KR101307886B1 - Active Energy Ray-Curable Resin Composition And Use Thereof - Google Patents

Abstract

An object of the present invention is to provide a resin composition which can be hardened by active energy rays such as ultraviolet rays or the like to obtain a tough coating or molding material.

Epoxy resin (A) having at least glycidoxy benzene or glycidoxy naphthalene as a phenol aralkyl type epoxy resin having a structure in which an aralkyl group is bonded as a bonding group and a structure represented by the following formula (1): ), And a compound (B) having an unsaturated double bond that can be reacted with an active energy ray.

In the case where the hydroxyl equivalent of the phenol aralkyl type epoxy resin is X (g / eq.), The epoxy equivalent of the epoxy resin is Y (g / eq.), And the softening point is Z (° C), the relationship satisfies (α):

100 ≤ (X / Y) x Z ≤ 1100

Active energy ray, curable resin composition

Description

Active Energy Ray-Curable Resin Composition And Use Thereof}

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition using a phenol aralkyl type epoxy resin having excellent balance of a hydroxyl group, an epoxy group, and a softening point as a curing agent, and a use thereof, particularly a cured product.

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and to improve communication speeds. Accordingly, the demand for solder resists covering the circuits itself is increasing, which is higher than conventional demands. The ability to withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required, and a film forming material having stronger hardening properties has been sought.

In these materials, the method of obtaining the hardened | cured material physical property using the hardening reaction by active energy rays, such as an ultraviolet-ray, and the thermosetting reaction by the compound which has an epoxy group in combination is generally used (patent document 1 and 2). ).

In particular, a phenol aralkyl type epoxy resin (e.g., NC-3000 manufactured by Nippon Kayaku Co., Ltd., etc.) is used as the epoxy resin material used herein, and an attempt to obtain an excellent mechanically and thermally tough cured product is also known ( Patent document 3).

Patent Document 1: Japanese Patent Application No. 56-40329

Patent Document 2: Japanese Patent Application Publication No. 57-45795

Patent Document 3: Japanese Patent No. 2952094

DISCLOSURE OF INVENTION

Problems to be solved by the invention

Although the curable resin composition which uses the said phenol aralkyl type epoxy resin can obtain comparatively tough hardened | cured material, hardened hardened | cured material property is calculated | required. In addition, in the film formation use, especially a soldering resist use, the physical property of the solvent volatilized only after a film formation also becomes an important factor. Concretely, when it is more flexible than necessary at this stage, it will cause peeling and the fouling of a patterning film. Especially in the use of what is called a dry film, since the process called transfer enters, this characteristic is more important.

An object of the present invention is to provide a resin composition which eliminates these problems and obtains a coating or molding material that is hardened by active energy rays such as ultraviolet rays and the like.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors found that the active-energy-ray-curable resin composition containing the epoxy resin which has a specific structure can obtain strong hardened | cured material, and also has the outstanding resin physical property only in the state which dried a solvent. It has been found that the present invention has been completed.

That is, this invention is a phenol aralkyl type epoxy resin which has at least glycidoxy benzene or glycidoxy naphthalene the structure which couple | bonded the aralkyl group as a bonding group, and the structure represented by following General formula (1), It relates to an active energy ray-curable resin composition comprising a satisfying epoxy resin (A) and a compound (B) having an unsaturated double bond that can be reacted by an active energy ray:

Conditions: Respective relationships are obtained when the hydroxyl equivalent of the phenol aralkyl type epoxy resin is X (g / eq.), The epoxy equivalent of the epoxy resin is Y (g / eq.), And the softening point is Z (° C). The following formula (α) is satisfied:

100 ≤ (X / Y) x Z ≤ 1100

In addition, the present invention is the aforementioned active energy, wherein the phenol aralkyl type epoxy resin (A) is an epoxy resin obtained by the reaction of phenol aralkyl resin having a structure represented by the following general formula (2) with epihalohydrin. It relates to a precurable resin composition:

또는

이고;Ar

or

ego;

In the above formulas (2) to (4),

m represents the integer of 1-3 as the number of substituents R,

n represents the average value of the repeating number of 1-10,

R respectively represents a hydrogen atom, a halogen atom, a C1-C15 hydrocarbon group, a trifluoromethyl group, an aryl group, or an allyl group, and each R may respectively mutually be same or different. Ar may be the same or different, and in other cases, the groups of the formulas (3) and (4) are arranged in any order.

Moreover, in this invention, the said phenol aralkyl type epoxy resin (A) makes the phenol aralkyl resin of the structure shown by following General formula (2), and the phenol aralkyl type epoxy resin of the structure shown by following General formula (2 ') react, It relates to the obtained active energy ray curable resin composition:

In the above formulas,

또는

이고,Ar

or

ego,

또는

이고,Ar '

or

ego,

m represents the integer of 1-3 as the number of substituents R,

n represents the average value of the repeating number of 1-10,

R each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an aryl group or an allyl group, and each R may be the same or different from each other, and Ar may be the same or different. In other cases, the groups of the formulas (3) and (4) are arranged in any order,

n 'represents the average value of the repeating number of 1-10, and Ar' may be same or different, and in another case, groups of general formula (3 ') and (4') are arranged in arbitrary order.

Moreover, this invention relates to the said active-energy-ray-curable resin composition in which all R of the said phenol aralkyl type epoxy resin (A) is a hydrogen atom.

The present invention also relates to the active energy ray-curable resin composition wherein all Ar in the phenol aralkyl type epoxy resin (A) is a structure of formula (3), and all Ar 'is a structure of formula (3').

Moreover, this invention is the said active energy ray curable compound (B) which is a compound which contains the substituent which can react with the said epoxy resin (A), and the unsaturated double bond which can react with an active energy ray together in the same molecule. It relates to a curable resin composition.

Moreover, this invention relates to the said active energy ray hardening-type resin composition which is a molding material.

Moreover, this invention relates to the said active energy ray hardening type resin composition which is a film forming material.

Furthermore, this invention relates to the said active energy ray hardening type resin composition which is a resist material composition.

Moreover, this invention relates to the hardened | cured material of the said active energy ray hardening type resin composition.

The invention also relates to a multilayer material having a layer of the cured product.

Effects of the Invention

The active-energy-ray-curable resin composition containing the epoxy resin which has the specific structure of this invention not only obtains a hardened | cured material, but also has the outstanding resin physical property only in the state which dried a solvent. The hardened | cured material obtained from the active-energy-ray-curable resin composition of this invention can be used suitably as a film forming material which requires thermal and mechanical toughness.

More preferably, it can be used for the purpose of obtaining especially high characteristics, such as a soldering resist for printed wiring boards, the interlayer insulation material for multilayer printed wiring boards, the soldering resist for flexible printed wiring boards, a plating resist, and the photosensitive optical waveguide.

Carrying out the invention  Best embodiment for

In the active energy ray-curable resin composition of the present invention, the epoxy resin (A) which is an essential component is a phenol having a structure in which at least phenols or naphthols are bonded to an aralkyl group as a bonding group and a structure represented by the following general formula (1). For alkyl type epoxy resins, it is essential that the following relation holds:

The hydroxyl equivalent of the said epoxy resin is computed from the hydroxyl equivalent equivalent obtained by X (The epoxy equivalent of the corresponding epoxy resin, the epoxy group in an epoxy resin, and an acetic acid of equivalent equivalent are made to react, and ring-opening an epoxy group, and measuring by the method according to JISK0070.) Value (unit: g / eq.), The epoxy equivalent of the epoxy resin measured in the Y (method according to JIS K-7236. Unit: g / eq.), And the softening point of Z (according to JIS K-7234). Value measured by the method, where each unit satisfies the following formula (α):

100 ≤ (X / Y) x Z ≤ 1100

In the epoxy resin (A) used by this invention, the balance of an epoxy equivalent, a hydroxyl equivalent, and molecular weight (softening point) is important. That is, the ratio of the epoxy group and hydroxyl group contained in a molecule | numerator becomes an important parameter.

Bonding of the said Formula (1) is a structure obtained when an epoxy resin, a phenol compound, or an alcohol compound reacts. In general, a high molecular weight grade, for example, is a bond produced when synthesizing a solid bisphenol-A epoxy resin (or phenoxy resin), and the method includes a one-stage method and a fusion method (also referred to as an advanced method or a two-stage method).內 弘 編 Well, see pages 24-25, 30-31). An epoxy resin (A) is a compound using this one step method or the fusion method. In the present invention, either a single step method or a fusion method may be used. However, when synthesized in a single step method, it is preferable to use the fusion method because the reaction that the by-product is obtained tends to occur easily.

