TW201731898A - Curable composition and use of same - Google Patents

Abstract

The purpose of the present invention is to provide a curable composition which is capable of providing a cured product having low warping properties and excellent long-term electrical insulation reliability, while being suppressed in bleeding during screen printing. A curable composition according to the present invention contains the following components (a)-(d). Component (a): a polyurethane having a carbonate bond and a functional group that is reactive with an epoxy group Component (b): a solvent containing the component (b1) described below Component (c): a compound having two or more epoxy groups in each molecule Component (d): at least one component selected from among inorganic fine particles, organic fine particles and organic/inorganic composite fine particles Component (b1): at least one component selected from among 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate.

Description

Sturdy composition and use thereof

The present invention relates to a hardenable composition and its use.

Conventionally, a resist ink for forming a protective film or the like on a wiring board is an inorganic filler, and is used as a means for improving the screen printing property (preventing leakage during screen printing) for fine pitching of wiring. (For example, refer to Patent Documents 1 and 2). However, there are problems in that impurities or re-agglomerates from the inorganic filler become defects and the electrical insulating properties of the resist are lowered. Further, a method of forming a resist on a wiring board is generally performed by screen printing.

In addition, a technique of providing a special filler in a resist ink is known as a means for improving the screen printing property and electrical insulation reliability for fine pitching (for example, see Patent Document 3).

However, with the development of the semi-additive method, it is expected that the distance between wirings of the flexible wiring board will become narrower (for example, a pitch of 20 μm or less).

With this narrower pitch, it is necessary to develop a more excellent resist ink (curable composition) for leakage prevention during screen printing.

In addition, when focusing on a polyurethane having a functional group and a carbonate bond which is required for the hardening reaction of a resist, a polyamino group having an acid anhydride group and/or an isocyanate group and a carbonate bond is contained. The curable composition of the acid ester is known (for example, refer to Patent Documents 5, 6, and 7). However, none of Patent Documents 4 to 7 does not describe leakage prevention during screen printing.

In addition, as a curable composition having a small amount of leakage during screen printing, a curable composition containing γ-butyrolactone or a specific polyurethane is known (for example, see Patent Document 8). However, γ-butyrolactone has a problem of producing 4-hydroxybutyric acid of an anesthetic by hydrolysis.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-113338

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-214413

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-100038

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-198105

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2006-117922

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2007-39673

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-201847

[Patent Document 8] International Publication No. 2010/73981

[Summary of the Invention]

An object of the present invention is to provide a curable composition which exhibits less leakage at the time of screen printing even without using γ-butyrolactone as a solvent.

More specifically, it is an object of the present invention to provide a cured product which is excellent in low warpage and long-term electrical insulation reliability even when γ-butyrolactone as a solvent is not used, and has less leakage during screen printing. a hardening composition.

As a result of intensive studies to solve the above problems, the present inventors have found that a curable composition containing a polyurethane having a specific structure and a specific solvent is printed on a flexible wiring by a screen printing method. On the board, the printed matter (curable composition) has less leakage, and the warpage of the flexible wiring board when the curable composition is hardened is small, and the cured product obtained by curing the curable composition is long-term electricity. The insulating property is excellent, and the present invention has been completed.

That is, the present invention relates to, for example, the following (1) to (12).

(1) A curable composition comprising the following components (a) to (d),

Ingredient (a): a polyurethane having a functional group reactive with an epoxy group and a carbonate bond

Ingredient (b): a solvent containing the following component (b1)

Component (c): a compound having two or more epoxy groups in one molecule

Ingredient (d): selected from inorganic microparticles, organic microparticles and organic. At least one component of the inorganic composite fine particles

Component (b1): at least one component selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate.

(2) The curable composition of (1), wherein the component (b) comprises the following component (b2), the component (b2): selected from the group consisting of diethylene glycol diethyl ether acetate and dipropylene glycol methyl ether acetate At least one component of the ester.

(3) The curable composition according to (1) or (2), wherein the component (b) comprises the following component (b3), component (b3): diethylene glycol diethyl ether.

(4) The curable composition according to any one of (1) to (3) wherein the functional group reactive with the epoxy group is selected from the group consisting of a carboxyl group, an isocyanate group, a blocked isocyanate group, and a ring. At least one functional group in which the acid anhydride group and the phenolic hydroxyl group are grouped.

(5) The hardenable composition of (3), wherein the ratio of the total mass of the aforementioned component (b1) and component (b3) to the mass of the component (b2) (the total mass of (b1) and (b3): The quality of (b2) is 80:20~30:70.

(6) The curable composition according to any one of (1) to (5), wherein the curable composition is 100% by mass or more, and contains 20 to 70% by mass of the component (b) and the component ( The ratio of the number of functional groups reactive with an epoxy group contained in a) to the number of epoxy groups in the component (c) (a functional group reactive with an epoxy group) The base/epoxy group is 1/3 to 2/1, and contains 1 to 150 masses based on 100 parts by mass of the total amount of the components remaining after the component removal component (d) contained in the self-curable resin composition. Ingredients (d).

(7) The curable composition according to any one of (1) to (6) wherein the component (d) is cerium oxide microparticles.

(8) The curable composition according to any one of (1) to (7), wherein the component (c) is a compound having at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure.

(9) The curable composition of (8), wherein the component (c) is a compound having a tricyclodecane structure and an aromatic ring structure.

(10) A cured product obtained by curing the curable composition according to any one of (1) to (9).

(11) A cured wiring board coated with a cured material, wherein at least a part of a surface of the flexible wiring board on which the wiring is formed is formed on the flexible substrate, as in (10) The hardened material is covered.

(12) A method of producing a flexible wiring board coated with a protective film, which is obtained by printing a curable composition according to any one of (1) to (9) to a flexible wiring board At least a part of the tinned wiring pattern portion forms a printed film on the pattern, and the printed film is cured by heating at 80 to 130 ° C to form a protective film.

In the curable composition of the present invention, when the curable composition of the present invention is printed on a flexible wiring board by screen printing without using γ-butyrolactone as an anesthetic material, leakage of the printed matter can be suppressed.

Moreover, when the curable composition of the present invention is used, the warpage of the flexible wiring board on which the composition is printed during curing is small. Further, the cured product obtained by curing the curable composition is excellent in long-term electrical insulating properties.

Therefore, the curable composition of the present invention can be used as a resistive ink for insulation protection of a wiring represented by a solder resist ink, and the cured product of the present invention can be used as a protective film for a barrier for insulation protection of wiring.

[Formation of the Invention]

Next, the present invention will be specifically described.

The present invention (I) can provide a cured product having low warpage and excellent long-term electrical insulation reliability, and a hardening composition having less leakage during screen printing, and the present invention (II) is based on the present invention (I) The cured product obtained by curing the curable composition, (III) is a flexible wiring board in which at least a part of the cured product of the invention (II) is coated, and the flexible wiring board of the invention (IV) is produced. method.

Hereinafter, the present invention (I) to (IV) will be described in order.

[Invention (I)]

The present invention (I) is a curable composition containing the following components (a) to (d).

Ingredient (a): having a functional group capable of reacting with an epoxy group and a carbonate Polyurethane

Ingredient (b): a solvent containing the following component (b1)

Component (c): a compound having two or more epoxy groups in one molecule

Ingredient (d): selected from inorganic microparticles, organic microparticles and organic. At least one component of the inorganic composite fine particles

Component (b1): at least one component selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate.

The curable composition of the present invention (I) can provide a cured product excellent in low warpage and long-term electrical insulation reliability, and has less leakage at the time of screen printing. The curable composition (I) of the present invention is preferred because it does not substantially use γ-butyrolactone as a solvent and achieves the above characteristics. That is, the curable composition of the present invention (I) is preferably γ-butyrolactone of less than 1000 wtppm, particularly preferably γ-butyrolactone.

Explain the following ingredients.

<ingredient (a)>

The curable composition of the present invention (I) contains, as component (a), a polyurethane having a functional group capable of reacting with an epoxy group and a carbonate bond (hereinafter sometimes referred to simply as "polyurethane" A").

The "functional group reactive with an epoxy group" in the component (a) is not particularly limited as long as it can react with the epoxy group of the component (c) to be described later. Examples of the functional group reactive with the epoxy group include a carboxyl group, an isocyanate group, a blocked isocyanate group, and a cyclic group. An acid anhydride group, a phenolic hydroxyl group or the like. The functional group which can react with the epoxy group may contain only one type or two or more types in the component (a).

When considering the reactivity with a compound having two or more epoxy groups in one molecule of the component (c), among these, a preferred functional group is a carboxyl group, a blocked isocyanate group, and a cyclic acid anhydride group. . Further, in consideration of the balance between the storage stability and the reactivity of the component (a), the functional group is preferably a carboxyl group or a blocked isocyanate group, and a particularly preferred functional group is a carboxyl group.

The method for producing the polyurethaneuric acid A is not particularly limited, and for example, a (poly)carbonate polyol, a polyisocyanate compound, a diol having a functional group reactive with an epoxy group, and if necessary, a poly(poly) can be used. The carbonate polyol and a polyol, a monohydroxy compound, and a monoisocyanate compound other than a diol which can react with a functional group reactive with an epoxy group are reacted and synthesized. Further, another method is a polyamine group which can be obtained by reacting a (poly)carbonate polyol, a polyisocyanate compound, a polyol other than a (poly)carbonate polyol, a monohydroxy compound, or a monoisocyanate compound. In the formic acid ester, a functional group reactive with an epoxy group is introduced to synthesize it.

