurethane Co., Ltd.), 24.89 g (0.143 mol) and 159.93 g of γ-butyrolactone, and dissolved all the raw materials at 150 ° C, and allowed to react for 4 hours to form A polyisocyanate of a urethane bond.

Next, the temperature of the reaction liquid is lowered to 60 ° C, and then added. After 63.71 g (0.332 mol) of anhydrous trimellitic acid was completely dissolved, MILLIONATE MT 23.00 g (0.092 mol) and COSMONATE T-80 10.67 g (0.061 mol) and γ-butyrolactone 342.98 g were added, and the temperature was raised to 120 ° C. All the raw materials were dissolved and reacted for 1 hour.

Thereafter, the temperature of the reaction liquid was raised to 180 ° C, and the mixture was allowed to react at 180 ° C for 2 hours. Next, the temperature of the reaction liquid was lowered to 120 ° C, and 3.13 g of 2-butanone oxime (manufactured by Wako Pure Chemical Industries, Ltd.) was added to complete the reaction, and the mixture was cooled to room temperature to obtain a solid content of 40% by mass. A solution of an amine bond and a compound of a quinone bond and a carboxyl group (hereinafter, "compound (CA-2)").

The obtained compound (CA-2) had a number average molecular weight of 9,200, a degree of dispersion of 3.1, and an acid value of a solid content of 31 mgKOH/g.

(Comparative Synthesis Example 3) <CA-3 Solution>

In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, a molar ratio of 3:1 was used to contain a constituent unit derived from 1,4-cyclohexanedimethanol and a composition derived from 1,6-hexanediol. Polycarbonate diol UM-CARB90 (3/1) (manufactured by Ube Industries, Ltd., average molecular weight: about 900) 156.98 g (0.175 mol), as 4,4'-dicyclohexylmethane diisocyanate 91.70 g (0.350 mol) of Desmodule-W (manufactured by Susei BAYER Carbamate Co., Ltd.) and 165.80 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and dissolved all the raw materials at 150 ° C And allowed to react for 4 hours to form a polyisocyanate having a urethane bond.

Next, the temperature of the reaction solution is lowered to 80 ° C, and then added. Desmodule-W 45.85g (0.175mol), anhydrous trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 33.60g (0.175mol) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) 162.33g, heated to 150 ° C, All the raw materials were dissolved and allowed to react for 3 hours.

When the temperature of the reaction liquid was lowered to 80 ° C, 16.40 g (0.158 mol) of neopentyl glycol (manufactured by Kanto Chemical Co., Ltd.) as a diol was added, and the temperature was raised to 120 ° C to dissolve all the raw materials and react 4 hour. Then, the temperature of the reaction liquid was lowered to 80 ° C, and 9.67 g (0.105 mol) of glycerol (manufactured by Kanto Chemical Co., Ltd.) and 26.07 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) were added as a triol. The reaction was allowed to proceed after 110 °C. The reaction was carried out while confirming the presence of the isocyanate group in the reaction liquid by IR measurement, and the reaction was terminated at the time when the isocyanate group in the reaction system could not be confirmed, and 177.1 g of γ-butyrolactone was added to obtain a solid form. A solution of a compound having a hydroxyl group, a guanamine bond, and a quinone bond and a hydroxyl group (hereinafter referred to as "compound (CA-3)") at a concentration of 40% by mass.

The obtained compound (CA-3) had a number average molecular weight of 8,000, a degree of dispersion of 4.4, an acid value of a solid content of 27 mgKOH/g, and a hydroxyl value of 16 mgKOH/g.

<Manufacture of main agent blend> (main agent blend 1)

160.0 parts by mass of a mixed compound (A-1), cerium oxide powder (manufactured by AEROSIL® Co., Ltd., trade name: AEROSIL® R-974), 6.3 parts by mass, melamine as a hardening accelerator (Nissan Chemical Industry Co., Ltd.) 0.72 parts by mass and 8.4 parts by mass of diethylene glycol diethyl ether, using a three-roll mill (manufactured by Inoue Co., Ltd., type: S-4 3/4×11), for compound (A-1) ) mixing cerium oxide powder and a hardening accelerator. Thereafter, 2.0 parts by mass of an antifoaming agent (trade name: TSA750S, manufactured by Momentive Performance Materials Co., Ltd.) was added, and the mixture was mixed using a spatula. This blend was used as the main agent blend C1.