In the active energy ray-curable resin composition of the present invention, the amount of the bond containing a hydroxyl group such as the formula (1) contained in the molecular skeleton of the epoxy resin (A) is, for example, an alkali developing solder resist or the like. And its developability and sensitivity. However, when there are many this bonding patterns, the density | concentration of the epoxy group in molecular skeleton becomes low, and the problem arises in the hardenability. Therefore, the ratio of hydroxyl equivalent and epoxy group becomes important. In addition, the softening point contributes to the tuck property, but not only it, but also contributes to the functional group density of the epoxy equivalent and the hydroxyl equivalent, and contributes to the developability during alkali development. Therefore, even if the softening point is too high or too low, it becomes a problem.

That is, the balance of epoxy equivalent, hydroxyl equivalent, and molecular weight (softening point) becomes important.

When this value exceeds 1100, the fluidity | liquidity of resin at the time of image development in alkali or a solvent will worsen, development time will become long, and it will become a problem in terms of productivity. On the contrary, when it does not reach 100, sclerosis | hardenability worsens. Another problem arises in that the sensitivity becomes poor and the pattern formation is impossible. In addition, in some cases, the jaw property may deteriorate.

Although the range is 100-1100 in said Formula ((alpha)), More preferably, it is the range of 400-1000.

Moreover, the active-energy-ray-curable resin composition of this invention which uses the epoxy resin (A) which satisfy | fills the conditions mentioned above for a hardening | curing agent has the outstanding toughness in the film | membrane physical property.

Epoxy resin (A) uses a phenol aralkyl resin as a raw material, reacts this and epihalohydrin, and combines phenol aralkyl resins three-dimensionally (single-stage), or phenol aralkyl resin and phenol are It can obtain by making an alkyl type epoxy resin react (fusion method). A "phenol aralkyl resin" used as a raw material is a resin having a molecular structure in which an aromatic ring is bonded to phenols and naphthols through a methylene bond, an ethylidene bond, a propylidene bond, or the like, for example, having a substituent R Phenols or naphthols and bishalogen methyl, bishalogen ethyl or bishalogen propyl such as phenyl, biphenyl, fluorenyl or naphthyl; Bisalkoxy methyl, bisalkoxy ethyl or bisalkoxy propyl such as phenyl, biphenyl, fluorenyl or naphthyl; It can obtain by condensation reaction of bishydroxy methyl, bishydroxy ethyl, bishydroxy propyl, etc., such as phenyl, biphenyl, fluorenyl, or naphthyl. As the phenol aralkyl resin, phenols or naphthols, preferably phenols, and particularly preferably those obtained by condensation reaction of a compound having a phenol and a biphenyl skeleton, preferably a biphenyl type phenol such as the formula (2) Aralkyl resins are particularly preferred.

In the formula (2), each R independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, a halogen atom, an aryl group, or an allyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C15 hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert- butyl group, isobutyl group, cyclobutyl group , n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group And an alkyl group on a chain or a ring such as a cyclooctyl group. Examples of the aryl group include a phenyl group, a naphthyl group and a toluyl group. Among them, a hydrogen atom, a methyl group, an allyl group or a tert-butyl group is preferable, and a hydrogen atom is particularly preferable. The substitution position of R is not particularly limited, but each has an ortho position or a meta position of a hydroxyl group independently. n represents 1-10 as an average value, and 1-5.0 are preferable.

A commercial item is also available for such a phenol aralkyl resin, Specifically, Mitsui Chemical Co., Ltd. XLC series, Meiwa Chemical Co., Ltd. MEH-7851, Nippon Kayaku Co., Ltd. KAYAHARD GPH 65, etc. are mentioned. Can be.

Subsequently, in the said fusion method, the phenol aralkyl type epoxy resin used as a raw material of an epoxy resin (A) is demonstrated. The raw material phenol aralkyl type epoxy resin is resin which has the structure which glycidylated the phenolic hydroxyl group of the said phenol aralkyl resin, and the compound represented by General formula (2 ') is preferable. As such a phenol aralkyl type epoxy resin, for example, there is an epoxy resin represented by the following general formula (7):

Wherein n represents a repeating number.

Since this epoxy resin is excellent in all the characteristics, such as the flame retardance, adhesiveness, and water resistance, these days, it is preferable as an epoxy resin attracting attention.

Preferred raw material phenol aralkyl resins and raw material phenol aralkyl type epoxy resins of the epoxy resin (A) are generally synthesized by the methods described in Japanese Patent No. 3 122 834 and Japanese Patent Application Laid-Open No. 2001-40053. Specifically, 4,4'-bismethoxymethylbiphenyl and phenols are condensed under acidic conditions, or 4,4'-bishalogen methylbiphenyl and phenols are condensed under acidic conditions. There is condensation reaction of phenols. By making the obtained preferable phenol aralkyl resin react with epihalohydrin, a preferable raw material phenol aralkyl type epoxy resin, Preferably the compound represented by the said General formula (7) is obtained. As resin represented by General formula (7), there exist NC-3000 and NC-3000H by Nippon Kayaku Co., Ltd. as a commercial item.

Hereinafter, the manufacturing method of an epoxy resin (A) is demonstrated.

As mentioned above, the single-stage method and the fusion method can be adapted to the manufacturing method of an epoxy resin (A). However, in the conventional one-stage method and the fusion method, the bifunctional epoxy resin and the phenol resin are targeted. In the case where the polyfunctionality is used as the raw material as in the epoxy resin (A), the polyfunctional phenol resin and the epitaxial compound may be used in the one-stage method. In the fusion method, it is necessary to consider the reaction rate of low-hydrin according to the reaction rate of a polyfunctional epoxy resin and a polyfunctional phenol resin.

First, the case of a one-stage method is demonstrated in detail. An epoxy resin (A) is obtained by making the said phenol aralkyl resin and epihalohydrin react in presence of an alkali metal hydroxide. In this one-step method, the amount of epihalohydrin and alkali metal hydroxide used is a factor for determining the introduction rate of the structure of the formula (1).

In the reaction for obtaining the epoxy resin (A), epichlorohydrin, α-methyl epichlorohydrin, γ-methyl epichlorohydrin, epibromohydrin, and the like can be used as the epihalohydrin. In epichlorohydrin which is industrially available, it is preferable. The usage-amount of epihalohydrin is 1.0-5.0 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenol aralkyl resin, Preferably it is 1.5-3.5 mol. When the amount of epihalohydrin is less than 1.0 mole, the content ratio of the structure of the formula (1) becomes too small, the curability and the heat resistance decrease are observed, and the characteristics in the case of using a resist may be deteriorated. When it exceeds 5.0 mol, the content rate of an epoxy group will become too much.

Examples of the alkali metal hydroxide that can be used in the reaction include sodium hydroxide and potassium hydroxide, and a solid may be used or an aqueous solution thereof may be used. In the case of using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously discharged under reduced pressure or normal pressure, followed by separating the water to remove water, and It is also possible to continuously recycle rhohydrin into the reaction system. The use amount of alkali metal hydroxide is 0.3-2.5 mol normally, Preferably it is 0.5-2.0 mol with respect to 1 mol of hydroxyl groups of a raw material phenol aralkyl resin. When the usage-amount of alkali metal hydroxide is out of this range, the curability may fall and electrical reliability may fall.

The softening point of the epoxy resin (A) depends on its molecular weight. That is, when molecular weight is large, a softening point becomes high and when it is small, it falls.

In the case of this one-step method, the molecular weight of an epoxy resin (A) is the molecular weight of a raw material phenol resin, the usage-amount of epihalohydrin (it tends to decrease in molecular weight in many cases), and the usage-amount of the alkali metal with respect to epihalohydrin. (When there is little tendency for molecular weight to become small), etc. can be controlled.

In order to accelerate the reaction, it is preferable to add quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.2-10 g.

At this time, it is preferable to proceed with the reaction by adding alcohols such as methanol, ethanol and isopropyl alcohol, and a non-crotonic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane and the like.

