JP5062714B2 - Active energy ray-curable resin composition and use thereof - Google Patents

Description

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

  With the aim of reducing the size and weight of portable devices and improving communication speed, printed wiring boards are required to have high precision and high density. With this, the demand for solder resists that cover the circuit itself has become increasingly sophisticated. Performance that can withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability is required more than required, and a film-forming material with tougher cured material properties is required. It was.

  For these materials, a method is generally used in which a hardened physical property is obtained by using a composite of a curing reaction by active energy rays such as ultraviolet rays and a thermosetting reaction by a compound having an epoxy group. (Patent Documents 1 and 2)

  In particular, an attempt to obtain an excellent mechanically and thermally toughened cured product by using a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku) as an epoxy resin material used here is also known. ing. (Patent Document 3).

Japanese Patent Publication No. 56-40329 Japanese Patent Publication No.57-45795 Japanese Patent No. 2952094

Although the curable resin composition using the phenol aralkyl type epoxy resin can obtain a relatively tough cured material, further toughened cured material properties are required. Furthermore, in film formation applications, particularly solder resist applications, physical properties in a state where the solvent is simply volatilized after the film formation is also an important factor. Specifically, if it is more flexible than necessary at this stage, peeling or patterning film contamination occurs. In particular, in the use of so-called dry film, this characteristic is more important because a transfer process is included.
An object of the present invention is to provide a resin composition that does not have these problems and can be cured by an active energy ray such as ultraviolet rays to obtain a tough film or a molding material.

に示される構造を有するフェノールアラルキル型エポキシ樹脂であって、以下の条件を満たすエポキシ樹脂（Ａ）、および活性エネルギー線により反応可能な不飽和二重結合を有する化合物（Ｂ）を含有することを特徴とする活性エネルギー線硬化型樹脂組成物に関する。
該フェノールアラルキル型エポキシ樹脂の水酸基当量をＸ（ｇ／ｅｑ．）、該エポキシ樹脂のエポキシ当量をＹ（ｇ／ｅｑ．）、軟化点をＺ（℃）とした場合にそれぞれの関係が下記式（α）を満たす。
１００≦（Ｘ／Ｙ）×Ｚ≦１１００・・・・（α）
さらに、本発明は、上記フェノールアラルキル型エポキシ樹脂（Ａ）が下記式（２）

（式（２）〜（４）中、ｍは置換基Ｒの数を表し１〜３の整数を、ｎは１〜１０の繰り返し数の平均値を示し、Ｒはそれぞれ水素原子、ハロゲン原子、炭素数１〜１５の炭化水素基、トリフルオロメチル基、アリル基またはアリール基のいずれかを表し、個々のＲはそれぞれ互いに同一であっても異なっていても良い。またＡｒは同一でも異なっていてもよく、異なっている場合、式（３）、（４）の基は任意の順で配列しているものとする。）
に示す構造のフェノールアラルキル樹脂とエピハロヒドリンとの反応により得られるエポキシ樹脂である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、上記フェノールアラルキル型エポキシ樹脂（Ａ）が、下記式（２）

（式（２）〜（４）中、ｍは置換基Ｒの数を表し１〜３の整数を、ｎは１〜１０の繰り返し数の平均値を示し、Ｒはそれぞれ水素原子、ハロゲン原子、炭素数１〜１５の炭化水素基、トリフルオロメチル基、アリル基またはアリール基のいずれかを表し、個々のＲはそれぞれ互いに同一であっても異なっていても良い。またＡｒは同一でも異なっていてもよく、異なっている場合、式（３）、（４）の基は任意の順で配列しているものとする。）
に示す構造のフェノールアラルキル樹脂と下記式（２’）