More specifically, the polyurethaneuric acid A can be produced, for example, by the following method.

A method for producing a polyurethane having a polyurethane which is a carboxyl group reactive with an epoxy group, for example, by a known urethane in dibutyltin dilaurate In the presence or absence of a catalyst, a (mixed) solvent containing at least one selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate is used. , (poly)carbonate polyol, polyisocyanate compound, carboxyl group-containing diol, if necessary The (poly)carbonate polyol and a polyol other than a carboxyl group-containing diol, a monohydroxy compound, and a monoisocyanate compound are reacted and synthesized. Although this reaction is carried out without a catalyst, it is preferable to improve the physical property value at the time of actual use of the cured film obtained from the curable composition (polyurethane solution) of the present invention (I).

In the present invention, "(poly)carbonate" is used in the sense of a monocarbonate having one carbonate bond in a molecule and a polycarbonate having two or more carbonate bonds in a molecule. The (poly)carbonate polyol of the raw material of the polyurethane resin A is not particularly limited as long as it is a compound having one or more carbonate bonds in the molecule and two or more alcoholic hydroxyl groups. That is, the (poly)carbonate polyol is a compound selected from at least one of a monocarbonate polyol and a polycarbonate polyol. (Poly) carbonate polyols, for example, (poly)carbonate diol having two hydroxyl groups in one molecule, (poly)carbonate triol having three or more hydroxyl groups in one molecule, and (poly)carbonate four Alcohol, etc.

The above (poly)carbonate polyol can be obtained by reacting a polyol mixture of a diol or a main component as a diol with a carbonate or phosgene. For example, when a diol is used as a raw material of a (poly)carbonate polyol which reacts with the above-mentioned carbonate or phosgene, a (poly)carbonate diol is produced, and the structure is represented by the following formula (1).

In the formula (1), (n+1) of R ¹ are each independently a residue after removing a hydroxyl group from the corresponding diol, and preferably each independently is an alkylene group having a carbon number of 3 to 18, and n is Natural number, usually n is an integer from 3 to 50.

The diol used in the production of the (poly)carbonate diol represented by the above formula (1), specifically, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Alcohol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol , 2-methyl-1,8-octanediol, 2-ethyl-4-butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,10- Decylene glycol or 1,2-tetradecanediol and the like.

The above (poly)carbonate polyol may also be a (poly)carbonate polyol (copolymerized (poly)carbonate polyol) having a plurality of alkylene groups in its skeleton. The use of the copolymerized (poly)carbonate polyol is preferably from the viewpoint of preventing crystallization of the polyurethane grease A. Further, when considering the solubility of the reaction solvent (3-methoxy-3-methyl-1-butyl acetate or ethylene glycol butyl ether acetate) of the polyurethane formate A synthesis reaction, Preferably, the branch skeleton is a (poly)carbonate polyol having a hydroxyl group at the end of the branch.

The (poly)carbonate polyols described above may be used singly or in combination of two or more.

a polyisocyanate compound of a raw material of polyurethane grease, as long as it is When the compound having two or more isocyanate groups is not particularly limited. Specific examples of the polyisocyanate compound include, for example, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl group). Base) cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, diphenylmethane- 4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biuret of isophorone diisocyanate, hexamethylene diisocyanate Diurea, isomeric isocyanate of isophorone diisocyanate, trimeric isocyanate of hexamethylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornene diisocyanate, and the like.

In order to maintain the high electrical insulating properties of the cured product of the present invention (II) to be described later, the polyisocyanate compound is preferably 1,4-cyclohexane diisocyanate, isophorone diisocyanate or methylene bis (4-ring). Hexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, diphenylmethane-4,4'-diisocyanate , 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexane Methylene diisocyanate and norbornane diisocyanate are more preferably methylene bis(4-cyclohexyl isocyanate), diphenylmethane-4,4'-diisocyanate and norbornane diisocyanate.

The polyisocyanate compound may be used singly or in combination of two Used on.

The polyurethane grease A is a polyaminocarbamate having a carboxyl group which is a functional group reactive with an epoxy group, and as the raw material, a carboxyl group-containing diol can be used as described above. The carboxy group-containing diol is not particularly limited as long as it is a compound having one or more carboxyl groups in the molecule and has two alcoholic hydroxyl groups.

Specific examples of the diol having a carboxyl group include, for example, dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and N,N-bis(hydroxyethyl)glycine. Among these, hydroxymethylpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferable from the viewpoint of the solubility of the reaction solvent used in the synthesis of the polyurethaneuric acid A. These carboxy group-containing diols may be used singly or in combination of two or more.

The polyhydric alcohol other than the (poly)carbonate polyol to be used as the raw material of the polyurethane urethane A is not particularly limited as long as it is a polyhydric alcohol other than the (poly)carbonate polyol. As a raw material of the polyurethane grease, a (poly)carbonate polyol and a polyol other than the diol having a functional group reactive with an epoxy group may be used as long as it is a (poly)carbonate polyol. The polyol other than the diol having a functional group reactive with an epoxy group, and is not particularly limited. Further, as a raw material of the polyurethane grease A, a polyhydric alcohol other than the (poly)carbonate polyol and the carboxyl group-containing diol which are used as necessary, as long as it is a (poly)carbonate polyol, and contains a carboxyl group The polyol other than the alcohol is not particularly limited. Specific examples of such polyols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentane. Alcohol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol , 2-ethyl-4-butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,10-nonanediol or 1,2-tetradecanediol A compound having three or more alcoholic hydroxyl groups in one molecule such as diol, trimethylolpropane, trimethylolethane, glycerol or pentaerythritol.

In general, the polyol of the above-mentioned polyol can be used for the production of polyurethane A directly or in addition to the polyol component remaining in the production of the (poly)carbonate polyol. Further, these polyols may be used singly or in combination of two or more.

As a raw material of the polyurethaneuric acid A, the monohydroxy compound used as necessary, as long as it has one alcoholic hydroxyl group in the molecule, does not have a reaction with an isocyanate group rather than an alcoholic hydroxyl group. The compound of the functional group is not particularly limited. Specific examples of the monohydroxy compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, ethylene glycol monoethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monopropyl ether.

These monohydroxy compounds may be used singly or in combination of two or more.

As a raw material of the polyurethane grease A, a monoisocyanate compound to be used as necessary, and cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, tolyl isocyanate, or the like can be used. In view of the discoloration resistance upon heating of the curable composition of the present invention (I), cyclohexyl isocyanate and octadecyl isocyanide are preferred. Acid ester.

As described above, the polyurethane grease A is a polyaminourethane having a carboxyl group which is a functional group reactive with an epoxy group, for example, by the presence of a known urethane catalyst or In the absence of (poly)carbonic acid, using at least one (mixed) solvent selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate The ester polyol, the polyisocyanate compound, the carboxyl group-containing diol, a polyol (poly)carbonate polyol, and a carboxyl group-containing diol other than a polyol, a monohydroxy compound, or a monoisocyanate compound are reacted and synthesized. The order in which the raw materials are put into the reactor is not particularly limited, and usually, a (poly)carbonate polyol, a carboxyl group-containing diol, and, if necessary, a (poly)carbonate polyol and a polyol other than the carboxyl group-containing diol are introduced. In the reactor, it is dissolved in a solvent. Then, the polyisocyanate compound is added dropwise at 20 to 140 ° C, more preferably 60 to 120 ° C, and then the above components are reacted at 50 to 160 ° C, more preferably 60 to 150 ° C.

The input of the raw material is adjusted by the molecular weight and acid value of the polyurethane for a purpose. The molecular weight of the target polyurethane can be adjusted by using a monohydroxy compound. That is, when the desired number average molecular weight is obtained (or the number average molecular weight close to the target), the isocyanate group at the terminal is blocked, and a monohydroxy compound may be added in order to suppress an increase in the number average molecular weight.

In the case of using a monohydroxy compound, the polyisocyanate compound is different from the total number of hydroxyl groups of the (poly)carbonate polyol, the carboxyl group-containing diol, and the (poly)carbonate polyol and the polyol other than the carboxyl group-containing diol. The number of cyanate groups can be small, or the same or more, without problems.

Further, in the case where the monohydroxy compound is excessively used, the unreacted monohydroxy compound remains as a result. However, the excess monohydroxy compound may be used as a part of the solvent as it is, or may be removed by distillation or the like.

The monohydroxy compound is introduced into the polyurethane A system in order to suppress an increase in the molecular weight of the polyurethane (that is, to stop the reaction). In order to introduce a monohydroxy compound into the polyurethane, the monohydroxy compound is dropped into the solution at 20 to 150 ° C, more preferably 70 to 140 ° C, and then the reaction is terminated while maintaining the same temperature.