In the case of using alcohols, the amount thereof is usually 2 to 50% by weight, preferably 4 to 20% by weight relative to the amount of epihalohydrin. In addition, when using a non-crotonic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After reacting these epoxidation reactions with water or without washing with water, epihalohydrin, a solvent and the like are removed under reduced pressure. Moreover, in order to make an epoxy resin with few hydrolyzable halogens again, the recovered epoxy resin is dissolved in a solvent such as toluene and methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, and the ring closure is carried out. You can also make sure. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally, Preferably it is 0.05-0.2 mol with respect to 1 mol of hydroxyl groups of the phenol aralkyl resin used for epoxidation. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and an epoxy resin (A) is obtained by distilling off a solvent again under heating and pressure reduction.

Hereinafter, the fusion method will be described in detail.

This method is a method of reacting the raw material phenol aralkyl aralkyl type epoxy resin and phenol aralkyl resin as mentioned above. In this fusion method, the ratio of a raw material phenol aralkyl type epoxy resin and a phenol aralkyl resin becomes an element which determines the introduction ratio of the structure of the said General formula (1). That is, when the amount of hydroxyl groups of the phenol aralkyl resin is small relative to the epoxy group of the phenol aralkyl type epoxy resin, the proportion of the structure of the formula (1) decreases, and too much may cause gelation. From this point, when the reaction ratio of both is defined by the ratio of the epoxy group and the hydroxyl group, phenolic hydroxyl group / epoxy group = about 0.01 to 0.15 is preferable.

In the fusion method, the amount of the raw material phenol aralkyl type epoxy resin and the phenol aralkyl resin in the weight ratio is 0.001 to 0.5 parts by weight, preferably 0.01 to 0.30 parts by weight, with respect to 100 parts by weight of the former. Especially preferably, it is 0.03-0.20 weight part.

A commercially available compound may be used for the raw material phenol aralkyl type epoxy resin, or phenol aralkyl resin may be epoxidized and used. When synthesize | combining, it can carry out by the following method, for example.

The raw material phenol aralkyl type epoxy resin can be obtained by making phenol aralkyl resin and epihalohydrin react. As epihalohydrin, epichlorohydrin, (alpha) -methyl epichlorohydrin, (gamma) -methyl epichlorohydrin, epibromohydrin, etc. can be used, Epichlorohydrin which is industrially available is preferable. . The usage-amount of epihalohydrin is 2.0-20.0 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 2.5-10.0 mol.

Examples of the alkali metal hydroxide that can be used for the reaction include sodium hydroxide and potassium hydroxide, and a solid may be used, or an aqueous solution thereof may be used. In the case of using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously discharged under reduced pressure or normal pressure, followed by separation to remove water, and It is also possible to continuously recycle rhohydrin into the reaction system. The usage-amount of alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.95-2.0 mol.

In order to promote the reaction, it is preferable to add quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a phenol aralkyl resin, Preferably it is 0.2-10 g.

At this time, it is preferable to proceed with the reaction by adding alcohols such as methanol, ethanol and isopropyl alcohol, and non-crotonic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane and the like.

When using alcohols, the usage-amount is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. In addition, when using a non-crotonic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. The reaction product of these epoxidation reactions is removed after washing with or without water washing to remove epihalohydrin, a solvent and the like. Furthermore, in order to make an epoxy resin with few heat-decomposable halogens again, the recovered epoxy resin is dissolved in a solvent such as toluene and methyl isobutyl ketone, and an aqueous solution of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide is added to carry out the reaction. Closing the ring can also be assured. In this case, the usage-amount of alkali metal hydroxide is 0.01-0.3 mol normally, Preferably it is 0.05-0.2 mol with respect to 1 mol of hydroxyl groups of the phenol aralkyl resin used for epoxidation. Reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and a phenol aralkyl type epoxy resin is obtained by distilling a solvent off again under heating pressure reduction. An epoxy resin (A) can be obtained by making the obtained epoxy resin react with a phenol aralkyl resin.

This reaction uses a catalyst as necessary. Specific examples of the catalyst that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; Quaternary phosphonium salts such as triphenylethylphosphonium chloride and triphenylphosphonium bromide; Alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate and cesium carbonate; Imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; Tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylenediamine, triethanolamine and 1,8-diazabicyclo (5,4,0) undec-7; Organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine; Metal compounds such as octylic acid tin; Tetra substituted phosphonium tetra substituted borate, such as tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, and N-methyl morpholine Tetraphenyl boron salts such as tetraphenylborate and the like. Although the usage-amount when using these catalysts changes with kinds of the catalyst, generally 10 ppm-30,000 ppm with respect to total resin amount, Preferably 100 ppm-5,000 ppm are used as needed. In this reaction, even if a catalyst is not added, since the reaction proceeds, it is preferable to suitably use it in accordance with the desired reaction temperature and the amount of the reaction solvent.

In this fusion method, a solvent may or may not be used. When using a solvent, any solvent can be used as long as it does not affect this reaction, For example, the solvent as shown below can be used.

Polar solvents, ethers; Dimethyl sulfoxide, N, N'-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, diglyme, triglyme, propylene glycol monomethyl ether and the like,

Ester organic solvents; Ethyl acetate, butyl acetate, butyl lactate, γ-butyrolactone, and the like,

Ketone organic solvents; Methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.

Aromatic organic solvents; Toluene, xylene, etc.

The amount of the solvent used is 0 to 300% by weight, preferably 0 to 100% by weight based on the total resin weight.

The reaction temperature and the reaction time need to be appropriately selected depending on the resin concentration and the amount of the catalyst, and generally cannot be specified. The reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is preferable that reaction time is short from the problem of productivity. Moreover, reaction temperature is 0-250 degreeC normally, Preferably it is 30-200 degreeC.

After completion | finish of reaction, the epoxy resin solution obtained using the solvent can adjust the density | concentration of a solution as needed as it is, and can be used for the active energy ray curable resin composition of this invention as a solution containing an epoxy resin (A). Moreover, an epoxy resin (A) can be isolated by removing a catalyst etc. by water washing etc. as needed and distilling a solvent off under heating and pressure reduction again.

As a compounding ratio of the epoxy resin (A) suitable for the active energy curable resin composition of this invention, when the non-volatile content of an active energy curable resin composition is 100 weight%, it is 2-75 weight%, More preferably, it is 5-30 weight %to be. When it is lower than this range, the effect of this invention is hard to be exhibited, and when it is high, physical property is hard to be exhibited as an active-energy-ray-curable resin composition. Non-volatile content here is a component whose boiling point exceeds 300 degreeC.

In the active energy curable resin composition of this invention, an epoxy resin (A) can also be used together with another epoxy resin. Specific examples of other epoxy resins that can be used together include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Hydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene and the like and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaraldehyde, phthalate Polycondensates with aldehydes, crotonaldehydes, cinnamic aldehydes, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, Polymers with divinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl Polycondensates with ketones, methyl isobutyl ketone, acetophenone, benzophenone, etc., phenols and aromatic dimethanols (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyldimethanol, α, polycondensates of α, α ', α'-biphenyldimethanol, etc., polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), bisphenols and various aldehydes. Glycidyl ether type epoxy resin which glycidylated polycondensate, alcohol, etc., alicyclic epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, etc. are used, but these are the epoxy resins normally used It is not limited to. These may be used independently and may use 2 or more types. When using another epoxy resin together, the epoxy resin (A) of this invention is 30 weight% or more normally in all the epoxy resins mix | blended, Preferably it is 50 weight% or more.

The compound (B) (henceforth a reactive compound (B)) which has an unsaturated double bond which can react with the active energy ray used by this invention is a general term of the compound which shows reactivity with an active energy ray. These are used for the purpose of imparting curability, ie reactivity, to the composition by the active energy ray.

Specific examples of the reactive compound (B) that can be used include so-called reactive oligomers such as acrylates of radical reaction type, other epoxy compounds of cationic reaction type, and vinyl compounds sensitive to both thereof.

Examples of the acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like. "(Meth) acrylate" means acryl or methacryl, acrylate or methacrylate, respectively).

As monofunctional (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol ( Meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. There is this.

As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) ) Acrylate, diethylenedi (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy Ε-caprolactone addition of di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and hydroxybivar acid neophene glycol Di (meth) acrylate of water, poly (meth) acrylate of reactant of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, Trimethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tetra ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adduct thereof.

Vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like. Examples of styrenes include styrene, methyl styrene, ethyl styrene, and the like. Other vinyl compounds include triallyl isocyanurate, trimetaaryl isocyanurate, and the like.

Moreover, as what is called reactive oligomer, urethane acrylate which has the functional group and urethane bond which can be functionally activated to an active energy ray in the same molecule, polyester acrylate which has the functional group and ester bond which can be functionally similar to an active energy ray together in the same molecule,

And other epoxy acrylates derived from other epoxy resins and having functional groups capable of acting on active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

As a compounding ratio of the reactive compound (B) used for the active-energy-ray-curable resin composition of this invention, when the non volatile matter of the said resin composition is 100 weight%, it is 15-98 weight% normally, Preferably it is 20-60 weight %to be. When less than this, hardening by an active energy ray is hard to be performed and when exceeding this, the desired characteristic as a composition may not be acquired. The non volatile matter shown here is a thing of the component whose boiling point exceeds 300 degreeC.

Among these, when the compound which contains the substituent which can react with the epoxy group of an epoxy resin (A), and the unsaturated double bond which can react with an active energy ray together in the same molecule is used as a reactive compound (B), Since a thermosetting reaction occurs, the effect of this invention can be exhibited higher.

In the above, examples of the substituent capable of reacting with an epoxy group include a carboxyl group, an amino group, and a hydroxyl group.

As an example of the reactive compound (B) which has a carboxyl group, the semi-ester compound (for example, hydroxyethyl (meth) which made polycarboxylic acid anhydride react with unsaturated carboxylic acids, such as (meth) acrylic acid, and hydroxyl-containing (meth) acrylates, etc. Acrylate succinic acid half ester), and a half ester compound derived from epoxy (meth) acrylate and the like. The hydroxyl-containing compound and polybasic acid anhydride (c) which are preferably used here are explained in full detail below.

Moreover, as a reactive compound (B) which has an amino group, (meth) acrylamide etc. are mentioned.

Moreover, as a reactive compound (B) containing a hydroxyl group, hydroxyalkyl (meth) acrylates, such as hydroxyethyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acryl The compound which made reactive carboxyl group-containing compounds, such as (meth) acrylate, react with epoxy resin represented by epoxy acrylates, such as a latent and dipentaerythritol penta (meth) acrylate, etc. are mentioned.

The active-energy-ray-curable resin composition of this invention is obtained by mixing each said component uniformly at a predetermined | prescribed ratio, and it hardens easily with an active energy ray. Specific examples of the active energy rays include ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, electromagnetic waves such as laser rays, and particle beams such as α-rays, β-rays, and electron beams. In consideration of the preferable use of the present invention, among these, ultraviolet rays, laser beams, visible rays, or electron beams are preferable.

In the present invention, the molding material refers to an uncured composition in a mold, or to press an mold to mold an object, to cause a curing reaction with an active energy ray, and to mold or to focus the light, such as a laser, on the uncured composition. Refers to a material used for the purpose of irradiating and forming a curing reaction.

Specific applications include lens materials such as convex lenses, concave lenses, micro lenses, Fresnel lenses, and lenticular lenses, light guide materials used in liquid crystal displays, and the like, and uncured compositions such as sheets, films, and disks processed into plates. Fine molding is performed by pressing the processed 'shape', and so-called nanoinprint materials and encapsulants for protecting the devices, in particular encapsulation materials such as light emitting diodes and photoelectric conversion devices, are exemplified.

In the present invention, the film forming material is used for the purpose of covering the substrate surface. Specific applications include ink materials such as gravure inks, flexo inks, silkscreen inks and offset inks, coating materials such as hard coats, top coats, overprint varnishes, clear coats, laminates, and various other adhesives and adhesives for optical discs ( Examples thereof include adhesive materials such as thin coatings, resist materials such as solder resists, etching resists, and precision mechanical resists. In addition, what is called a dry film also apply | coats a film forming material to a peelable base material temporarily, and forms it, after bonding to the base material made into the original, and forming a film.

Since the hydroxyl group concentration contained in an epoxy resin (A) exists in a suitable range especially as a dry film use, since a comparatively strong dry film is obtained, it is especially preferable.

In the present invention, the resist material composition refers to an active energy ray sensitive to be drawn by partially irradiating active energy rays such as ultraviolet rays after forming a coating layer of the composition on a substrate and using physical properties of the irradiated portion and the unirradiated portion. Type composition is shown. Specifically, it is a composition used for the purpose of drawing and removing an irradiation part or a non-irradiation part by any method, for example, the method which melt | dissolves with a solvent, an alkali solution, etc.

The active energy ray-curable resin composition for resists of the present invention can be adapted to various materials that can be patterned, and is particularly useful for solder resist materials and interlayer insulating materials for build up methods. It is also used in electrical, electronic and optical materials such as printed wiring boards, optoelectronic substrates and optical substrates as optical waveguides.

As a method to apply to such a material, when manufacturing a printed wiring board using the active-energy-ray-curable resin composition of this invention containing the solvent mentioned later, for example, first, the screen printing method to a printed wiring board, The active energy ray-curable resin composition of this invention is apply | coated to the film thickness of 0.5-160 micrometers by methods, such as the spray method, the roll coat method, the electrostatic coating method, the curtain coat method, and a composition layer is 50-110 degreeC normally, Preferably Forms a coating film by drying at 60-100 degreeC. Thereafter, a high-energy ray such as ultraviolet rays is irradiated directly or indirectly to the coating film through a photomask on which an exposure pattern such as a negative film is formed at an intensity of about 10 to 2000 mJ / cm 2, and a developing solution described below for the unexposed part. Using, for example, development by spraying, rocking dipping, brushing, scrubbing, or the like. Subsequently, ultraviolet rays are irradiated again as needed, and then heat treated at 100 to 200 ° C., preferably 140 to 180 ° C., thereby providing excellent gold plating properties and providing excellent heat resistance, solvent resistance, acid resistance, adhesion, flexibility, and the like. The printed wiring board which has a permanent protective film which satisfy | fills a characteristic is obtained.

The aqueous alkali solution used for the above development includes inorganic alkali aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, tetramethylammonium hydroxide and tetraethylammonium hydro. An organic alkali aqueous solution, such as an oxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine, can be used.

Although it does not restrict | limit especially as a method of forming a film, Intaglio printing methods, such as gravure, Iron plate printing methods, such as a flexographic, stencil printing methods, such as a silkscreen, Flatbed printing methods, such as an offset, Roller coater, Various coating methods, such as a knife coater, a die coater, a curtain coater, and a spin coater, can be employ | adopted arbitrarily.

The hardened | cured material of the active-energy-ray-curable resin composition of this invention means what irradiated and hardened | cured at least an active energy ray to the active-energy-ray-curable resin composition of this invention.

In the present invention, the multilayer material refers to a material having at least two or more layers obtained by forming and curing the active energy ray-curable resin composition shown in the present invention on a substrate.

Hereinafter, the case where the active energy ray curable resin composition of this invention is used as a resist material composition is described in detail.

It is preferable to use a carboxyl group-containing compound as a reactive compound (B) for the resist material composition of this invention. This is useful not only for reacting the carboxyl group with the epoxy resin (A) but also for imparting alkali solubility when dissolving the active energy ray non-irradiated portion in an aqueous resist or the like and patterning the resist. Because.

Especially for solder resist applications requiring toughness, the reactive compound (B) has a monocarboxylic acid compound (b) having an epoxy compound (a) having two or more epoxy groups in a molecule and an unsaturated double bond capable of reacting with an active energy ray in the molecule. Compound (B-1), such as reaction product obtained by making polybasic acid anhydride (c) react with the epoxy carboxylate compound obtained by making) react,

In addition, an epoxy carboxylate compound obtained by reacting an epoxy compound (d) having two epoxy groups in a molecule with a monocarboxylic acid (b) having an ethylenically unsaturated group in a molecule, a diisocyanate compound (e) and two hydroxyl groups in a molecule The carboxylic acid compound (f) which has, the arbitrary diol compound (g), and the compound (B-2) obtained by reaction with arbitrary acid anhydrides like the said polybasic acid anhydride (c), etc. are mentioned.

In the above, it is preferable that each component (a)-(c) used for a compound (B-1) is a compound soldier as follows.