（式（２’）〜（４’）中、ｍ及びＲは式（２）〜（４）におけるのと同じ意味を示し、ｎ'は１〜１０の繰り返し数の平均値を示す。またＡｒ’は同一でも異なっていてもよく、異なっている場合、式（３’）、（４’）の基は任意の順で配列しているものとする。）
に示す構造のフェノールアラルキル型エポキシ樹脂とを反応させ得られたものであるジ上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、上記フェノールアラルキル型エポキシ樹脂（Ａ）の全てのＲが水素原子である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、上記フェノールアラルキル型エポキシ樹脂（Ａ）の全てのＡｒが式（３）の構造であり、全てのＡｒ’が式（３’）の構造である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、上記活性エネルギー線硬化性化合物（Ｂ）が、該エポキシ樹脂（Ａ）と反応可能な置換基と、活性エネルギー線により反応可能な不飽和二重結合を同一分子内に併せて含有する化合物である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、成型用材料である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、皮膜形成用材料である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、レジスト材料組成物である上記に記載の活性エネルギー線硬化型樹脂組成物に関する。
さらに本発明は、上記に記載の活性エネルギー線硬化型樹脂組成物の硬化物に関する。
さらに本発明は、上記に記載の硬化物の層を有する多層材料に関する。 In order to solve the above-mentioned problems, the present inventors have obtained an active energy ray-curable resin composition containing an epoxy resin having a specific structure, and can obtain a tough cured product, and further only by drying the solvent. The present invention was completed by finding that the resin has excellent resin properties even in the state.
That is, the present invention relates to a structure in which at least glycidoxybenzenes or glycidoxynaphthalenes are bonded with an aralkyl group as a bonding group, and the formula (1)

A phenol aralkyl-type epoxy resin having a structure shown in the following, which contains an epoxy resin (A) satisfying the following conditions, and a compound (B) having an unsaturated double bond capable of reacting with active energy rays The present invention relates to a characteristic active energy ray-curable resin composition.
When the hydroxyl group 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 respective relationships are as follows: (Α) is satisfied.
100 ≦ (X / Y) × Z ≦ 1100... (Α)
Further, in the present invention, the phenol aralkyl type epoxy resin (A) is represented by the following formula (2):

(In the formulas (2) to (4), m represents the number of substituents R and represents an integer of 1 to 3, n represents an average value of the number of repetitions of 1 to 10, and R represents a hydrogen atom, a halogen atom, It represents any of a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, and each R may be the same as or different from each other, and Ar may be the same or different. If they are different, the groups of formulas (3) and (4) shall be arranged in any order.)
The active energy ray-curable resin composition as described above, which is an epoxy resin obtained by a reaction between a phenol aralkyl resin having a structure shown in FIG.
Furthermore, in the present invention, the phenol aralkyl type epoxy resin (A) is represented by the following formula (2):

(In the formulas (2) to (4), m represents the number of substituents R and represents an integer of 1 to 3, n represents an average value of the number of repetitions of 1 to 10, and R represents a hydrogen atom, a halogen atom, It represents any of a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, and each R may be the same as or different from each other, and Ar may be the same or different. If they are different, the groups of formulas (3) and (4) shall be arranged in any order.)
And a phenol aralkyl resin having the structure shown below and the following formula (2 ′)

(In the formulas (2 ′) to (4 ′), m and R have the same meaning as in the formulas (2) to (4), and n ′ represents an average value of the number of repetitions of 1 to 10. Ar 'May be the same or different, and when they are different, the groups of formulas (3') and (4 ') are arranged in any order.)
It relates to the active energy ray-curable resin composition described above, which is obtained by reacting with a phenol aralkyl type epoxy resin having a structure shown in FIG.
The present invention further relates to the active energy ray-curable resin composition as described above, wherein all Rs of the phenol aralkyl type epoxy resin (A) are hydrogen atoms.
Furthermore, the present invention relates to the active energy ray curing as described above, wherein all Ars in the phenol aralkyl type epoxy resin (A) have the structure of the formula (3) and all Ar ′ have the structure of the formula (3 ′). Type resin composition.
Furthermore, the present invention combines the active energy ray-curable compound (B) with a substituent capable of reacting with the epoxy resin (A) and an unsaturated double bond capable of reacting with the active energy ray in the same molecule. It relates to the active energy ray-curable resin composition as described above, which is a compound to be contained.
The present invention further relates to the active energy ray-curable resin composition described above, which is a molding material.
The present invention further relates to the active energy ray-curable resin composition described above, which is a film forming material.
The present invention further relates to the active energy ray-curable resin composition described above, which is a resist material composition.
Furthermore, this invention relates to the hardened | cured material of the active energy ray hardening-type resin composition as described above.
The present invention further relates to a multilayer material having a layer of the cured product as described above.