Further, in order to introduce a monohydroxy compound into the polyurethane, it is compared with a (poly)carbonate polyol, a carboxyl group-containing diol, and a (poly)carbonate polyol and a polyol other than the carboxyl group-containing diol. The number of total hydroxyl groups must be such that the number of isocyanate groups of the polyisocyanate compound is less than that, so that the terminal of the polyglycolate molecule becomes a hydroxyl group. In order to terminate the reaction between the total hydroxyl groups of the (poly)carbonate polyol, the carboxyl group-containing diol, and the (poly)carbonate polyol and the polyol other than the carboxyl group-containing diol and the isocyanate group of the polyisocyanate compound, When the hydroxyl group at the terminal of the polyurethane is reacted with the monoisocyanate compound, the monoisocyanate compound is dropped into the solution of the polyurethane at 20 to 150 ° C, more preferably 70 to 140 ° C, and then kept in the solution. The reaction was terminated at the same temperature.

For example, the number average molecular weight of the polyurethaneuric acid A obtained above is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, particularly preferably from 5,000 to 30,000.

The "number average molecular weight" as used herein means a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC). When the number average molecular weight is less than 1,000, the elongation, flexibility, and strength of the cured film are impaired, and when the number average molecular weight exceeds 100,000, the polyurethane is applied to the solvent (for example, the component in the curable composition (b1) The solubility of (b2)) is lowered, and the viscosity is high even when dissolved, and the use of the curable composition of the invention (I) is limited.

Further, in the present specification, when there is no special statement, the measurement conditions of the GPC are as follows.

Device name: Japan Separation Co., Ltd. HPLC unit HSS-2000

Column: Shodex Column LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus made by Japan Spectrophotometer

Temperature: 40.0 ° C

Sample volume: sample loop 100 μL

Sample concentration: adjusted to about 0.1% by mass.

The acid value of the polyurethane A is preferably from 5 to 120 mgKOH/g, more preferably from 10 to 50 mgKOH/g. When the acid value is less than 5 mgKOH/g, the reactivity of the component (c) or the like described later as a curing agent to the other components contained in the curable composition of the invention (I) is lowered, and the curable composition is The heat resistance of the cured product is lowered. In addition, when the acid value exceeds 120 mgKOH/g, the cured film becomes Hard and brittle.

The polyurethane A coefficient has an average molecular weight of 1,000 to 100,000, and the acid value is 5 to 120 mgKOH/g of the polyurethane, more preferably the number average molecular weight is 3,000 to 50,000, and the acid value is 10 to 50 mgKOH. / g of polyurethane.

Further, in the present specification, the acid value of the polyurethane A is a value of the acid value measured by the potentiometric titration method of JIS K0070.

Further, the polyurethane is a method for producing a polyurethane having a blocked isocyanate group which is a functional group reactive with an epoxy group, for example, by containing the aforementioned (poly)carbonate The ratio of the number of hydroxyl groups in the raw material of the polyol and the polyisocyanate compound to the number of isocyanate groups (the number of hydroxyl groups / the number of isocyanate groups) is set to be less than 1.0 to produce a terminal isocyanate group-containing polyurethane, and then The terminal isocyanate group can be obtained by blocking the block using an isocyanate group.

It is preferred that the reaction temperature at which the isocyanate group is blocked is carried out at a temperature lower than the dissociation temperature of the block agent.

Further, the polyurethane having a molecular terminal block may be a polyurethane which uses the carboxyl group-containing diol as a raw material, or a polyurethane which does not use the carboxyl group-containing diol.

The blocker of the above isocyanate group may, for example, be a pyrazole compound such as dimethylpyrazole, an active methylene compound such as dimethyl malonate, ethyl acetate or ethyl acetonate or a methyl ethyl group. A quinone compound such as a ketoxime or the like, a caprolactam compound such as ε-caprolactam or a phenolic compound such as p-hydroxybenzoic acid methyl ester, p-benzoic acid ethyl ester or p-benzoic acid butyl ester.

Among these, preferred compounds are those in which the solvent is dried or the hardening reaction in the case of producing the cured product of the present invention (II) is vaporized and released to the hardened material, and the examples thereof are dimethyl. Pyridyl, methyl ethyl ketone oxime, dimethyl malonate, acetyl ketone and ε-caprolactam are more preferably dimethylpyrazole or methyl ethyl ketoxime. These may be used alone or in combination of two or more.

As described above, the functional group reactive with the epoxy group may be a cyclic acid anhydride group, but the polyurethane A is a polyurethane having a cyclic acid anhydride group which is a functional group reactive with an epoxy group. In the case, for example, [0023] to [0067] of JP-A-2003-198105 and the polyaminourethane having a quinone imine bond and having a cyclic acid anhydride group and a carbonate bond described in Example 1 can be cited.

Further, the amount of the component (a) in the curable composition of the invention (I) is preferably 100% by mass based on the curable composition, and the component (a) is preferably 20 to 75% by mass, and preferably 35 to 65% by mass. Better.

<ingredient (b)>

The curable composition of the invention (I) contains a solvent as the component (b). Component (b) contains the following component (b1).

Component (b1): at least one component selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate

The component (b) is a solvent in the curable composition of the invention (I), and the component (b1) is contained as an essential component, and may contain another solvent.

Further, the component (b) may contain the following component (b2).

Component (b2): at least one component selected from the group consisting of diethylene glycol diethyl ether acetate and dipropylene glycol methyl ether acetate

Further, the component (b) may also contain the component (b3).

Ingredient (b3): diethylene glycol diethyl ether

The curable composition of the invention (I) contains the solvent as the component (b), but the component (b) may contain the component (b2) and the component (b3) as long as it contains the component (b1).

By using the component (b1), the curable composition of the invention (I) is used as a resist ink for insulation protection of wiring, and when printing by a screen printing method, leakage of ink can be remarkably suppressed. Further, 3-methoxy-3-methyl-1-butyl acetate or ethylene glycol butyl ether acetate has a ignition point of 70 ° C or more, and is preferably a safety surface.

In addition, depending on the temperature of the printing place, etc., the solvent used in the ink, that is, the component (b) is only the component (b1), and the ink is continuously printed by the screen printing method. The drying speed is large, and the number of sheets that can be continuously printed is small, and there are restrictions. In order to avoid such a problem, as the component (b) (solvent), a ratio of 3-methoxy-3-methyl group may be used in combination within a range which does not affect the solubility of the above component (a) or the leakage of the aforementioned ink. -1-butyl acetate or ethylene glycol butyl ether acetate, a less volatile solvent, and is preferably used in combination.

In the curable composition of the invention (I), a solvent other than the component (b1) is used as an optional component in order to suppress the component (b1) in the curable composition of the invention (I) in the general screen printing method. Production The volatilization causes a lot of changes in the viscosity of the curable composition. For the purpose, in the case of using a solvent other than the component (b1), the solvent preferably has a boiling point of 200 to 250 °C.

Examples of such a solvent include diethylene glycol diethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl-n-propyl ether, and diethylene glycol butyl group. Ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of diethylene glycol diethyl ether acetate and dipropylene glycol methyl ether acetate is preferred.

Further, at least one component selected from the group consisting of diethylene glycol diethyl ether acetate and dipropylene glycol methyl ether acetate is also referred to as "component (b2)".

The curable composition of the present invention (I) contains the component (b1) and the component (b2), and is preferable from the viewpoint of the continuous printing property of the ink and the suppression of leakage of the ink.

In consideration of the balance between the continuous printing property of the ink and the leakage inhibition of the ink, the ratio of use of the component (b1) to the component (b2) is preferably such that when the component (b3) is contained, the amount of the component (b3) is used. It cannot be generalized, but in general, in terms of mass ratio, component (b1): component (b2) = 100:0 to 20:80, and more preferably component (b1): component (b2) = 80:20 ~30:70 range.

Further, the curable composition of the present invention (I) may further contain components other than the components (b1) and (b2) insofar as the solubility of the component (a) is not impaired and the continuous printing performance of the ink is not impaired. Solvent.

Such a solvent may, for example, be 3-methoxybutylacetic acid. Ester, 4-methoxybutyl acetate, 2-ethoxyethyl acetate, diethylene glycol diethyl ether, and the like. Among these, diethylene glycol diethyl ether is preferred.

Further, diethylene glycol diethyl ether is also referred to as "ingredient (b3)".

Considering the balance between the continuous printability of the ink and the leakage inhibition of the ink, the ratio of the total mass of the component (b1) and the component (b3) to the mass of the component (b2) (the total mass of (b1) and (b3): The mass of (b2) is preferably from 100:0 to 20:80, more preferably from 80:20 to 30:70.

The solvent used in the curable composition of the invention (I), that is, the total amount of the component (b1), the component (b2) and the component (b3) with respect to 100% by mass of the total amount of the component (b) Preferably, it is 70% by mass or more, and more preferably 80% by mass or more. Further, the total amount of the component (b1), the component (b2), and the component (b3) may be 100% by mass.

In addition, when the curable composition of the present invention (I) is 100% by mass, the component (b) is preferably 20 to 70% by mass, more preferably 30 to 55% by mass.

In addition, the "boiling point" described in this specification means the boiling point at normal pressure (that is, 101,325 Pa) when it is not specifically stated.

<ingredient (c)>

The curable composition of the present invention (I) contains a compound having two or more epoxy groups in one molecule of the component (c). Further, the number of epoxy groups in the molecule of the component (c) is preferably 4 or less. Component (c) functions as a curing agent in the curable composition of the invention (I).