It is preferable that especially an epoxy equivalent is 100-900 g / equivalent epoxy compound (a) of an epoxy compound (a). When the epoxy equivalent is less than 100, the molecular weight of the compound (B-1) obtained is small and the film formation may be difficult and flexibility may not be sufficiently obtained, and when the epoxy equivalent exceeds 900, having an ethylenically unsaturated group There exists a possibility that the introduction ratio of a monocarboxylic acid compound (b) may become low and photosensitivity may fall.

As a specific example of the epoxy compound (a) which has two or more epoxy groups in a molecule | numerator, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a tris hydroxyphenylmethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, bisphenol A novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin, glyoxal-phenol type epoxy resin, heterocyclic epoxy resin Etc.

As a phenol novolak-type epoxy resin, for example, Epikron N-770 (made by Dainippon Ink & Chemicals Co., Ltd.), DEN438 (made by Dow Chemical Co., Ltd.), Epicoat 154 (made by Yucca shell epoxy company), EPPN-201, RE- 306 (manufactured by Nippon Kayaku Co., Ltd.). As a cresol novolak-type epoxy resin, Epiclon N-695 (made by Dainippon Ink & Chemicals Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S (made by Nippon Kayaku Co., Ltd.), UVR-6650 (Union carbide, for example) Company) and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical), Epicoat E1032H60 (manufactured by Yuca Shell Epoxy), and the like. As a dicyclopentadiene phenol type epoxy resin, Epiclon EXA-7200 (made by Dainippon Ink & Chemical Co., Ltd.), TACTIX-556 (made by Dow Chemical), etc. are mentioned, for example.

As a bisphenol-type epoxy resin, for example, Epicoat 828, Epicoat 1001 (made by Yucatel Epoxy), UVR-6410 (made by Union Carbide), DER-331 (made by Dow Chemical Co., Ltd.), YD-8125 (made by Tokyo Chemical Co., Ltd.) Bisphenol-F type epoxy resins such as bisphenol-A type epoxy resins, UVR-6490 (manufactured by Union Carbide), and YDF-8170 (manufactured by Tokyo Chemical Co., Ltd.).

Examples of the biphenol type epoxy resins include bixylenol epoxy resins of YX-4000 (manufactured by Yucca Shell Epoxy), YL-6121 (manufactured by Yucca Shell Epoxy), and the like. As bisphenol A novolak-type epoxy resin, Epiclon N-880 (made by Dainippon Ink & Chemicals Co., Ltd. product), Epicoat E157S75 (made by Yucca shell epoxy company), etc. are mentioned, for example.

As a phenol aralkyl type epoxy resin, For example, phenol biphenyl aralkyl type epoxy resins, such as NC-3000 and NC-3000-H (made by Nippon Kayaku Co., Ltd.), XLC-3L (phenol aralkyl by Mitsui Chemical) Resins) glycidylate and the like.

Examples of naphthalene skeleton-containing epoxy resins include NC-7000, NC-7300 series (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by Dainippon Ink & Chemicals Co., Ltd.). As an alicyclic epoxy resin, EHPE-3150 (made by Daicel Chemical Industries, Ltd.) etc. is mentioned, for example. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

Examples of the monocarboxylic acid compound (b) include a reactant of acrylic acid, crotonic acid, α-cyano cinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, a saturated or unsaturated dibasic anhydride, a (meth) acrylate derivative having one hydroxyl group in one molecule, and a half molar reactant. Although there are esters, semi-esters which are sugar molar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, and the like, (meth) acrylic acid and (meth) in terms of sensitivity when the photosensitive resin composition is used. Particular preference is given to reaction products of acrylic acid and ε-caprolactone or cinnamic acid.

The polybasic acid anhydride (c) can be used as long as it has one or more acid anhydride structures in the molecule, but any succinic anhydride, acetic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,3,4, -butanetetracarboxylic dianhydride, 3,3 ', 4,4' Diphenylsulfontetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4 , 4'-diphenylethertetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane , 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b- Trad dihydro-5- (tetrahydro-2,5-dioxo-3-furanyl) - naphtho a [1,2-c] polybasic acid anhydride selected from the group consisting of furan-1,3-dione it is especially preferred.

Moreover, it is preferable that each component (b)-(g) used by a compound (B-2) is a compound soldier as follows.

It is preferable that especially the epoxy equivalent of the epoxy compound (d) which has two epoxy groups in a molecule | numerator is 100-900 g / equivalent epoxy compound (d). When the epoxy equivalent is less than 100, the molecular weight of the curable compound (b) to be obtained is low and there is a possibility that the film formation becomes difficult and flexibility may not be sufficiently obtained, and when the epoxy equivalent is more than 900, having an ethylenically unsaturated group There exists a possibility that the introduction ratio of a monocarboxylic acid compound (b) may become low and photosensitivity may fall.

As a specific example of the epoxy compound (d) which has two epoxy groups in a molecule | numerator, For example, phenyl diglycidyl ether, such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, etc. , Bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoro Bisphenol type epoxy compounds, such as the epoxy compound of propane, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2, 2-bis (4-hydroxyphenyl)- Halogenated bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds such as epoxy compounds of 1,1,1,3,3,3-hexafluoropropane, brominated bisphenol-A epoxy resins, and brominated bisphenol-F epoxy resins; Cyclohexanedimethanol diglyci Aliphatic diglycides such as alicyclic diglycidyl ether compounds such as ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether Polysulfide type diglycidyl ether compounds, such as a dil ether compound and polysulfide diglycidyl ether, a biphenol type epoxy resin, etc. are mentioned.

Commercially available products of these epoxy compounds include, for example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-304 (all made by Mitsui Chemical), DER-331, DER-332, DER-324 (all Dow Chemical company make), epicron 840, epicron 850 (all Dainippon ink) UVR-6410 (union) Bisphenol-A type epoxy resins, such as carbide company make), RE-310S (made by Nippon Kayaku Co., Ltd.), and YD-8125 (made by Tokyo Chemical Co., Ltd.), UVR-6490 (made by Union Carbide company), YDF-2001, YDF-2004, YDF Bisphenol-F type epoxy resins, such as -8170 (all are manufactured by Toyo Kasei Co., Ltd.), epicron 830, and epicron 835 (all are manufactured by Dainippon Ink, HBPA-DGE (made by cyclic petrochemicals), Lika resin HBE-100 (new) Brominated bisphenol-A epoxy resins such as hydrogenated bisphenol-A epoxy resins such as Nippon Rika), DER-513, DER-514, and DER-542 (all manufactured by Dow Chemical Corporation), vertical Side 2021 (product made from Daicel), alicyclic epoxy resins such as Lika resin DME-100 (product made by Shin-Nippana), EX-216 (product made by Nagase Chemical Co., Ltd.), ED-503 (product made by Asahi Denka Co.), Lika resin W- Aliphatic diglycidyl ether compounds, such as 100 (made by Shin Nippon Rika), EX-212, EX-214, and EX-850 (all are manufactured by Nagase Chemical Co., Ltd.), FLEP-50, and FLEP-60 (all are manufactured by Tore Thiolcol) And non-phenolic epoxy compounds such as polysulfide diglycidyl ether compounds and YX-4000 (manufactured by Japan Epoxy Resin).

As a diisocyanate compound (e), if it has two isocyanate groups in a molecule | numerator, all can be used, and several diisocyanate compound can be made to react simultaneously. Among them, the diisocyanate compound (e) having particularly excellent flexibility and the like is phenylene diisocyanate, triylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene Diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, aryl cyan diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane Or norbornane-diisocyanate methyl is preferred.

As the carboxylic acid compound (f) having two hydroxyl groups in the molecule, any alcoholic hydroxyl group or phenolic hydroxyl group and a diol compound having a carboxyl group at the same time can be used, but an alcoholic hydroxyl group having excellent aqueous alkali developability is particularly preferable, and dimethyl Diol compounds such as olpropionic acid and dimethylolbutanoic acid.