The active energy ray-curable resin composition containing an epoxy resin having a specific structure of the present invention has excellent resin properties not only in obtaining a tough cured product but also in a state where the solvent is only dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a film-forming material that requires thermal and mechanical toughness.
More preferably, it can be used for applications requiring particularly high characteristics such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides.

に示される構造を有するフェノールアラルキル型エポキシ樹脂であって、以下の関係式が成り立つことを必須とする。
該エポキシ樹脂の水酸基当量をＸ（該当するエポキシ樹脂のエポキシ当量と、エポキシ樹脂中のエポキシ基と当量の酢酸を反応させ、エポキシ基を開環させた後、ＪＩＳ Ｋ ００７０に準じた方法で測定して得られた水酸基当量から算出した値。単位：ｇ／ｅｑ．）、該エポキシ樹脂のエポキシ当量をＹ（ＪＩＳ Ｋ−７２３６に準じた方法で測定した値。単位：ｇ／ｅｑ．）、軟化点をＺ（ＪＩＳ Ｋ−７２３４に準じた方法で測定した値。単位：℃）とした場合にそれぞれの関係が下記式（α）を満たす。
１００≦（Ｘ／Ｙ）×Ｚ≦１１００・・・・（α）
本発明において使用するエポキシ樹脂（Ａ）においてはエポキシ当量、水酸基当量、分子量（軟化点）のバランスが重要になる。すなわち、分子中に含まれるエポキシ基と水酸基の比率が重要なパラメータとなる。 In the active energy ray-curable resin composition of the present invention, the epoxy resin (A), which is an essential component, has a structure in which at least phenols or naphthols are bonded with an aralkyl group as a bonding group, and the following formula (1)

The phenol aralkyl type epoxy resin having the structure shown in FIG.
The hydroxyl group equivalent of the epoxy resin is X (measured by a method according to JIS K 0070 after reacting an epoxy equivalent of the corresponding epoxy resin and an epoxy group in the epoxy resin with an equivalent amount of acetic acid to open the ring of the epoxy group) Calculated from the hydroxyl group equivalent obtained in the above (unit: g / eq.), The value obtained by measuring the epoxy equivalent of the epoxy resin by a method according to JIS K-7236 (unit: g / eq.), When the softening point is Z (value measured by a method according to JIS K-7234. Unit: ° C.), each relationship satisfies the following formula (α).
100 ≦ (X / Y) × Z ≦ 1100... (Α)
In the epoxy resin (A) used in the present invention, the balance of epoxy equivalent, hydroxyl equivalent, and molecular weight (softening point) is important. That is, the ratio of the epoxy group and the hydroxyl group contained in the molecule is an important parameter.

  The bond of the formula (1) is a structure obtained when an epoxy resin reacts with a phenol compound or an alcohol compound. Generally, it is a bond formed when a high molecular weight grade, for example, solid bisphenol A type epoxy resin (or phenoxy resin) is synthesized, and this method is also called a one-step method or a fusion method (Advanced method or two-step method). (See pages 24-25 and 30-31, edited by Hiroshi Kakiuchi). The epoxy resin (A) is a compound utilizing this one-stage method or fusion method. In the present invention, either the one-stage method or the fusion method may be used. However, when the synthesis is carried out by the one-stage method, the reaction to obtain a by-product tends to occur, so the fusion method should be used. Is preferred.

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. In this case, it contributes to physical properties such as developability and sensitivity. However, when there are too many bonding modes, the concentration of epoxy groups in the molecular skeleton is reduced, which causes a problem in curability. Therefore, the ratio between the hydroxyl equivalent and the epoxy group becomes important. In addition, the softening point contributes to tackiness, but not only that, it contributes to the functional group density of the epoxy equivalent and hydroxyl equivalent, and also contributes to developability during alkali development. Therefore, it is a problem whether the softening point is too large or too small.
That is, the balance of epoxy equivalent, hydroxyl equivalent, and molecular weight (softening point) is important.