(Main agent blend 2~7 and comparative main agent blend 1~3)

The blending was carried out in the same manner as in the main component blend 1 according to the blending composition shown in Table 1. Each of them is used as a main agent blend 2 to 7, and a comparative main component blend is 1 to 3.

In addition, the values in the table represent "parts by mass".

<Manufacture of hardener solution> (Admixment Example 1 of Hardener Solution) <B-1 Solution>

An epoxy resin having a structure of the following formula (7) (manufactured by Mitsubishi Chemical Corporation, specification name: JER604, epoxy equivalent: 120 g/eqv), 16.85 parts by mass, and two ethylene, were added to a container having a stirrer, a thermometer, and a capacitor. The mixture was stirred at 18.25 parts by mass of diol diethyl ether.

While stirring was continued, the temperature in the vessel was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. After confirming that JER604 was completely dissolved, it was cooled to room temperature, and a solution containing JER604 at a concentration of 48% by mass was obtained. This solution was used as the hardener solution B-1.

(Admixment Example 2 of Hardener Solution) <B-2 Solution>

An epoxy resin containing N,N-diepoxypropyl-4-(epoxypropyloxy)aniline as a main component in a container equipped with a stirrer, a thermometer, and a capacitor (manufactured by Mitsubishi Chemical Corporation, specifications) Name: JER630, epoxy equivalent 98 g / eqv) 16.85 parts by mass, diethylene glycol diethyl ether 18.25 parts by mass, stirring was started.

While stirring was continued, the temperature in the vessel was raised to 40 ° C using an oil bath. After the internal temperature was raised to 40 ° C, stirring was continued for 30 minutes. Thereafter, it was confirmed that JER630 was completely dissolved, and after cooling to room temperature, a solution containing JER630 having a concentration of 48% by mass was obtained. This solution was used as the hardener solution B-2.

<Mixing of a mixture containing a main agent blend and a hardener> (Example 1 of the curable composition)

88.71 parts by mass of the main agent blend C1 and 3.51 parts by mass of the hardener solution B-1 were placed in a plastic container. Further, 3.0 parts by mass of diethylene glycol diethyl ether and diethylene glycol ethyl ether acetate were added as a solvent in order to mix the other blending examples described later and to compare the curable composition and viscosity of the blending examples. 1.5 parts by mass. The mixing was carried out by stirring at room temperature for 5 minutes using a spatula to obtain a curable composition (hereinafter referred to as "curable composition F1").

(Examples 2 to 8 and Comparative Examples 1 to 3)

The blending was carried out according to the blending composition shown in Table 2 in the same manner as in Example 1 of the curable composition. The blend prepared in Examples 2 to 8 of the curable composition was used as the curable composition F2 to F8, respectively, and the blend prepared in Comparative Examples 1 to 3 of the curable composition was used as the curable composition G1~. G3. Here, in the curable compositions F8 and G3, the blocked isocyanate "7950" manufactured by Baxenden Co., Ltd. (component B) is further blended.

In addition, the values in the table represent "parts by mass".

In addition, the curable compositions F1 to F8 and the curable composition G1 to G3 The blending composition is shown in Table 2. Further, the mass fraction of each of the curable compositions F1 to F8 and the curable compositions G1 to G3 is summarized in Table 3. Further, the number of epoxy groups/carboxyl groups in Tables 2 and 3 were determined from the acid value.

(Examples 1 to 8 and Comparative Examples 1 to 3)

The curable compositions F1 to F8 and the curable compositions G1 to G3 are used. The evaluation of flexibility, disconnection inhibition, warpage, and long-term electrical insulation reliability were performed by the method described below. The results are shown in Table 4.