As the optional diol compound (g), any aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms can be used, and ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-heptanediol, 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzopinacol, cyclo Pentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,4-dimethanol, hydroxyl group at the terminal Butadiene-acrylonitrile copolymer having, spiroglycol having a hydroxyl group at the terminal, dioxane glycol having a hydroxyl group at the terminal, tricyclodecane- dimethanol having a hydroxyl group at the terminal, a macromonomer having a hydroxyl group at the terminal and polystyrene on the side chain And a hydroxyl group at the terminal, and the polystyrene-acrylonitrile copolymer Diol compounds, such as a macromonomer which has, or these reactants, such as these diol compounds, and oxides, such as ethylene oxide and a propylene oxide, etc. are mentioned.

When using the active-energy-ray-curable resin composition of this invention as a soldering resist use, it is preferable that the reactive compound (B-1) and (B-2) use the thing whose solid content acid value is 50-150 mgKOH / g. desirable. When the solid acid value is less than 50 mg · KOH / g, the solubility in an aqueous alkali solution is insufficient, and when patterning, there is a fear of remaining as a residue, and in the worst case, patterning may be impossible. Moreover, when solid content acid value exceeds 150 mgKOH / g, it is unpreferable because there exists a possibility that the solubility to aqueous alkali solution may become high too much, and the photocured patterning may peel.

Generally as a reactive compound (B-1), it is marketed as acid-modified epoxy acrylates. Specifically, KAYARAD PCR-1169H (manufactured by Nippon Kayaku Co., Ltd.) as a phenol novolak-type acid modified epoxy acrylate, such as cresol novolak-type acid-modified epoxy acrylate, and KAYARAD CCR-1159H (manufactured by Nippon Kayaku Co., Ltd.), and special bisphenol-type acid As modified epoxy acrylates, such as KAYARAD ZAR-1559H (manufactured by Nippon Kayaku Co., Ltd.) and KAYARAD ZFR-1540H (manufactured by Nippon Kayaku Co., Ltd.), trisphenol methane-type acid-modified epoxy acrylates include KAYARAD TCR-1310H (manufactured by Nippon Kayaku Co.). have.

In addition, in order to make the active energy ray hardening-type resin composition of this invention suitable for various uses, other components can be added with an upper limit of 70 weight% (unsealed). Other components include photopolymerization initiators, other additives, coloring materials, and the like. Other components which can be used below are illustrated.

Examples of the radical type photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 Acetophenones such as -one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; There are known general radical photoreaction initiators such as phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

An initiator may be used individually by 1 type and may use 2 or more types together.

In addition, although it does not have the unsaturated double bond which can react with an active energy ray according to the objective to be used, it is also preferable to mix | blend the compound which has a substituent which can react with the epoxy group of an epoxy resin (A). As a substituent which can react with an epoxy group, a carboxy group, an amino group, a hydroxyl group, etc. are mentioned, for example. Among these, in consideration of the reactivity of the epoxy group, a carboxyl group or an amino group is preferable, and a carboxyl group is particularly preferable.

As such a compound, for example, an aromatic carboxylic acid such as aliphatic carboxylic acid such as lauric acid, stearic acid, sebacic acid, tetra and hexahydrophthalic acid, phthalic acid, or a carboxyl group-containing monomer component such as (meth) acrylic acid is copolymerized. And copolymers.

Other additives include, for example, thermosetting catalysts such as melamine, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, fillers such as aluminum hydroxide, aluminum oxide, silica, clay, and thixotropy such as aerosils. And polymerization inhibitors such as phthalocyanine blue, phthalocyanine green, titanium oxide, silicone, and fluorine-based leveling agent, antifoaming agent, hydroquinone, hydroquinone monomethyl ether, and the like.

Moreover, as a pigment material, For example, organic pigments, such as a phthalocyanine series, an azo system, a quinacridone system, inorganic pigments, such as titanium oxide, carbon black, bengal, zinc oxide, barium sulfate, and talc, well-known general coloring, And extender pigments.

Other resins (so-called inatopolymers) which do not exhibit reactivity with active energy rays and epoxy groups, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, dia Reel phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products thereof may also be used. It is preferable to use these in the range up to 40 weight% (withstand weight).

In addition, depending on the purpose of use, in order to measure the viscosity, a volatile solvent may be added in the range of 40% by weight, more preferably up to 20% by weight based on the total weight of the composition.

Examples of the volatile solvent that can be used include ketones such as acetone, ethyl methyl ketone and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dipropylene. Glycol ethers such as glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cello Esters such as sorb acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutaric acid, dialkyl succinate, dialkyl adipic acid, cyclic esters such as γ-butyrolactone, petroleum ether, petroleum naphtha Petroleum solvents such as hydrogenated petroleum naphtha, solvent naphtha, etc. , These may be used alone, it may be used in combination of two or more.

In addition, an epoxy resin (A) may be previously mixed with an active energy ray hardening-type resin composition, and may be mixed and used just before use. Among these, a main component solution containing the above-mentioned (B) component as a main component, and an epoxy curing catalyst such as melamine and the like, and a two-component type curing agent solution mainly based on the epoxy resin (A) are used. It is also preferable to mix and use.

Although the energy-beam curable resin composition of this invention hardens only by irradiation of energy rays, such as an ultraviolet-ray, an epoxy group is heat-treated at 50-200 degreeC, Preferably it is 140-180 degreeC after energy ray irradiation as needed. The thermosetting reaction can be carried out to obtain a hardened product that is more robust in a short time. In addition, when using the composition of this invention for a resist use, this heat effect process is performed after performing the image development process after energy-beam irradiation.

Hereinafter, although an Example demonstrates this invention further more concretely, "part" is a weight part and "%" is a weight% unless there is particular notice. In addition, the softening point and the epoxy equivalent were measured on condition of the following.

1) Epoxy equivalent: It measured by the method according to JISK-7236.

2) Hydroxyl equivalent: The epoxy equivalent of the said epoxy resin, the epoxy group in an epoxy resin, and the acetic acid of equivalent equivalent were made to react, and after ring-opening an epoxy group, it calculated from the hydroxyl equivalent equivalent obtained by measuring by the method according to JISK0070.

3) Softening point: measured by the method according to JIS K-7234

4) The measurement conditions of GPC are as follows.

Model: SHODEX SYSTEM-21 Column: KF-804L KF-803L (x 2) Connection eluent: THF (tetrahydrofuran); 1 mL / min. 40 ° C. detector: UV (254 nm; UV-41)

Sample: approximately 0.4% THF solution (20 μl inject)

Calibration curve: using standard polystyrene made by SHODEX

Synthesis Example 1: Synthesis of exemplary horticultural epoxy resin

288 g of phenol-biphenyl novolak type epoxy resin (NC-3000H epoxy equivalent made by Nippon Kayaku Co., Ltd.) as an epoxy resin of the formula (2 ') while nitrogen purge to a flask equipped with a stirrer, a reflux condenser and a stirring device. / eq., softening point 68 DEG C, Ar 'of formula (2') are all phenol aralkyl resins of 472.5 parts of formula (3 '), R are all hydrogen atoms), and phenol-biphenyl novolac 27.5 parts of Resin (KAYAHARD GPH65 hydroxyl equivalent by Nippaya Kayaku Co., Ltd., Ar (2) of Formula (2), and R are all hydrogen atoms), 100 parts of methyl ethyl ketone, and uniform at 70 degreeC After melt | dissolving easily, 1 part of triphenyl phosphines were added and it stirred at 100 degreeC for 40 hours. After the reaction was completed, oxygen purge was performed, and triphenylphosphine was oxidized, and then 500 parts of the target epoxy resin (EP1) was obtained by distilling off the solvent. The epoxy equivalent of epoxy resin (EP1) was 326 g / eq., The softening point was 80 degreeC, the value of formula ((alpha)) was 648, and melt viscosity (150 degreeC) was 0.86 Pa.s.

Synthesis Example 2: [Synthesis of epoxy resin and horticultural

477.5 parts of phenol-biphenyl novolak type epoxy resin (NC-3000H epoxy equivalent 288 g / eq. Softening point 68 degreeC by Nippon Kayaku Co., Ltd.), performing nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. , 22.5 parts of phenol-biphenyl novolak resin (KAYAHARD GPH65 hydroxyl equivalent 202 g / eq. Manufactured by Nippon Kayaku Co., Ltd.) and 50 parts of methyl ethyl ketone were added and dissolved uniformly at 70 ° C, and 0.5 parts of triphenylphosphine were added thereto, and 105 It stirred at 30 degreeC. Epoxy resin varnish (VE1) was obtained by adding 169 parts of methyl ethyl ketones and adjusting resin concentration to 70 weight%. Some solvents were distilled off and the epoxy resin (EP2) contained in the varnish was obtained. The epoxy equivalent was 312 g / eq., The softening point was 72 ° C., the value of formula (α) was 880, and the melt viscosity (150 ° C.). Was 0.51 Pa.s.