Examples of the compound having two or more epoxy groups in one molecule include phenol novolac type epoxy resin and o-cresol novolac type epoxy resin, phenol, cresol, xylenol, and resorcinol. , catechol, phenols and/or α-naphthol, β-naphthol, dihydroxynaphthalene and the like naphthols and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde (Salicylaldehyde), etc. a phenolic aldehyde-type epoxy resin obtained by condensing or co-condensing a novolak resin obtained under an acidic catalyst; bisphenol A, bisphenol F, bisphenol S, alkyl substituted or unsubstituted Di-epoxypropyl ethers such as benzenediol and decidine phenols (bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol S epoxy compound, biphenyl epoxy compound, hydrazine) Type epoxy compound); diglycidyl ether of alcohol such as butanediol, polyethylene glycol, polypropylene glycol; glycerol of carboxylic acid such as phthalic acid, isophthalic acid or tetrahydrophthalic acid An ester type epoxy resin; an active hydrogen bonded to a nitrogen atom such as aniline, bis(4-aminophenyl)methane or iso-cyanuric acid An epoxy resin of a propyl-substituted compound or the like, an epoxy group of a propylene-propyl group or a methyl epoxypropyl group; an active hydrogen bonded to a nitrogen atom of an aminophenol such as a p-aminophenol, and a phenolic hydroxyl group An epoxy epoxide type or methyl epoxy propyl type epoxy resin of a compound in which an active hydrogen is substituted with a glycidyl group; a vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro (3,4- An alicyclic epoxy resin such as epoxy)cyclohexane-m-dioxane; a glycidyl ether of p-xylylene and/or m-xylylene-modified phenol resin; a terpene-modified phenol a glycidyl ether of a resin; a glycidyl ether of a dicyclopentadiene-modified phenol resin; a glycidyl ether of a cyclopentadiene-modified phenol resin; a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; The naphthalene ring contains a propylene resin of a phenol resin; a halogenated phenol novolak type epoxy resin; a hydroquinone type epoxy resin; a trimethylolpropane type epoxy resin; and an olefin bond is oxidized by peracid such as peracetic acid. Linear aliphatic epoxy resin; Phenylmethane type epoxy resin; epoxide of aralkyl type phenol resin such as phenol aralkyl resin, naphthol aralkyl resin; sulfur atom containing epoxy resin; tricyclic [5, 2, 1, 0 ^2,6 ]decane dimethanol diglycidyl ether; 1,3-bis(1-adamantyl)-4,6-bis(epoxypropyloxy)benzene, 1-[2',4 '-Bis(epoxypropyloxy)phenyl]adamantane, 1,3-bis(4'-epoxypropyloxyphenyl)adamantane and 1,3-double [2',4'- An epoxy resin having an adamantane structure such as bis(epoxypropyloxy)phenyl]adamantane.

Among these, a compound having a ring structure selected from at least one of an aromatic ring structure and an alicyclic structure is preferred.

When the long-term electrical insulating properties of the cured product of the present invention (II) are emphasized, the dicyclopentadiene-modified phenol is among the compounds having a ring structure selected from at least one of an aromatic ring structure and an alicyclic structure. a glycidyl ether of a 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(epoxypropyloxy)benzene, 1-[2',4'-bis(glycidoxy)phenyl]adamantane, 1, 3-Bis(4'-epoxypropyloxyphenyl)adamantane and 1,3-bis[2',4'-bis(glycidoxy)phenyl]adamantane, etc. with adamantane A structural epoxy resin (that is, a compound having a tricyclo[3,3,1,1 ^3,7 ]decane structure and an aromatic ring structure and having two or more epoxy groups), etc. The compound having an alkane structure and an aromatic ring structure can provide a cured product having a low water absorption ratio, and is preferably a compound of the following formula (2).

In the formula (2), l is a natural number, and is usually 0 to 3.

In addition, in the case of the reactivity with the component (a) in the curable composition of the invention (I), among the compounds having a ring structure selected from at least one of an aromatic ring structure and an alicyclic structure Epoxy propyl type or methyl epoxy propyl type epoxy resin in which an active hydrogen bonded to a nitrogen atom of aniline or bis(4-aminophenyl)methane is substituted with a glycidyl group, Active hydrogen bonded to a nitrogen atom of an aminophenol such as p-aminophenol and The active hydrogen of the phenolic hydroxyl group is preferably a compound having an amine group or an aromatic ring structure such as a glycopropyl type or a methyl epoxypropyl type epoxy resin substituted with a glycidyl group-substituted compound, etc., particularly preferably A compound of the following formula (3).

The component (c) may be used alone or in combination of two or more.

In the curable composition of the invention (I), the compounding amount of the component (c) per 100 parts by mass of the component (a) varies depending on the amount of the functional group reactive with the epoxy group in the component (a). Can not be generalized.

However, the number of functional groups which can be reacted with an epoxy group contained in the component (a) and the number of epoxy groups contained in the component (c) (a compound having two or more epoxy groups in one molecule) The ratio (functional group/epoxy group reactive with an epoxy group) is preferably 1/3 to 2/1, and more preferably 1/2.5 to 1.5/1. When the ratio is less than 1/3, when the curable composition of the present invention (I) is subjected to a curing reaction, there is a high possibility that the unreacted component (c) remains. Further, when the ratio is more than 2/1, the unreacted functional group in the component (c) which reacts with the epoxy group remains a lot, and the electrical insulating property is not preferable.

<ingredient (d)>

The curable composition of the invention (I), wherein the component (d) is selected from the group consisting of inorganic fine particles, organic fine particles and organic. At least one component of the inorganic composite fine particles.

Also, organic. Examples of the inorganic composite fine particles include fine particles in which a powdery inorganic compound is physically coated with an organic compound, fine particles in which a powdery inorganic compound is surface-treated with an organic compound, and a powdery organic compound physically covered with an inorganic compound. Microparticles, etc.

The inorganic fine particles used in the curable composition of the invention (I) are not particularly limited as long as they are dispersed and formed into a paste in the curable composition of the invention (I).

Examples of such 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 nitriding. Bismuth (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, carbon (C), etc. These may be used alone or in combination of two or more.

The organic fine particles used in the curable composition of the invention (I) are not particularly limited as long as they are dispersed in the curable composition of the invention (I).

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. The resin is preferably a polyimine resin or a precursor thereof, a polyamidamine resin or a precursor thereof, and a polyamide resin from the viewpoint of heat resistance and mechanical properties.

The average particle diameter of the component (d) (a component selected from at least one of inorganic fine particles, organic fine particles, and organic and inorganic composite fine particles) is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm.

The component (d) is preferably cerium oxide microparticles, and has no effect on the electrical insulating properties of the cured product.

In addition, the curable composition of the present invention (I) is 100 parts by mass based on the total amount of the components remaining after the total component removal component (d) contained in the curable resin composition, and the component (d) usually contains 1 part by mass. ~150 parts by mass, preferably 1 to 120 parts by mass, more preferably 1 to 60 parts by mass. In the above range, the balance between the fluidity at the time of screen printing of the composition and the shape retainability of the ink after printing is preferable.

<Other ingredients>

The curable composition of the present invention (I) may contain components other than the above components (other components).

The curable composition of the invention (I) may further contain a hardening The agent preferably contains a hardening accelerator.

The curing accelerator is not particularly limited as long as it can promote the reaction with the epoxy group of the component (c) and the functional group of the component (a) which can react with the epoxy group.

In the case where the functional group which the component (a) can react with the epoxy group is a carboxyl group, the hardening accelerator may, for example, be melamine, acetamide, benzoguanamine or 2,4-diamino-6- Methyl propylene oxiranyl-S-triazine, 2,4-methylpropenyloxyethyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, 2,4-Diamino-6-vinyl-s-triazine. a triazine-based compound such as an isomeric cyanuric acid addition product; imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2- Hexamethyl imidazole, 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-cyanoethyl-2-ethyl-4-methylimidazolium Pyromellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-Ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-di Amino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzyl Imidazolium chloride, N,N'-bis(2-methyl-1-imidazolylethyl)urea ,N,N'-bis(2-methyl-1-imidazolylethyl)hexan Adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4.5-dihydroxymethylimidazole, 2-methylimidazole. Iso-cyanuric acid adduct, 2-phenylimidazole. Iso-cyanuric acid adduct, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Iso-cyanuric acid adduct, 2-methyl-4-carbamimidazole, 2-ethyl-4-methyl-5-methylpyridyl imidazole, 2-phenyl-4-methylformamido Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 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 Imidazole-based compound of 2-phenylimidazolium bromide salt, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, etc.; 1,5-diazabicyclo (4.3.0) An amidine compound such as a terpene-5 and a salt thereof, a 1,8-diazabicyclo (5.4.0) undecene-7 and a salt thereof, and the like, and a derivative thereof; a compound containing a tertiary amino group such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol; triphenylphosphine, diphenyl (p-tolyl)phosphine, cis (alkylphenyl)phosphine, cis (alkoxyphenyl)phosphine, cis (alkyl.alkoxyphenyl)phosphine, cis (dialkylphenyl)phosphine , ginseng (trialkylphenyl) phosphine, ginseng (tetraalkylphenyl) phosphine, Paraxyl (dialkyloxyphenyl) phosphine, quinone (trialkoxyphenyl) phosphine, cis (tetraalkoxyphenyl) phosphine, trialkyl phosphine, dialkyl aryl phosphine, alkyl diaryl An organic phosphine compound such as phosphine; dicyandiamide or the like.