When this value exceeds 1100, the ease of resin flow during development with an alkali or a solvent is deteriorated, the development time is lengthened, and a problem arises in terms of productivity. Conversely, if it is less than 100, the curability is poor. Or, the sensitivity is deteriorated, and there is a problem that a pattern cannot be formed in detail. In some cases, tackiness may deteriorate.
In the formula (α), the range is from 100 to 1100, more preferably from 400 to 1000.
Furthermore, the active energy ray-curable resin composition of the present invention using the epoxy resin (A) satisfying the above conditions as a curing agent has excellent toughness in film properties.

  The epoxy resin (A) uses a phenol aralkyl resin as a raw material and reacts with epihalohydrin to bond the phenol aralkyl resins three-dimensionally (one-step method) or reacts the phenol aralkyl resin with the phenol aralkyl type epoxy resin. (Fusion method). The phenol aralkyl resin used as a raw material is a resin having a molecular structure in which an aromatic ring is bonded to phenols or naphthols through a methylene bond, an ethylidene bond, a propylidene bond, or the like. For example, phenols having a substituent R Or naphthols and bishalogenomethyl, bishalogenoethyl or bishalogenopropyl such as phenyl, biphenyl, fluorenyl or naphthyl; bisalkoxymethyl, bisalkoxyethyl or bisalkoxypropyl such as phenyl, biphenyl, fluorenyl or naphthyl Can be subjected to a condensation reaction with a bishydroxymethyl body such as phenyl, biphenyl, fluorenyl or naphthyl, a bishydroxyethyl body or a bishydroxypropyl body. As the phenol aralkyl resin, phenols or naphthols, preferably phenols, particularly preferably those obtained by condensation reaction of phenol and a compound having a biphenyl skeleton are preferable. 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 allyl group or an aryl group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group having 1 to 15 carbon atoms is methyl group, 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, cyclooctyl group, etc. And a linear or cyclic alkyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a toluyl group. Among these, a hydrogen atom, a methyl group, an allyl group or a tert-butyl group is preferable, and a hydrogen atom is particularly preferable. Although the substitution position of R is not particularly limited, the ortho position or the meta position of the hydroxyl group is independently taken. n is an average value of 1 to 10, preferably 1 to 5.0.
Such a phenol aralkyl resin is commercially available, and specific examples include XLC series manufactured by Mitsui Chemicals, MEH-7851 manufactured by Meiwa Kasei Co., Ltd., and KAYAHARD GPH65 manufactured by Nippon Kayaku Co., Ltd.

  Next, a phenol aralkyl type epoxy resin that is a raw material of the epoxy resin (A) in the fusion method will be described. The raw material phenol aralkyl type epoxy resin is a resin having a structure in which the phenolic hydroxyl group of the phenol aralkyl resin is glycidylated, and a compound represented by the formula (2 ') is preferable. As such a phenol aralkyl type epoxy resin, for example, the formula (7)

（式中ｎは繰り返し数を表す。）
で表されるエポキシ樹脂が挙げられる。このエポキシ樹脂は、近年、その難燃性、密着性、耐水性等、諸特性に優れることから注目されているエポキシ樹脂であり好ましい。

(In the formula, n represents the number of repetitions.)
The epoxy resin represented by these is mentioned. In recent years, this epoxy resin has been attracting attention because of its excellent properties such as flame retardancy, adhesion, and water resistance, and is preferable.

  A preferable raw material phenol aralkyl resin and raw material phenol aralkyl type epoxy resin of the epoxy resin (A) are generally synthesized by a method described in Japanese Patent No. 3122834 and JP-A No. 2001-40053. Specifically, 4,4′-bismethoxymethylbiphenyl and phenols are condensed under acidic conditions, or 4,4′-bishalogenomethylbiphenyl and phenols are condensed under acidic conditions; A condensation reaction of phenols may be mentioned. By reacting the obtained preferable phenol aralkyl resin with epihalohydrin, a preferable raw material phenol aralkyl type epoxy resin, preferably a compound represented by the formula (7), is obtained. As resin represented by Formula (7), Nippon Kayaku Co., Ltd. NC-3000 and NC-3000H are mentioned as a commercial item.