Synthesis Example 3: Synthesis of exemplary horticultural epoxy resin

288 g of phenol-biphenyl novolak type epoxy resin (NC-3000H epoxy equivalent made by Nippon Kayaku Co., Ltd.) as an epoxy resin of the formula (2 ') while nitrogen purge to a flask equipped with a stirrer, a reflux condenser and a stirring device. / eq., softening point 68 DEG C, Ar 'in formula (2') are all 450 parts of formula (3 '), R is hydrogen atom), phenol aralkyl resin of formula (2), phenol-biphenyl novolac 50 parts of resin (Kayahard GPH65 hydroxyl group equivalent by Nippon Kayaku Co., Ltd., equivalent to 202 g / eq. Of Formula (2), and all of R in the formula (3) and R are all hydrogen atoms) and 100 parts of methyl ethyl ketone were added and uniformly maintained at 70 ° C. After dissolving, 1 part of triphenylphosphine was added, and it stirred at 100 degreeC for 80 hours. Oxygen purge was performed after completion | finish of reaction, after triphenylphosphine was oxidized, 500 parts of target epoxy resins (EP3) were obtained by distilling a solvent off. The epoxy equivalent of epoxy resin (EP3) was 376 g / eq., The softening point was 91 degreeC, the value of Formula ((alpha)) was 405 and melt viscosity (150 degreeC) was 3.34 Pa.s.

Comparative Synthesis Example 1: Synthesis of exemplary horticultural epoxy resin

249 parts of phenol aralkyl resin (it synthesize | combines by the method of patent document: Unexamined-Japanese-Patent No. 2003-301031, purging with nitrogen gas in the flask equipped with the stirrer, the thermometer, and the condenser. The hydroxyl equivalent 240 g / eq. Softening point 94 degreeC) , Ar in formula (2) are all of formula (3), R is all hydrogen atom, N = 4.9 (average value), 555 parts of epichlorohydrin (about 6 moles to the equivalent of hydroxyl group monophenol), methanol 55 parts were added, it melt | dissolved under stirring, and it heated up to 73 degreeC. Then 40 parts of sodium hydroxide on the flakes were added in portions over 90 minutes, and then the reaction was carried out again at 70 ° C for 1 hour. After completion of the reaction, water was washed with 300 parts of water, and excess solvent such as epichlorohydrin was distilled off from the oil layer using a rotary evaporator at 140C under reduced pressure. 600 parts of methyl isobutyl ketones were added and dissolved in the residue, and it heated up to 70 degreeC. 10 parts of 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, followed by washing with water until the wash water became neutral, and the obtained solution was subjected to methyl isobutyl ketone or the like under reduced pressure at 180 ° C using a rotary evaporator. 301 parts of epoxy resins (EP4) for comparison were obtained by distilling off. The epoxy equivalent of the obtained epoxy resin was 311 g / eq., The softening point was 75 degreeC, the value of Formula ((alpha)) was 1295, and melt viscosity (150 degreeC) was 0.52 Pa.s.

Synthesis Example 4: Synthesis of epoxy, urethane hybrid carboxylic acid-containing active energy ray-curing compound (B-2)

As an epoxy compound (d) which has two or more epoxy groups in a molecule | numerator in a 3L-flask equipped with a stirring apparatus and a reflux tube, RE-310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184.0g) by Nippon Kayaku Co., Ltd. / Equivalent) 148.0 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, 1.02 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor and triphenyl as a reaction catalyst 1.53 g of phosphines were added and reacted at a temperature of 98 ° C until the acid value of the reaction solution became 0.5 mg · KOH / g or less to obtain an epoxy carboxylate compound (theoretical molecular weight: 509.2).

Subsequently, 755.5 g of carbitol acetate as a solvent in this reaction solution, and 268.3 g of 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.16) as a carboxylic acid compound (f) having two hydroxyl groups in the molecule As an inhibitor, 1.08 g of 2-methylhydroquinone and 140.3 g of spiroglycol (molecular weight: 304.38) were added as a diol compound (g), and it heated up at 45 degreeC. 485.2 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) was slowly dripped at this solution so that reaction temperature might not exceed 65 degreeC. After completion of the dropwise addition, the temperature was raised to 80 ° C. and reacted for 6 hours until absorption of 2250 cm ⁻¹ was lost by infrared absorption spectrometry, containing 65% by weight of an aqueous alkali solution soluble resin (B-2). A resin solution was obtained. The acid value was measured, resulting in 52.0 mg · KOH / g (solid acid value: 80.0 mg · KOH / g).

Example 1 and Comparative Example 1 : Preparation of dry film for resist and preparation of resist bonded substrate

Synthesis Examples 1 to 3, Comparative Synthesis Example 1, and commercially available epoxy resin (trade name NC-3000, manufactured by Nippon Kayaku Co., Ltd., and Ar 'in formula (2') are all formula (3 '), and R is all hydrogen atom and epoxy. Equivalent to 273 g / eq., Hydroxyl equivalent 9583.7 g / eq., Softening point of 57 ° C., and the value of the formula (α) was obtained in Synthesis Example 4 as 20 g of each phenol aralkyl type epoxy resin of 2001) and a reactive compound (B). Epoxy, urethane complex type carboxylic acid-containing active energy ray-curable compound (B-2), 34.44 g, and 3.54 g of KAYARAD HX-220 (trade name: Nippon Kayaku Co., Diacrylate Monomer), Irgacure as photopolymerization initiator 4.72 g of 907 (Shiba Specialty Chemicals Co., Ltd.) and 0.47 g of Kayakure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 1.05 g of melamine as a heat curing catalyst and 20.95 g of methyl ethyl ketone as a viscosity-adjusting solvent were added and kneaded in a roll mill. Uniformly dispersed, active energy ray diameter for the present invention and the comparative for resist To give a resin composition.

The obtained composition was uniformly coated on a polyethylene terephthalate (PET) film to be a support film by a wire bar coat, passed through a hot air drying furnace having a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. The polyethylene film which becomes a protective film was attached on the base layer, and the dry film for resist was obtained. The obtained dry film was laminated | stacked on the whole surface of a board | substrate, peeling a protective film on the polyimide printed circuit board (copper circuit thickness: 12 micrometers, polyimide film thickness: 25 micrometers) using the heating roll of temperature 40 degreeC. .

After lamination, after exposing 500 mJ of vertical ultraviolet rays through the patterned mask, the PET film was peeled off and the peelability was evaluated, and then developed and washed with 1% by weight aqueous sodium carbonate solution. Then, epoxy resin was hardened and reacted by the 150 degreeC hot air dryer, and the film was obtained.

The obtained sample was evaluated by the following evaluation items.

-Peelability evaluation: The peelability from a PET film is shown.

○: fall off cleanly,

(Triangle | delta): A dry film will be torn, if it is not peeled off carefully slowly,

X: No peeling off.

-Bendability evaluation: shows the bending state of the film after curing at 150 ℃.

○: Almost no warping.

(Triangle | delta): There exists some curvature,

X: The warpage is large.

-Evaluation of bendability: Fold the film after curing at 150 ° C, fold it strongly with a fingernail, fold it again to the opposite side at the same position, and again with a fingernail. Visually evaluate the state of the cured film of the folded portion.

○: no crack peeling,

(Triangle | delta): Slight cracks are seen,

X: Falling and cracking.

-Heat resistance evaluation The film after 150 degreeC hardening was immersed in the 260 degreeC solder bath for 1 minute, and cooled, and the cellophane tape peeling test was done.

○: no peeling off,

(Triangle | delta): There is a little fall,

X: greatly lost.

The evaluation results are summarized in the table below.

Example 1-1 Examples 1-2 Example 1-3 Comparative Example 1-1 Comparative Example 1-2 Epoxy resin Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Comparative Synthesis Example 1 NC-3000 Peelability Evaluation ○ ○ ○ △ △ Bendability evaluation ○ ○ △ △ △ Bendability rating ○ △ △ X X Heat resistance evaluation ○ ○ ○ △ X

From the above result, it turns out that the active-energy-ray-curable resin composition of this invention using the epoxy resin which has a specific structure forms a tough film compared with the resin composition using the commercially available epoxy resin which has the same frame | skeleton.