<Evaluation of flexibility>

It is a copper sheet laminated with flexible copper (manufactured by Sumitomo Metal Mining Co., Ltd., specification: ESPERFLEX, copper thickness: 8 μm, polytheneimide thickness: 38 μm) to a width of 75 mm and a length of 110 mm. The curable composition F1 was applied by screen printing so that the thickness of the coating film after hardening was 15 μm, and it was kept at room temperature for 10 minutes, and placed in a hot air circulating dryer at 120 ° C for 60 minutes. hardening. The PET film of the backing of the test piece was peeled off, and a strip of a width of 10 mm was cut with a paper cutter, and the film surface was bent about 180 degrees to the outside, and compressed by a compressor at 0.5 ± 0.2 MPa for 3 seconds. bell. The bent portion was observed with a microscope of 30 times in a bent state to confirm the occurrence of cracks. The results are shown in Table 4.

Moreover, the same evaluation was performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. The results of these are also shown in Table 4.

<Disconnection suppression evaluation of wiring of wiring board (MIT test)>

A micro-comb pattern described in JPCA-ET01 manufactured by a laminated board made of flexible copper (manufactured by Sumitomo Metal Mining Co., Ltd., specification: ESPERFLEXUS, copper thickness: 8 μm, polytheneimide thickness: 38 μm) A substrate having a shape (wide copper wiring width / copper wiring width = 15 μm / 15 μm) is subjected to tin plating treatment, and the curable composition F1 is used on the flexible wiring board The screen printing method is applied so that the thickness from the polyimide film surface of the coating film becomes 10 μm (after drying). The obtained coating film was formed into a wiring board, and placed in a hot air circulating dryer at 80 ° C for 30 minutes, and then the coating film was cured by being placed in a hot air circulating dryer at 120 ° C for 120 minutes.

Using this test piece, the test conditions described in JIS C-5016 were carried out under the following test conditions.

(Test conditions)

Testing machine: MITTESTERBE202 manufactured by TESTER Industry Co., Ltd.

Bending speed: 10 times / min

Load: 200g

Bending angle: ±90°

Radius of the tip end of the clamp: 0.5mm

The number of times of bending was increased by 10 times each time under the above test conditions, and the presence or absence of cracks in the wiring was visually observed, and the number of times of bending at the time of occurrence of cracks was recorded. The results are reported in Table 3.

Moreover, the same evaluation was performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. The results of these are listed together in Table 4.

<Evaluation of warpage>

The curable composition F1 was applied onto the substrate by screen printing using a #180 mesh polyester plate, and the substrate was placed in a hot air circulating dryer at 80 ° C for 30 minutes. Thereafter, the substrate is placed in a hot air circulating drying at 120 ° C. The applied curable composition F1 was cured for 60 minutes. For the substrate, a 25 μm thick polyimide film [Kapton® (registered trademark) 100EN, manufactured by DU PONT-TORAY Co., Ltd.] was used.

The hardened coating film was cut into a diameter of 50 mm Φ on each of the substrates by a round cutter. A shape that is warped into a convex or concave shape is formed near the center of the circle. The cured film is formed on the substrate cut by the circulator, and is placed in a state in which the lower side is convex after 1 hour, that is, the surface near the center where the cured film is formed on the substrate is placed in contact with the horizontal surface, and the measurement is performed. The maximum and minimum values of the warpage height from the horizontal plane are averaged. When the symbol indicates the direction of warpage and the lower side is placed in a convex state, the copper substrate or the polyimide film has a "+" when the cured film is on the upper side and "-" when the cured film is on the lower side. . Then, if the warpage is less than +3.0 mm, it is given.

The results are shown in Table 4.

Moreover, the same evaluation was performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. The results of these are also shown in Table 4.

<Evaluation of long-term electrical insulation reliability>

A micro-comb pattern described in JPCA-ET01 manufactured by a laminated board made of flexible copper (manufactured by Sumitomo Metal Mining Co., Ltd., specification: ESPERFLEXUS, copper thickness: 8 μm, polytheneimide thickness: 38 μm) A substrate having a shape (wide copper wiring width/copper wiring width width = 15 μm/15 μm) is subjected to a tin plating treatment, and the curable composition F1 is coated by the screen printing method on the flexible wiring board. The thickness of the polyimide surface of the film becomes Coating was carried out in a thickness of 15 μm (after drying). The obtained coating film was formed into a wiring board, placed in a hot air circulating dryer at 80 ° C for 30 minutes, and then placed in a hot air circulating dryer at 120 ° C for 120 minutes to apply the applied curable composition F1. hardening.