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

Among these hardening accelerators, when the electrical insulating property of the cured product of the present invention (II) to be described later is also considered, the preferred hardening accelerator is melamine, an imidazole compound, a cyclic ruthenium compound and the like. a derivative, an organic phosphine compound and a compound containing a tertiary amino group, more preferably melamine, 1,5-diazabicyclo (4.3.0) nonene-5 and its salt, 1,8-diazabicyclo ring (5.4.0) Undecene-7 and its salts.

The amount of the hardening accelerator to be added is not particularly limited as long as it can achieve a hardening promoting effect. However, from the viewpoints of the curability of the curable composition of the invention (I) and the electrical insulating properties or water resistance of the cured product of the invention (II), the essential components of the curable composition of the invention (I) are The total amount of the component (a) and the component (c) is preferably 100 parts by mass, more preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3.0 parts by mass. When the amount is less than 0.05 parts by mass, the curing may be difficult in a short period of time. When the amount is more than 5 parts by mass, the cured product obtained by curing the composition may have insufficient electrical insulating properties or water resistance.

The curable composition of the present invention (I) can be used as a composition for an insulating protective film such as a resist for insulating protection of wiring, for example, since a curable composition of a cured product having excellent electrical insulating properties can be obtained.

When the curable composition of the present invention (I) is used as a composition for a barrier for insulating protection of wiring (that is, a resist ink composition for insulation for wiring), in order to eliminate or suppress the occurrence of printing For the purpose of foaming, an antifoaming agent can be used, and it is preferably used.

The above antifoaming agent is as shown in the text, as long as it has elimination It is not particularly limited as long as it suppresses the foaming action when the resist ink composition for insulating protection of the printed wiring is suppressed.

Specific examples of the antifoaming agent used in the curable composition of the present invention (I) include, for example, BYK-077 (manufactured by BYK Japan Co., Ltd.), SN DEFOAMER 470 (manufactured by SAN NOPCO Co., Ltd.), and TSA 750S (manufactured by Momentive Performance Materials Co., Ltd.). Polyoxane-based defoamer such as Silicone oil SH-203 (manufactured by Dow Corning Toray Co., Ltd.), Dappo SN-348 (manufactured by SAN NOPCO Co., Ltd.), Dappo SN-354 (manufactured by SAN NOPCO Co., Ltd.), and Dappo SN-368 ( Acetylene polymerization system defoamer such as SANPARCO230HF (made by Nippon Chemical Co., Ltd.), Surfynol DF-110D (made by Nisshin Chemical Industry Co., Ltd.), and Surfynol DF-37 (made by Nissin Chemical Industry Co., Ltd.) A diol-based antifoaming agent, a fluorine-containing polyfluorinated defoaming agent such as FA-630, or the like.

When an antifoaming agent is used, it is preferably a component, and in consideration of the effect of the antifoaming agent and the influence on other physical properties, the component (a), the component (b), the component (c), and the component (c) of the present invention (I) The total amount of the component (d) is 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

Further, in the curable composition of the invention (I), a surfactant such as a flat agent may be added if necessary, indigo blue, indocyanine green, iodine green, disazo yellow, crystal violet, carbon black, naphthalene. A well-known coloring agent such as black.

When a flat agent is used, the preferred amount thereof is compared with the effect of the flat agent and other physical properties, relative to the invention (I). The total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

When a coloring agent is used, it is preferably in an amount of, in consideration of the effect of the coloring agent and other physical properties, the component (a), the component (b), the component (c), and the component ((I)) The total amount of d) is 100 parts by mass, preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.7 part by mass.

Further, when it is necessary to suppress oxidative degradation of the component (a) and discoloration during heating, an antioxidant such as a phenol-based antioxidant, a phosphite-based antioxidant, or a thioether-based antioxidant may be added, and it is preferably added.

When an antioxidant is used, its preferred amount is the component (a), the component (b), the component (c), and the component (I) of the present invention (I) in consideration of the effect of the coloring agent and the influence on other physical properties. The total amount of d) is preferably 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

Also, if necessary, a flame retardant or a slip agent may be added.

The curable composition of the present invention (I) can be obtained by uniformly kneading and mixing a part or all of the components by a roll mill, a bead mill or the like. In the case of mixing one of the ingredients, the remaining ingredients can be mixed in actual use.

<Viscosity of the curable composition of the present invention (I)>

The viscosity of the curable composition of the invention (I) at 25 ° C, usually It is 10,000 to 100,000 mPa ‧ , preferably 20,000 to 60,000 mPa ‧ s. Further, in the present specification, the viscosity of the curable composition of the present invention (I) at 25 ° C is a Cone/Plate type viscometer (model of Brookfield Co., Ltd.: DV-II + Pro shaft type: CPE-52). The viscosity measured after 7 minutes from the start of the rotation at a number of revolutions of 10 rpm.

<Thixotropic index of the curable composition of the present invention (I)>

In addition, when the curable composition of the present invention (I) is used as a resist ink composition for insulation of a wiring, in order to improve the printability of the curable composition of the invention (I), the composition is It is preferred that the thixotropy index is set within a certain range.

Further, the "thixotropy index" described in the present specification is defined as the number of revolutions at 25 ° C measured using a Cone/Plate type viscometer (model of Brookfield Corporation; model of DV-II+Pro shaft; CPE-52). The viscosity at 1 rpm is the ratio of the viscosity at 10 rpm at 25 ° C (viscosity at 1 rpm / viscosity at rpm).

When the curable composition of the present invention (I) is used as a resist ink composition for insulation of wiring, the thixotropy index of the composition is good in order to improve the printability of the curable composition of the invention (I). It is preferably 1.1 or more, more preferably 1.1 to 3.0, and particularly preferably 1.1 to 2.5. When the curable composition of the present invention (I) is used as a solder resist ink composition, when the thixotropic index of the curable composition is less than 1.1, the composition is flowed after printing the curable composition. It is impossible to achieve a certain film thickness or to maintain a printed pattern. Further, when the thixotropy index of the curable composition is more than 3.0, the defoaming property of the coating film of the composition after printing may be deteriorated.

[Invention (II)]

Next, the cured product of the present invention (II) will be described.

The present invention (II) is a cured product obtained by curing the curable resin composition of the present invention (I).

The cured product of the present invention (II) is generally obtained by removing a part or the whole amount of the solvent in the curable composition of the invention (I), and then performing a hardening reaction by heating. In the case where the cured product of the present invention (II) is obtained as a coating film, for example, a coating film of a cured product can be obtained through the following first to third steps.

First step

The step of obtaining a coating film by printing the curable composition of the present invention (I) on a substrate or the like.

Second step

The coating film obtained in the first step is placed in an environment of 50 ° C to 100 ° C to evaporate the solvent in the coating film to obtain a portion of the solvent or a total amount of the removed coating film.

Third step

The coating film obtained in the second step is thermally cured in an environment of from 100 ° C to 250 ° C to obtain a thermally cured coating film (that is, a coating film of a cured product).

The first step is a step of printing a curable composition of the present invention (I) on a substrate or the like to obtain a coating film.

The printing method of the curable composition of the present invention (I) is not particularly limited, and for example, the curable composition can be coated by a screen printing method, a roll coater method, a spray method, a curtain coating method, or the like. The film is obtained by coating on a substrate or the like.

In the second step, the coating film obtained in the first step is placed in an environment of 50 ° C to 100 ° C to evaporate the solvent in the coating film to obtain a portion of the solvent or a total amount of the removed coating film. The time for removing the solvent is preferably 4 hours or shorter, more preferably 2 hours or shorter. Further, the time for removing the solvent is preferably 0.2 hours or longer, more preferably 0.4 hours or longer.

Further, the third step is a step of thermally hardening the coating film obtained in the second step in an environment of from 100 ° C to 250 ° C to obtain a thermally cured coating film (that is, a coating film of a cured product). The heat hardening time is preferably in the range of 20 minutes to 4 hours, and more preferably in the range of 30 minutes to 2 hours.

[Invention (III) and (IV)]

Finally, a flexible wiring board of the invention (III) and a method of manufacturing the flexible wiring board of the invention (IV) will be described.

In the invention (III), at least a part of the surface on which the wiring of the flexible wiring board formed by the wiring is formed on the flexible substrate is formed. A flexible wiring board covered with a cured product coated with a cured product of the present invention (II).

The present invention (IV) is a method for producing a flexible wiring board covered with a protective film, which is obtained by printing the curable composition of the present invention (I) onto a tinned wiring of a flexible wiring board. At least a part of the pattern portion forms a printed film on the pattern, and the printed film is cured by heating at 80 to 130 ° C to form a protective film.

The curable composition of the invention (I) can be used, for example, as a resist ink for insulation protection of wiring, and the cured product of the invention (II) can be used as an insulating protective film. In particular, for example, at least a part of the wiring of the flexible wiring board coated with a chip on film can be used as a resist for insulation protection of wiring.

The specific steps performed in the method for producing a flexible wiring board of the present invention (IV) will be described below. For example, a flexible wiring board formed with a protective film can be obtained through the following steps A to C.

Step A

The step of printing a film by screen-printing the curable composition of the present invention (I) onto a wiring pattern portion of a flexible wiring board which has been previously tin-plated.