Below, the manufacturing method of an epoxy resin (A) is demonstrated.
As described above, the one-step method and the fusion method can be applied to the method for producing the epoxy resin (A). However, the conventional one-step method and fusion method are for bifunctional epoxy resins and phenol resins. When polyfunctional is used as the raw material as in the epoxy resin (A), the one-step method is a polyfunctional phenol resin. It is necessary to give sufficient consideration to the reaction ratio between the polyfunctional epoxy resin and the polyfunctional phenol resin in the fusion method.

First, the case of the one-stage method will be described in detail. The epoxy resin (A) can be obtained by reacting the above-described phenol aralkyl resin and epihalohydrin in the presence of an alkali metal hydroxide. In this one-stage method, the amount of epihalohydrin and alkali metal hydroxide used is a factor that determines the rate of introduction of the structure of formula (1).

  In the reaction for obtaining the epoxy resin (A), epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and epichlorohydrin which is easily available industrially is preferred in the present invention. 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 mol, the content ratio of the structure of (1) becomes too small, and the curability and heat resistance are lowered, and the characteristics of the resist may be lowered. When it exceeds 5.0 mol, the content ratio of the epoxy group is excessive.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When 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 distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.3-2.5 mol normally with respect to 1 mol of hydroxyl groups of raw material phenol aralkyl resin, Preferably it is 0.5-2.0 mol. If the amount of the alkali metal hydroxide used is outside this range, the curability and electrical reliability may be lowered.

The softening point of the epoxy resin (A) depends on its molecular weight. That is, when the molecular weight is large, the softening point is high, and when the molecular weight is small, the softening point is low.
In the case of this one-stage method, the molecular weight of the epoxy resin (A) is such that the molecular weight of the raw material phenol resin and the amount of epihalohydrin used (the molecular weight tends to decrease), the amount of alkali metal used for the epihalohydrin (the smaller the molecular weight, the smaller the molecular weight). For example).

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol aralkyl resin.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic 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 the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol aralkyl resin used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin (A).

Next, 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 the phenol aralkyl resin as described above. In this fusion method, the ratio of the raw material phenol aralkyl type epoxy resin and the phenol aralkyl resin is a factor that determines the introduction rate of the structure of the formula (1). That is, if the amount of the hydroxyl group of the phenol aralkyl resin is small with respect to the epoxy group of the phenol aralkyl type epoxy resin, the proportion of the structure of the formula (1) decreases, and if too large, gelation may be caused. From this point, when the reaction ratio of both is defined by the ratio of epoxy group and 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 phenol aralkyl resin used by weight is 0.001 to 0.5 parts by weight, preferably 0.01 to 100 parts by weight of the latter. 0.30 part by weight, particularly preferably 0.03 to 0.20 part by weight.

  The raw material phenol aralkyl type epoxy resin may be a commercially available compound or may be used after epoxidizing the phenol aralkyl resin. In the case of synthesis, for example, the following method can be used.

  The raw material phenol aralkyl type epoxy resin can be obtained by reacting a phenol aralkyl resin with an epihalohydrin. As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used, and epichlorohydrin which is easily available industrially 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 in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When 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 distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an 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 accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol aralkyl resin.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic 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 the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the phenol aralkyl resin used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain a phenol aralkyl type epoxy resin. An epoxy resin (A) can be obtained by reacting the obtained epoxy resin with a phenol aralkyl resin.

  This reaction uses a catalyst if necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7 ;, triphenylphosphine, diphenyl Organic phosphines such as sphin and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. The amount used in the case of using these catalysts depends on the kind of the catalyst, but is generally 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm, if necessary, based on the total resin amount. In this reaction, since the reaction proceeds without adding a catalyst, it is desirable to use it appropriately according to the preferred reaction temperature and amount of the reaction solvent.

In this fusion method, a solvent may or may not be used. When a solvent is used, any solvent can be used as long as it does not affect the reaction. For example, the following solvents can be used.
Polar solvents, ethers; dimethyl sulfoxide, N, N′-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, diglyme, triglyme, propylene glycol monomethyl ether, etc.
Ester organic solvents; ethyl acetate, butyl acetate, butyl lactate, γ-butyrolactone, etc.
Ketone organic solvent; aromatic organic solvent such as methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; 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 reaction time must be appropriately selected depending on the resin concentration and the amount of catalyst, and cannot be generally defined, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is preferable that the reaction time is short from the viewpoint of productivity. Moreover, reaction temperature is 0-250 degreeC normally, Preferably it is 30-200 degreeC.