Example 2 and Comparative Example 2: Preparation and alkaline developable resist rating of the liquid solder resist

Epoxy resin (Example) synthesized in Synthesis Example 1 or commercially available epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Comparative Example) 10 g, reactive compound (B-1), KAYARAD CCR-1159H (Example 2- 1 and Comparative Example 2), 30 g of KAYARAD ZAR-1559H (Example 2-2), KAYARAD ZCR-1361 (Example 2-3), 20 g of dipentaerythritol hexaacrylate as the other curable compound, UV-responsive type As an initiator, 3 g of Irgacure 907 and 0.5 g of DETX-S were mixed. Further 30 g of barium sulfate powder was added and mixed in three roll mills to prepare an alkali developing resist composition.

Moreover, this was coated on the copper-stripped laminated board with the hand applicator so that the film thickness at the time of drying may be set to 20 micrometers, and the solvent drying was performed in the electric oven at 80 degreeC for 30 minutes. After drying, ultraviolet rays having an irradiation dose of 1000 mJ were irradiated and cured by an ultraviolet ray vertical exposure apparatus (manufactured by Oksei Corporation) equipped with a high pressure mercury lamp to obtain a multilayer material. In the same manner, the mask pattern was covered from the top of the coated product after the drying was completed, and then vertically exposed in the same manner to obtain a patterned multilayer material.

In addition, the coating exposure by the mask pattern sprayed the 1 weight% sodium carbonate aqueous solution by the spray, and melted and developed the unexposed part.

The multilayer material after ultraviolet irradiation was heat-processed at 150 degreeC for 60 minutes, and after making an epoxy resin react, the physical property of hardened | cured material was evaluated as follows. The evaluation results are shown in the table below.

-Developability evaluation: The time (seconds) until image development is shown as image development time.

-Adhesive evaluation: The board | substrate after 150 degreeC hardening evaluated the adhesiveness with respect to a base material by the crosscut cellophane tape peeling test (JIS K5600-5-6: 1999).

○: 100/100, no crack fall off

(Triangle | delta): Some crack is seen more than 99/100,

X: Falling Less than 99/100.

-Heat resistance evaluation: The rosin type flux was apply | coated to the board | substrate after hardening at 150 degreeC, immersed in the solder bath of 260 degreeC for 1 minute, and then cooled, and the crosscut cellophane tape peeling test (JIS K5600-5-6: 1999) was performed. Was carried out.

○: 100/100, no crack fall off

(Triangle | delta): Some crack is seen more than 99/100,

X: Falling Less than 99/100.

Example 2-1 Example 2-2 Example 2-3 Comparative Example 2 Epoxy resin Synthesis Example 1 Synthesis Example 1 Synthesis Example 1 NC-3000 Developability evaluation 32 21 27 29 Adhesion evaluation ○ ○ ○ ○ Heat resistance evaluation ○ ○ ○ △

Example 3 and Comparative Example 3 : Preparation of dry film for moldings and preparation of resin molding material

10 g of the epoxy resin synthesized in Synthesis Example 1 or commercially available epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.), 20 g of tripropylene glycol diacrylate as the reactive compound (B), and (meth) acrylic acid copolymer as other additive materials (Mitsubishi Rayon Co., Ltd., Diamond BR-77) 20 g, 4.72 g of Irgacure 907 (made by Shiva Specialty Chemicals) as a photoinitiator, and 0.47 g of Kayakure DETX-S (made by Nippon Kayaku Co., Ltd.), melamine as a thermosetting catalyst Methyl ethyl ketone 5g was added as 1.05 g and a viscosity adjustment solvent, it knead | mixed in a mixer, and it disperse | distributed uniformly, and obtained the active energy ray hardening type resin composition for this invention and comparative materials for molding materials.

The obtained composition is uniformly coated on a polyimide film that becomes a substrate film by a wire bar coat, passed through a hot air drying furnace having a temperature of 50 ° C., and a resin layer having a thickness of 50 μm is formed, and then protected on the resin layer. The polyethylene film used as a film was attached and the dry film for molding materials was obtained.

This dry film was uneven | corrugated and laminated | stacked on the polytetrafluoroethylene board through the thermal roll of 80 degreeC, and the ultraviolet-ray of 1000mJ was exposed from the PET film side.

After hardening by ultraviolet-ray, it peeled from the uneven | corrugated polytetrafluoroethylene board, and heated at 150 degreeC again for 1 hour. The obtained sample was evaluated as follows. The evaluation results are shown in the table below.

The molded surface was folded outward at 180 degrees, and the molded product was visually observed.

○: no crack fall off,

X: A slight crack is seen.

Example 3 Comparative Example 3 Epoxy resin Synthesis Example 1 NC-3000 Bendability rating ○ X

From the above result, it turns out that the active energy ray hardening-type resin composition of this invention using the epoxy resin which has a specific structure can obtain a strong molded object compared with the resin composition using the commercially available epoxy resin which has the same frame | skeleton.

Although the active energy ray-curable resin composition of the present invention shows an alkali developable resist material and a use as a molding material, the active energy ray-curable resin composition may also be used as other molding materials and film-forming materials as the use of this property. It can use suitably for the uses, such as an optical component, a coating material, and a film.

Claims (11)

A structure in which at least glycidoxy benzene or glycidoxy naphthalene is bonded with an aralkyl group as a bonding group and the following general formula (1) An active energy ray-curable resin composition containing a phenol aralkyl type epoxy resin (A) having a structure represented by (A) and a compound (B) having an unsaturated double bond that can be reacted by an active energy ray, which satisfies the following conditions: An active energy ray curable resin composition, comprising: Conditions: When the hydroxyl equivalent of the phenol aralkyl type epoxy resin (A) is X (g / eq.), The epoxy equivalent is Y (g / eq.), And the softening point is Z (° C), the relationship is as follows. Formula (α) 100 ≤ (X / Y) x Z ≤ 1100 Satisfying, The phenol aralkyl type epoxy resin (A) is represented by the following general formula (2)

[In Formula (2), Ar is

or

ego; In the above formulas (2) to (4), m represents the integer of 1-3 as the number of substituents R, n represents the average value of the repeating number of 1-10, R each represents a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 15 carbon atoms, a trifluoromethyl group, an aryl group or an allyl group, and each R may be the same or different from each other, and Ar may be the same or different. And, in other cases, the groups of formulas (3) and (4) are arranged in any order] Phenolic aralkyl resin of the structure represented by following formula (2 ')

[Formula (2), Ar '

or

ego, In formulas (2 ') to (4'), m and R represent the same meaning as in the formulas (2) to (4), n 'represents an average value of the repeating number of 1 to 10, and Ar' may be the same or different, and in other cases, the groups of the formulas (3 ') and (4') are arranged in any order] Obtained by reacting a phenol aralkyl type epoxy resin having a structure represented by Compound (B) having an unsaturated double bond that can be reacted by the active energy ray is a (meth) acrylate of a radical reaction type, an epoxy compound of a cationic reaction type, a vinyl compound, a urethane (meth) acrylate, a polyester (meth) Acrylate or epoxy (meth) acrylate. delete delete The active energy ray-curable resin composition according to claim 1, wherein all R of the phenol aralkyl type epoxy resin (A) are hydrogen atoms. The active energy ray-curable resin composition according to claim 1 or 4, wherein all Ar in the phenol aralkyl type epoxy resin (A) is a structure of formula (3), and all Ar 'is a structure of formula (3'). The compound according to claim 1 or 4, wherein the active energy ray-curable compound (B) contains a substituent capable of reacting with the epoxy resin (A) and an unsaturated double bond that can be reacted by an active energy ray together in the same molecule. Phosphorus active energy ray curable resin composition. The active energy ray-curable resin composition according to claim 1 or 4, which is a molding material. The active energy ray-curable resin composition according to claim 1 or 4, which is a material for forming a film. The active energy ray-curable resin composition according to claim 1 or 4, which is a resist material composition. Hardened | cured material of the active-energy-ray-curable resin composition of Claim 1 or 4. The multilayer material which has a layer of hardened | cured material of Claim 10.