Step B

By placing the printed film obtained in the step A in an environment of 40 to 100 ° C, the solvent in the printed film is evaporated to obtain a part or a full amount of the solvent. The step of removing the printed film.

Step C

The printing film obtained in the step B is thermally cured in an environment of 80 to 130 ° C to form a protective film of the flexible wiring board.

The temperature at which the solvent of the step B is evaporated is usually 40 to 100 ° C, preferably 60 to 100 ° C, and more preferably 70 to 90 ° C in consideration of the evaporation speed of the solvent and the rapid movement of the secondary step (step C). The time for evaporating the solvent of the step B is not particularly limited, and is preferably from 10 to 120 minutes, more preferably from 20 to 100 minutes. Further, the operation of the above step B is an operation performed as necessary, and after the operation of the step A, the operation of the step C is carried out immediately, and the hardening reaction and the removal of the solvent may be performed together.

The conditions of the thermal hardening performed in the step C are carried out in the range of 80 to 130 ° C from the viewpoint of preventing diffusion of the plating layer and obtaining preferable low warpage and flexibility as a protective film. The heat hardening temperature is preferably from 90 to 130 ° C, more preferably from 110 to 130 ° C. The heat hardening time in the step C is not particularly limited, and is preferably from 20 to 150 minutes, more preferably from 30 to 120 minutes.

[Examples]

Next, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

<Measurement of acid value of component (a)>

The acid value of the component (a) contained in the curable composition is measured by the following method: a component obtained by subjecting the solvent in the polyurethane solution obtained in the synthesis example and the comparative synthesis example to distillation under reduced pressure under heating (a) The acid value of (polyurethane A).

The acid value was measured by potentiometric titration according to JIS K0070 using the component (a) obtained by the above method.

The apparatus used in the potentiometric titration method is as follows.

Device name: Kyoto Electric Industrial Co., Ltd. Potentiometer automatic titrator AT-510

Electrode: Composite glass electrode C-173 manufactured by Kyoto Electronics Industry Co., Ltd.

<Measurement of the average molecular weight of the component (a)>

The number average molecular weight of the component (a) contained in the curable composition is measured by measuring the component (a) (polyurethane formate A) obtained by measuring the acid value of the component (a).

The number average molecular weight of the component (a) is a number average molecular weight in terms of polystyrene measured by GPC, and the measurement conditions of GPC are as follows.

Device name: Japan Separation Co., Ltd. HPLC unit HSS-2000

Column: Shodex column LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0mL/min

Detector: RI-2031Plus, Japan Spectrophotometer

Temperature: 40.0 ° C

Sample volume: sample loop (loop) 100μL

Sample concentration: adjusted to about 0.1% by mass.

<Measurement of viscosity of solution containing component (a)>

The viscosity of the polyurethane solution obtained by the synthesis example and the comparative synthesis example was measured by the following method.

Approximately 0.8 g of a polyurethane solution was used, and a Cone/Plate type viscometer (model of Brookfield Corporation; model of DV-II+Pro shaft; CPE-52) was used, and the temperature was started at 25.0 ° C and 5 rpm. The viscosity of the component (a) solution (polyurethane solution) was measured by measuring the viscosity after 7 minutes from the start of the measurement.

<Measurement of viscosity of hardening composition>

The viscosity of the curable composition was measured by the following method.

Approximately 0.6 g of the curable composition was used, and measurement was started using a Cone/Plate type viscometer (model of Brookfield Co., Ltd.; model of DV-II+Pro shaft; CPE-52) at a temperature of 25.0 ° C and a number of revolutions of 10 rpm. The viscosity after 7 minutes from the start of the measurement was measured as the viscosity of the curable composition.

<Measurement of thixotropy index>

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

A curable composition of about 0.6 g was used, and a Cone/Plate type viscometer (manufactured by Brookfield Co.; DV-II+Pro shaft type; CPE-52), measurement was started under conditions of a temperature of 25.0 ° C and a number of revolutions of 10 rpm, and the viscosity after 7 minutes from the start of the measurement was measured, and the viscosity was 10 rpm. Then, measurement was started under the conditions of a temperature of 25.0 ° C and a number of revolutions of 1 rpm, and the viscosity after 7 minutes from the start of the measurement was measured, and the viscosity was measured as a rotation number of 1 rpm.

Further, the thixotropy index is obtained by the following calculation.

Thixotropy index = [viscosity of 1 rpm] ÷ [viscosity of 10 rpm]

<Synthesis of Polyurethanes Having Carboxyl Groups and Carbonate Bonds> (Implementation Synthesis Example 1)

In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, C-1015N (manufactured by Kuraray Co., Ltd., (poly)carbonate diol and a diol used as a raw material of the (poly)carbonate diol (1, a mixture of 9-decanediol and 2-methyl-1,8-octanediol, hydroxyl group 112.3 mgKOH/g) (molar ratio of raw material diol; 1,9-nonanediol: 2-A) Base-1,8-octanediol=15:85, the residual concentration of 1,9-nonanediol in the mixture is 2.1% by mass, and the residual concentration of 2-methyl-1,8-octanediol is 9.3% by mass) 248.0 g, 47.5 g of 2,2-dimethylolbutanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as a carboxyl group-containing diol, and a trishydroxyl group as a polyol other than a (poly)carbonate polyol and a carboxyl group-containing diol 2.7 g of ethane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a solvent of 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)), 550.0 g, heated Dissolve all raw materials to 100 °C.

The temperature of the reaction solution was lowered to 90 ° C by means of a dropping funnel 150.4 g of methylene bis(4-cyclohexyl isocyanate) (trade name: DESMODUR W) manufactured as a polyisocyanate compound was dropped over 30 minutes. After the reaction was carried out for 8 hours at 120 ° C, it was confirmed by IR (infrared spectroscopy) that the absorption of the C=O stretching vibration from the isocyanate group was almost impossible to observe, and then 1.5 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped. The reaction was carried out at 80 ° C for 3 hours to obtain a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution A1").

The viscosity of the obtained polyurethane solution A1 is 350,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane AU1") contained in the polyurethane solution A1 has a number average molecular weight of 14,000, and a polyurethane. The acid value of AU1 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A1 was 45.0% by mass.

(Implementation Synthesis Example 2)

In addition to the solvent, 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray)), 550.0 g was substituted with ethylene glycol butyl ether acetate (manufactured by DAICEL Co., Ltd.) In the same manner as in the synthesis of Synthesis Example 1, a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution A2") was obtained in the same manner as in the above-mentioned Synthesis Example 1.

The viscosity of the obtained polyurethane solution A2 is 350,000 mPa. s. Further, the polyurethane is contained in the solution A2. The number average molecular weight of the polyurethane having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane AU2") is 14,000, and the acid value of the polyurethane AU1 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A2 was 45.0% by mass.

(Implementation Synthesis Example 3)

In addition to 550.0 g of 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray)), a solvent was substituted with diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.) 275 g and 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)), 275 g, were carried out in the same manner as in Synthesis Example 1, to obtain a carboxyl group and a carbonate. A key polyurethane solution (hereinafter referred to as "polyurethane solution A3").

The obtained polyurethane solution A3 has a viscosity of 300,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane AU3") contained in the polyurethane solution A3 has a number average molecular weight of 14,000, and a polyurethane. The acid value of AU3 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A3 was 45.0% by mass.

(Implementation Synthesis Example 4)

In addition to the solvent 3-methoxy-3-methyl-1-butyl acetate (commodity Name: solfit AC (manufactured by Kuraray Co., Ltd.) 55 kg of 245 g of diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.) and 275 g of ethylene glycol butyl ether acetate (manufactured by DAICEL Co., Ltd.), and Synthesis Example 1 In the same manner, a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution A4") was obtained.

The viscosity of the obtained polyurethane solution A4 is 300,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane AU4") contained in the polyurethane solution A4 has a number average molecular weight of 14,000, and a polyurethane. The acid value of AU3 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A4 was 45.0% by mass.

(Implementation Synthesis Example 5)

In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, C-1015N (manufactured by Kuraray Co., Ltd., (poly)carbonate diol and raw material diol (1,9-nonanediol and 2-methyl-1) were charged. , a mixture of 8-octanediol) (molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15:85, hydroxyl value: 112.3 mgKOH/g , the residual concentration of 1,9-nonanediol 2.1% by mass, the residual concentration of 2-methyl-1,8-octanediol 9.3% by mass) 250.9 g, 2,2-dihydroxyl as a carboxyl group-containing diol 47.5 g of butylbutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.7 g of trimethylolethane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a polyol other than a (poly)carbonate polyol and a carboxyl group-containing diol, and a solvent Diethylene glycol ether acetate (DAICEL) 233) 233.75g and 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (Kuraray)) 233.75g and diethylene glycol diethyl ether (Japanese emulsifier company) 82.5 g, heated to 100 ° C, dissolve all the raw materials.

The temperature of the reaction liquid was lowered to 90 ° C, and methylene bis(4-cyclohexyl isocyanate) as a polyisocyanate compound (trade name of Susei BAYER urethane company; DESMODUR W) 147.4 was used as a polyisocyanate compound by a dropping funnel. g dripped in 30 minutes. After reacting at 120 ° C for 7 hours, it was confirmed that the isocyanate was almost disappeared, and then 1.5 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped, and further reacted at 80 ° C for 3 hours to obtain a polyurethane having a carboxyl group and a carbonate bond. Solution (hereinafter referred to as "polyurethane solution A5").