  After completion of the reaction, the epoxy resin solution obtained by using a solvent is used as it is, and the concentration of the solution is adjusted as necessary, and it can also be used as a solution containing the epoxy resin (A) in the active energy ray-curable resin composition of the present invention. it can. Moreover, an epoxy resin (A) can be isolated by removing a catalyst etc. by water washing etc. as needed, and also distilling a solvent off under heating and pressure reduction.

  The blending ratio of the epoxy resin (A) suitable for the active energy curable resin composition of the present invention is 2 to 75% by weight when the nonvolatile content of the active energy curable resin composition is 100% by weight, Preferably, it is 5 to 30% by weight. When the amount is less than this range, the effect of the present invention is hardly exhibited, and when the amount is larger, the physical properties are hardly exhibited as the active energy ray-curable resin composition. Here, the nonvolatile content is a component having a boiling point exceeding 300 ° C.

  In addition to this, the epoxy resin (A) in the active energy curable resin composition of the present invention can be used in combination with other epoxy resins. Specific examples of other epoxy resins that can be used in combination include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted) Naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polycondensates, phenols and various diene compounds (dicyclopentadiene, tellurium Polymers, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone) , Benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyldimethanol, α, α, α', α ' -Polycondensates with biphenyldimethanol, etc., polycondensates with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates with bisphenols and various aldehydes Alcohol Examples of the glycidyl ether-based epoxy resin, alicyclic epoxy resin, glycidylamine-based epoxy resin, and glycidyl ester-based epoxy resin include glycidylated epoxy resins, but are not limited to these as long as they are usually used epoxy resins. These may be used alone or in combination of two or more. When another epoxy resin is used in combination, the epoxy resin (A) of the present invention is usually 30% by weight or more, preferably 50% by weight or more in all the epoxy resins to be blended.

  The compound (B) having an unsaturated double bond capable of reacting with active energy rays used in the present invention (hereinafter referred to as reactive compound (B)) is a general term for compounds showing reactivity with active energy rays. . These are used for the purpose of imparting curability by active energy rays, that is, reactivity to the composition.

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

  Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like. (In this specification, the terms “(meth) acryl” and “(meth) acrylate” mean acryl or methacryl, acrylate or methacrylate, respectively).

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  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, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

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

Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Polyester acrylate,
Other examples include epoxy acrylates derived from 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.

  The compounding ratio of the reactive compound (B) used in the active energy ray-curable resin composition of the present invention is usually 15 to 98% by weight, preferably 100% by weight when the nonvolatile content of the resin composition is 100% by weight, preferably 20 to 60% by weight. When the amount is less than this, curing with active energy rays becomes difficult, and when the amount exceeds this, desired properties as a composition may not be obtained. The non-volatile content indicated here is a component having a boiling point exceeding 300 ° C.

  Among these, as the reactive compound (B), a compound containing a substituent capable of reacting with the epoxy group of the epoxy resin (A) and an unsaturated double bond capable of reacting with active energy rays in the same molecule. When used, a thermosetting reaction with the epoxy resin (A) occurs, so that the effect of the present invention can be exhibited to a higher degree.

In the above, examples of the substituent capable of reacting with the epoxy group include a carboxyl group, an amino group, and a hydroxyl group.
The reactive compound (B) having a carboxyl group is, for example, an unsaturated carboxylic acid such as (meth) acrylic acid or a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a polybasic acid anhydride or the like ( For example, hydroxyethyl (meth) acrylate succinic acid half ester), and half ester compounds derived from epoxy (meth) acrylate and the like can be mentioned. The hydroxyl group-containing compound and polybasic acid anhydride (c) preferably used here will be described in detail later.
Moreover, (meth) acrylamide etc. are mentioned as a reactive compound (B) which has an amino group.

  Furthermore, as the reactive compound (B) containing a hydroxyl group, hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate and the like, and compounds obtained by reacting a reactive carboxyl group-containing compound such as (meth) acrylate with an epoxy resin, represented by epoxy acrylates.