Using this test piece, a temperature and humidity constant test was performed using a MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV) under the conditions of a temperature of 120 ° C and a humidity of 85% RH by applying a bias voltage of 60 V. Table 4 shows the resistance values of the substrate of the above-described fine comb type pattern in the initial stage of the above-mentioned temperature and humidity constant test and after 100 hours, 250 hours, and 400 hours after the start.

Moreover, the same evaluation was performed using the curable compositions F2 to F8 and the curable compositions G1 to G3. The results of these are listed together in Table 4.

As is clear from the results of Table 4, the curable composition of the present invention is excellent in flexibility, wire breakage inhibition, and long-term electrical insulation reliability, and this cured product can be used as an insulating protective film for a flexible wiring board.

[Industrial availability]

The curable composition of the present invention is suitable for use in insulation protection of a flexible wiring board.

Claims (11)

A curable composition comprising: (Component A) having a structural unit represented by the following formula (1) and having at least one bond of a ruthenium bond and a guanamine bond, and having a compound having a functional group reactive with a curing agent, (a component B) a curing agent, (a component C) an organic solvent, and (component D) at least one type of fine particles selected from the group consisting of inorganic fine particles and organic fine particles (component B) a compound containing two or more epoxy groups per molecule, and (component C) is at least one organic solvent selected from the group consisting of an ether solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solvent. When the total amount of the component (A) and the component (B) is 100 parts by mass, the component (B) is contained in an amount of 1 to 55 parts by mass, and the component (A), the component (B), the component (C), and the component ( When the total amount of D) is 100 parts by mass, it contains 25 to 75 parts by mass of the component (C), and (component D) is relative to (component A), (component B), (component C), and (component D). The amount is 0.1 to 60% by mass, (In the formula (1), R ¹ each independently represents an organic residue derived from a diol having 3 to 36 carbon atoms, and R ² each independently represents a phenyl group or a pendant phenyl group having a substituent. The curable composition according to claim 1, wherein the functional group reactive with the curing agent is at least one selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an isocyanate group, a phosphonium group, and an amine group. The curable composition according to claim 1 or 2, wherein (component A) contains (a raw material a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, and (raw material b) a compound obtained by reacting the polyol represented by the formula (2) and (the raw material c) with a polyisocyanate as an essential component, (In the formula (2), (n+1) of R ¹ each independently represent an organic residue derived from a diol having 3 to 36 carbon atoms, and n of R ² each independently represent a phenylene group or have The substituent is a phenyl group, and n represents an integer from 1 to 60). a sclerosing composition as recited in claim 1 or 2, wherein A) further having a urethane bond. The curable composition according to claim 1 or 2, wherein (component A) has an acid value of 10 to 50 mgKOH/g. A cured film comprising the cured product of the curable composition according to any one of claims 1 to 5. A coating film for a flexible wiring board, characterized in that part or all of a surface of a flexible wiring board on which a wiring is formed on a flexible substrate is coated, as described in claim 1 The curable composition according to any one of 5, which is cured and obtained. A flexible wiring board characterized in that part or all of a surface on which a wiring is formed on a flexible wiring board in which a wiring is formed on a flexible substrate is covered with a coating film as recited in claim 7 With. The flexible wiring board according to claim 8, wherein the wiring is tin-plated copper wiring. A method of manufacturing a flexible wiring board covered with a coating film, comprising the following (step 1) and (step 3) and the necessary (step 2): (step 1) by requesting The sclerosing composition printed in any one of items 1 to 5 a step of forming a printed film on the pattern on at least a part of the wiring pattern portion of the flexible wiring board, and (step 2) placing the printed film obtained in the step 1 in an atmosphere of 40 to 100 ° C And the step of evaporating a part or the whole amount of the solvent in the printing film, (step 3) is performed by heating the printed film obtained in the step 1 or the printing film obtained in the step 2 at 100 to 170 ° C to form a coating. The step of the membrane. An electronic component characterized by having a cured film as recited in claim 6.