The viscosity of the obtained polyurethane solution A5 is 300,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane AU5") contained in the polyurethane solution A5 has a number average molecular weight of 11,000, and a polyurethane. The acid value of AU5 was 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A5 was 45.0% by mass.

(Implementation Synthesis Example 6)

In place of 233.75 g of 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)), ethylene glycol butyl ether acetate (manufactured by DAICEL Co., Ltd.) ) 233.75g, and implementation synthesis In the same manner as in Example 5, a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution A6") was obtained.

The viscosity of the obtained polyurethane solution A6 is 99,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond contained in the polyurethane solution A6 (hereinafter referred to as "polyurethane AU6") has a number average molecular weight of 11,000, and a polyurethane. The acid value of AU6 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution A6 was 45.0% by mass.

(Comparative Synthesis Example 1)

In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, C-1015N (manufactured by Kuraray Co., Ltd., (poly)carbonate diol and raw material diol (1,9-nonanediol and 2-methyl-1) were charged. , a mixture of 8-octanediol) (molar ratio of raw material diol; 1,9-nonanediol: 2-methyl-1,8-octanediol = 15:85, hydroxyl value: 112.3 mgKOH/g , the residual concentration of 1,9-nonanediol 2.1% by mass, the residual concentration of 2-methyl-1,8-octanediol 9.3% by mass) 252.8 g, 2,2-dihydroxyl as a carboxyl group-containing diol 47.5 g of butylbutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 550.0 g of diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.) as a solvent were heated to 100 ° C to dissolve all the raw materials.

The temperature of the reaction liquid was lowered to 90 ° C, and methylene bis(4-cyclohexyl isocyanate) as a polyisocyanate compound was obtained by a dropping funnel (manufactured by BAYER Amino Acid Co., Ltd.); DESMODUR W) 145.6g dripped in 30 minutes. After reacting at 120 ° C for 8 hours, it was confirmed that the isocyanate was almost disappeared, and then 4.0 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped, and further reacted at 80 ° C for 3 hours to obtain a polyamino group having a carboxyl group and a carbonate bond. A formic acid solution (hereinafter referred to as "polyurethane solution B1").

The viscosity of the obtained polyurethane solution B1 is 70,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond contained in the polyurethane solution B1 (hereinafter referred to as "polyurethane sulphonide BU1") has a number average molecular weight of 12,000, and a polyurethane. The acid value of BU1 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution B1 was 45.0% by mass.

(Comparative Synthesis Example 2)

In addition to 550.0 g of a solvent of diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.), 467.5 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) and diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.) 82.5 g were substituted. In the same manner as in Comparative Synthesis Example 1, a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution B2") was obtained.

The viscosity of the obtained polyurethane solution B2 is 93,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond contained in the polyurethane solution B2 (hereinafter referred to as "polyurethane (BU2)" has a number average molecular weight of 13,000, and a polyurethane. The acid value of BU2 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution B2 was 45.0% by mass.

(Comparative Synthesis Example 3)

In addition to 550.0 g of a solvent of diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.), it was substituted with diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.), 467.5 g, and dipropylene glycol methyl ether acetate (manufactured by DAICEL Co., Ltd.) 82.5 g. In the same manner as in Comparative Synthesis Example 1, a polyurethane solution having a carboxyl group and a carbonate bond (hereinafter referred to as "polyurethane solution B3") was obtained.

The viscosity of the obtained polyurethane solution B3 is 97,000 mPa. s. Further, the polyaminocarbamate having a carboxyl group and a carbonate bond contained in the polyurethane solution B3 (hereinafter referred to as "polyurethane (BU3)" has a number average molecular weight of 14,000, and a polyurethane. The acid value of BU3 is 40.0 mg-KOH/g.

Further, the solid content concentration in the polyurethane solution B3 was 45.0% by mass.

(Implementing the deployment example 1)

Mixed polyurethane solution A1 (111.1 g), cerium oxide powder (trade name: AEROSILR-974, manufactured by AEROSIL, Japan), 5.0 g, melamine (manufactured by Nissan Chemical Industries, Ltd.) as a curing accelerator, 0.38 g, and defoaming Agent (trade name of Momentive performance materials company; TSA750S) 0.70g, using three-roll mill (Inoue system The company's model: S-4 3/4×11), a mixture of cerium oxide powder, a hardening accelerator and an antifoaming agent for the polyurethane solution A1. This formulation serves as the main agent complex C1.

(Implementation of blending examples 2 to 6 and comparative blending examples 1 to 3)

The blending was carried out according to the blending composition shown in Table 1 by the same method as in Formulation Example 1. The formulations prepared by the blending examples 2 to 6 were used as the main component formulations C2 to C6, respectively, and the formulations prepared by the blending examples 1 to 3 were used as the main component formulations D1 to D3, respectively. Also, the numerical value in the table indicates g.

<Manufacture of hardener solution> (Fixing agent solution preparation example 1)

In a container equipped with a stirrer, a thermometer, and a condenser, an epoxy resin having a structure of the following formula (2) (a grade name of DIC Corporation; HP-7200H epoxy equivalent: 278 g/eq) 300 g, 3-methoxy 300 g of benzyl-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)) was started to stir.

While stirring was continued, the temperature in the vessel was raised to 70 ° C using an oil bath. After the internal temperature was raised to 70 ° C, stirring was continued for 30 minutes. Then, after confirming that HP-7200H was completely dissolved, it was cooled to room temperature, and a solution containing HP-7200H having a concentration of 50% by mass was obtained. This solution was used as the hardener solution E1.

In the formula (2), l is a natural number, and in HP-7200H, l is a main component of 0 to 3, and the average value of l is 1.

(Example 2 of the preparation of the hardener solution)

In addition to 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (Kuraray)) 300g was replaced by ethylene glycol butyl ether A solution containing HP-7200H having a concentration of 50% by mass was obtained in the same manner as in the preparation example 1 of the curing agent solution, except for 300 g of the acid ester (manufactured by DAICEL Co., Ltd.). This solution was used as the hardener solution E2.

(Example 3 of the preparation of the hardener solution)

In addition, 300 g of 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)) was substituted with diethylene glycol diethyl ether acetate (manufactured by DAICEL Co., Ltd.) 300 g. In the same manner as in the preparation example 1 of the curing agent solution, a solution containing HP-7200H at a concentration of 50% by mass was obtained. This solution was used as the hardener solution E3.

(Formulation Example 4 of Hardener Solution)

In addition, 300 g of 3-methoxy-3-methyl-1-butyl acetate (trade name; solfit AC (manufactured by Kuraray Co., Ltd.)) was substituted with γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) 180 g and two A solution containing HP-7200H having a concentration of 50% by mass was obtained in the same manner as in the preparation example 1 of the curing agent solution, except that 120 g of diol diethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was used. This solution was used as the hardener solution E4.

<Mixing of a solution containing a main agent formulation and a hardener> [Example 1] (Preparation (manufacturing) of hardening composition)

The main ingredient formulation C1 (117.2 g) and the hardener solution E1 (19.8 g) were placed in a plastic container.

Further, in order to mix the curable composition and viscosity obtained in the other examples and comparative examples, 3-methoxy-3-methyl-1-butyl acetate as a solvent was added (trade name; solfit AC ( Kuraray company))) 5.0g.

The mixture was stirred at room temperature for 5 minutes using a spatula to obtain a curable composition (hereinafter referred to as "curable composition F1").

The viscosity of the hardening composition F1 is 50,000 mPa. s. The thixotropy index was 1.35. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition F1 (carboxyl/epoxy group) Is 1.0.

[Example 2] (Preparation (manufacturing) of hardening composition)

The main ingredient formulation C2 (117.2 g) and the hardener solution E2 (19.8 g) were placed in a plastic container.

In addition, in order to mix the curable composition and viscosity obtained by the other examples and the comparative examples, 5.0 g of ethylene glycol butyl ether acetate (manufactured by DAICEL Co., Ltd.) as a solvent was added.

The mixture was stirred at room temperature for 5 minutes using a doctor blade to obtain a curable composition (hereinafter referred to as "curable composition F2").

The viscosity of the curable composition F2 is 50,000 mPa. s. The thixotropy index was 1.36. The number of the carboxyl group (the functional group reactive with the epoxy group) contained in the component (a) and the ring in the component (c) of the curable composition F2 The ratio of the number of oxy groups (carboxyl/epoxy group) was 1.0.

[Example 3] (Preparation (manufacturing) of hardening composition)

A curable composition (hereinafter referred to as "curable composition F3") was obtained in the same manner as in Example 1 except that the main ingredient formulation C1 was replaced with the main ingredient formulation C3.

The viscosity of the curable composition F3 is 50,000 mPa. s. The thixotropy index was 1.34. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition F3 (carboxyl/epoxy group) Is 1.0.

[Example 4] (Preparation (manufacturing) of hardening composition)

A curable composition (hereinafter referred to as "curable composition F4") was obtained in the same manner as in Example 2 except that the main component formulation C2 was replaced with the main component formulation C4.