  The active energy ray-curable resin composition of the present invention is obtained by uniformly mixing the above components at a predetermined ratio, and is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material that is used for applications in which it is irradiated with a focused light such as to cause a curing reaction to be molded.

  Specific applications include lens materials such as convex lenses, concave lenses, microlenses, Fresnel lenses, lenticular lenses, light guide materials used in liquid crystal display devices, uncured sheets, films, disks, etc. A so-called nanoimprint material that performs fine molding by pressing a finely processed “mold” into the composition, and further a sealing material for protecting the element, particularly a sealing material for a light emitting diode, a photoelectric conversion element, etc. are suitable. Can be cited as an important application.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, a film-forming material is temporarily applied to a peelable substrate to form a film, and then a so-called dry film in which a film is formed by being bonded to the originally intended substrate also corresponds to the film-forming material. .

  In particular, since the hydroxyl group concentration contained in the epoxy resin (A) is in an appropriate range for use as a dry film, a relatively tough dry film can be obtained, which is particularly preferable.

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the unirradiated part by some method, for example, a solvent or an alkaline solution.

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

As an application method to such a material, for example, when manufacturing a printed wiring board using the active energy ray-curable resin composition of the present invention containing a solvent as described later, first, a printed wiring board And applying the active energy ray-curable resin composition of the present invention to a film thickness of 0.5 to 160 μm by screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. A coating film is formed by drying a physical layer normally at 50-110 degreeC, Preferably it is 60-100 degreeC. Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² through a photomask having an exposure pattern such as a negative film, and the unexposed portion is described later. Using the liquid, development is performed, for example, by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further irradiation with ultraviolet rays is performed, and then heat treatment is usually performed at 100 to 200 ° C., preferably 140 to 180 ° C., so that the gold plating property is excellent, and the heat resistance, solvent resistance, acid resistance, and adhesion are improved. A printed wiring board having a permanent protective film that satisfies various properties such as flexibility is obtained.

  Examples of the alkaline aqueous solution used for development include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline solutions and tetramethylammonium. Organic alkaline aqueous solutions such as hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing at least active energy rays to the active energy ray-curable resin composition of the present invention.

  The multilayer material of the present invention refers to a material having at least two layers that can be obtained by forming and curing a film of the active energy ray-curable resin composition shown in the present invention on a substrate.

  The case where the active energy ray-curable resin composition of the present invention is used as a resist material composition is described in detail below.

  In the resist material composition of the present invention, a carboxyl group-containing compound is preferably used as the reactive compound (B). This is because, in resist applications, when the active energy ray non-irradiated part is dissolved with an alkaline aqueous solution or the like and patterning is performed, the carboxyl group not only reacts with the epoxy resin (A) but also imparts alkali solubility. It is also useful.

Especially for solder resist applications that require toughness, the reactive compound (B) is an unsaturated compound that can react with an epoxy compound (a) having two or more epoxy groups in the molecule by active energy rays. Compound (B-1) such as a reaction product obtained by reacting a polybasic acid anhydride (c) with an epoxycarboxylate compound obtained by reacting a monocarboxylic acid compound (b) having a double bond ,
An epoxy carboxylate compound obtained by reacting an epoxy compound (d) having two epoxy groups in the molecule with a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule, and a diisocyanate compound (e ), A carboxylic acid compound having two hydroxyl groups in the molecule (f), an arbitrary diol compound (g), and a compound obtained by reaction with an arbitrary acid anhydride such as the polybasic acid anhydride (c) (B-2) etc. are mentioned.

In the above, it is preferable that each component (a)-(c) used in a compound (B-1) is the following compound groups.
The epoxy compound (a) is particularly preferably an epoxy compound (a) having an epoxy equivalent of 100 to 900 g / equivalent. When the epoxy equivalent is less than 100, the molecular weight of the resulting compound (B-1) may be small and film formation may be difficult or flexibility may not be obtained sufficiently. When the epoxy equivalent exceeds 900, ethylenic properties may be obtained. There is a risk that the introduction rate of the monocarboxylic acid compound (b) having an unsaturated group is lowered and the photosensitivity is lowered.