The viscosity of the hardening composition F4 is 50,000 mPa. s. The thixotropy index was 1.35. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition F4 (carboxyl/epoxy group) Is 1.0.

[Example 5] (Preparation (manufacturing) of hardening composition)

A curable composition (hereinafter referred to as "curable composition F5") was obtained in the same manner as in Example 1 except that the main ingredient formulation C1 was replaced with the main ingredient formulation C5.

The viscosity of the curable composition F5 is 50,000 mPa. s. The thixotropy index was 1.34. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition F5 (carboxyl/epoxy group) Is 1.0.

[Example 6] (Preparation (manufacturing) of hardening composition)

A curable composition (hereinafter referred to as "curable composition F6") was obtained in the same manner as in Example 2 except that the main component formulation C2 was replaced with the main component formulation C6.

The viscosity of the hardening composition F6 is 50,000 mPa. s. The thixotropy index was 1.36. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition F6 (carboxyl/epoxy group) Is 1.0.

[Comparative Example 1] (Preparation (manufacturing) of hardening composition)

The main ingredient formulation D1 (117.2 g) and the hardener solution E3 (19.8 g) were placed in a plastic container.

Further, in order to mix the curable composition and viscosity obtained in the other examples and comparative examples, diethylene glycol ether as a solvent was added. Acetate (manufactured by DAICEL) 3.0 g.

The mixture was stirred at room temperature for 5 minutes using a doctor blade to obtain a curable composition (hereinafter referred to as "curable composition G1").

The viscosity of the hardening composition G1 is 50,000 mPa. s. The thixotropy index was 1.34. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition G1 (carboxyl/epoxy group) Is 1.0.

[Comparative Example 2] (Preparation (manufacturing) of hardening composition)

The main ingredient formulation D2 (117.2 g) and the hardener solution E4 (19.8 g) were placed in a plastic container.

In addition, in order to mix the curable composition and viscosity obtained by the other examples and the comparative examples, 5.0 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent was added.

The mixture was stirred at room temperature for 5 minutes using a doctor blade to obtain a curable composition (hereinafter referred to as "curable composition G2").

The viscosity of the curable composition G2 is 50,300 mPa. s. The thixotropy index was 1.35. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition G2 (carboxyl/epoxy group) Is 1.0.

[Comparative Example 3] (Preparation (manufacturing) of hardening composition)

A curable composition (hereinafter referred to as "curable composition G3") was obtained in the same manner as in Comparative Example 1, except that the main component formulation D1 was replaced with the main component complex D3.

The viscosity of the hardening composition G3 is 50,500 mPa. s. The thixotropy index was 1.36. The ratio of the number of carboxyl groups (functional groups reactive with an epoxy group) contained in the component (a) to the number of epoxy groups in the component (c) of the curable composition G3 (carboxyl/epoxy group) Is 1.0.

(Evaluation of the curable composition obtained in the examples and comparative examples)

The composition and physical properties of the curable composition obtained in the examples and the comparative examples are shown in Table 2 below.

Further, using the curable compositions F1 to F6 and the curable compositions G1 to G3, the printability, the warpage property, and the long-term electrical insulation reliability were evaluated by the method described below. The results are shown in Table 3 below.

<Evaluation of printability>

Micro-comb pattern produced by JPCA-ET01 manufactured by etching a flexible copper-clad laminate (Sui, Nippon Mining Co., Ltd. grade name: S, PERFLEX US copper thickness: 8 μm, polytheneimide thickness: 38 μm) A substrate having a shape of a shape (copper wiring width / copper wiring width = 15 μm / 15 μm) is coated on a tinned flexible wiring board, and a curable composition is applied by screen printing using a #100 mesh polyester plate. . The coating film was dried at 80 ° C for 30 minutes and then thermally cured at 120 ° C for 1 hour. The fine line portion after hardening was observed under a microscope, and the amount of exudation was measured, that is, the front end portion was leaked from the printing end surface to the composition. The distances up to this are evaluated based on the following criteria.

A: The amount of exudation is 40 μm or less.

B: The amount of exudation is more than 40 μm and less than 80 μm.

C: the amount of exudation is greater than 80 μm

The results are shown in Table 3.

<Evaluation of warpage>

The curable composition was applied onto the substrate by screen printing using a #100 mesh polyester plate, and the substrate was placed in a hot air circulating dryer at 80 ° C for 30 minutes. Then, the coated substrate was cured by placing the substrate in a hot air circulating dryer at 120 ° C for 60 minutes.

A 25 μm-thick polyimide film [Kapton (registered trademark) 100EN, manufactured by DUPONT-TORAY Co., Ltd.] was used as the substrate.

The curable composition was applied, and the film cured by a hot air circulation dryer was cut into a 50 mm Φ by a circular cutter. When cut into a circular shape, the vicinity of the center exhibits a deformation that is warped into a convex or concave shape. The cured film is formed on the substrate by a circular cutter, and after 1 hour, the convex state, that is, the state in which the vicinity of the center of the substrate on which the cured film is formed is in contact with the horizontal surface, is allowed to stand. The maximum and minimum values of the height of the warp caused by the horizontal plane are measured, and the average value is obtained. The symbol indicates the direction of warpage, and when the convex state is left to stand, the film is "+" when the cured film is on the upper side and "-" when the cured film is on the lower side with respect to the polyimide film.

The results are shown in Table 3.

<Evaluation of long-term electrical insulation reliability>

Micro-comb pattern produced by JPCA-ET01 manufactured by etching a flexible copper-clad laminate (Suitable Metal Mine Co., Ltd. grade name: S'PERFLEX US copper thickness: 8 μm, polytheneimide thickness: 38 μm) A flexible wiring board on which tin plating is applied to a substrate having a shape of a shape (copper wiring width / copper wiring width = 15 μm / 15 μm), and a curable composition is applied by a screen printing method to obtain a polystyrene composition. The thickness of the amine surface was 15 μm thick (after drying).

The coated flexible wiring board was 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 cure the coated hardenable composition. Test piece.

Using this test piece, a temperature and humidity routine test was carried out 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 with a bias voltage of 60 V. Table 3 shows the resistance values of the substrate of the above-described fine comb-shaped pattern in the initial stage of the conventional temperature and humidity test and after 30 hours, 50 hours, and 100 hours after the start.

As a result of Table 3, the curable composition of the present invention (I) does not use γ-butyrolactone, and can effectively prevent leakage during screen printing, and is excellent in low warpage at the time of curing. Further, the cured product obtained from the curable composition is excellent in long-term electrical insulation reliability.

Therefore, the cured product can be used as an insulating protective film for a flexible wiring board.

Claims (12)

A curable composition comprising the following components (a) to (d), component (a): a polyurethane condensate component (b) having a functional group reactive with an epoxy group and a carbonate bond: The solvent component (c) of the following component (b1): a compound component (d) having two or more epoxy groups in one molecule: selected from the group consisting of inorganic fine particles, organic fine particles, and organic. At least one component (b1) of the inorganic composite fine particles: at least one component selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate and ethylene glycol butyl ether acetate. The sclerosing composition of claim 1, wherein the component (b) comprises the following component (b2): component (b2): selected from the group consisting of diethylene glycol diethyl ether acetate and dipropylene glycol methyl ether acetate At least one component. The curable composition according to claim 1 or 2, wherein the component (b) comprises the following component (b3), component (b3): diethylene glycol diethyl ether. The sclerosing composition according to any one of claims 1 to 3, wherein the functional group reactive with the epoxy group is selected from the group consisting of a carboxyl group, an isocyanate group, a blocked isocyanate group, and a cyclic acid anhydride group. At least one functional group in which the phenolic hydroxyl groups are grouped. Such as the sclerosing composition of claim 3, wherein the former The ratio of the total mass of the component (b1) and the component (b3) to the mass of the component (b2) (the total mass of (b1) and (b3): the mass of (b2)) is 80:20 to 30:70. The curable composition according to any one of the first to fifth aspects of the invention, wherein the curable composition is 100% by mass, and contains 20 to 70% by mass of the component (b), and the component (a) The ratio of the number of functional groups reactive with the epoxy group to the number of epoxy groups in the component (c) (the functional group/epoxy group reactive with the epoxy group) is 1/3 to 2/ 1. The component (d) is contained in an amount of from 1 to 150 parts by mass based on 100 parts by mass of the total amount of the components remaining after the component-removing component (d) contained in the self-curable resin composition. The sclerosing composition according to any one of claims 1 to 6, wherein the component (d) is cerium oxide microparticles. The curable composition according to any one of claims 1 to 7, wherein the component (c) is a compound having at least one structure selected from the group consisting of an aromatic ring structure and an alicyclic structure. The sclerosing composition of claim 8, wherein the component (c) is a compound having a tricyclodecane structure and an aromatic ring structure. A cured product obtained by hardening a curable composition according to any one of claims 1 to 9. A flexible wiring board coated with a cured material, wherein a flexible wiring board formed by wiring on a flexible substrate is formed with wiring At least a portion of the surface is covered with a cured product as in claim 10 of the patent application. A method for producing a flexible wiring board coated with a protective film, which is subjected to tin plating treatment for printing a curable composition according to any one of claims 1 to 9 to a flexible wiring board At least a part of the wiring pattern portion forms a printing film on the pattern, and the printing film is cured by heating at 80 to 130 ° C to form a protective film.