  Specific examples of the epoxy compound (a) having two or more epoxy groups in the molecule include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane 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. Can be mentioned.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Company), Epicoat 154 (made by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.). ) And the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

  Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.), etc. Examples thereof include bisphenol-F type epoxy resin.

  Examples of the biphenol type epoxy resin include YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.), xylenol type epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like. Examples of the bisphenol A novolak type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.) and Epicoat E157S75 (manufactured by Yuka Shell Epoxy Co., Ltd.).

  Examples of the phenol aralkyl type epoxy resin include phenol-biphenyl aralkyl type epoxy resins such as NC-3000 and NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and XLC-3L (manufactured by Mitsui Chemicals, Inc.) Resin) and the like.

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000, NC-7300 series (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like. Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

  Examples of the monocarboxylic acid compound (b) include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and (meth) acrylate derivatives having one hydroxyl group in one molecule. And half-esters which are equimolar reactants, half-esters which are equimolar reactants of saturated or unsaturated dibasic acid and monoglycidyl (meth) acrylate derivatives, and the like. (Meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is particularly preferable.

  Any polybasic acid anhydride (c) may be used as long as it has at least one acid anhydride structure in the molecule. Succinic anhydride, acetic anhydride, phthalic anhydride, pyromellitic anhydride , Maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, ethylene glycol-bis (anhydro trimellitate), glycerin-bis (anhydro trimellitate) monoacetate, 1,2,3,4, -butane Tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4 , 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2-bis (3,4-amino) Lodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2 -Dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione The selected polybasic acid anhydride is particularly preferred.

Moreover, it is preferable that each component (b)-(g) used in a compound (B-2) is the following compound groups.
The epoxy compound (d) having two epoxy groups in the molecule is particularly preferably an epoxy compound (d) having an epoxy equivalent of 100 to 900 g / equivalent. If the epoxy equivalent is less than 100, the molecular weight of the resulting curable compound (B) may be small and film formation may be difficult and flexibility may not be obtained sufficiently. If the epoxy equivalent exceeds 900, ethylenic properties may be obtained. There is a risk that the introduction rate of the monocarboxylic acid compound (b) having an unsaturated group is lowered and the photosensitivity is lowered.

  Specific examples of the epoxy compound (d) having two epoxy groups in the molecule include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol-A type epoxy resins. Bisphenol epoxy such as bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3 , 3,3-Hexafluoropropane Alicyclic diesters such as hydrogenated bisphenol-type epoxy compounds such as epoxy compounds, halogenated bisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resins, brominated bisphenol-F type epoxy resins, and cyclohexanedimethanol diglycidyl ether compounds Glycidyl ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, aliphatic diglycidyl ether compounds such as diethylene glycol diglycidyl ether, polysulfide diglycidyl ether compounds such as 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, and Epomic R-304 (all Mitsui Chemicals), DER-331, DER-332, DER-324 (all manufactured by Dow Chemical), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide), RE -310S (manufactured by Nippon Kayaku), YD-8125 (manufactured by Tohto Kasei), etc., bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide), YDF-2001, YDF-2004, YDF-8170 (any) Also manufactured by Toto Kasei) Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (both manufactured by Dainippon Ink), hydrogenated bisphenol-A types such as HBPA-DGE (manufactured by Maruzen Petrochemical Co., Ltd.) and Rica Resin HBE-100 (manufactured by Nippon Nippon Chemical Co., Ltd.) Epoxy resin, brominated bisphenol-A type epoxy resin such as DER-513, DER-514, and DER-542 (all manufactured by Dow Chemical Co.), Celoxide 2021 (manufactured by Daicel), Rica Resin DME-100 (manufactured by Shin Nippon Rika) ), Alicyclic epoxy resins such as EX-216 (manufactured by Nagase Kasei), ED-503 (manufactured by Asahi Denka), Rica Resin W-100 (manufactured by Shin Nippon Rika), EX-212, EX-214, EX-850 ( Aliphatic diglycidyl ether compounds such as Nagase Kasei), FLEP-50, FLEP-60 Both east Thiokol Co.) polysulfide type diglycidyl ether compounds such as biphenol type epoxy compounds such as YX-4000 (manufactured by Japan Epoxy Resins) and the like.

  As the diisocyanate compound (e), any compound having two isocyanate groups in the molecule can be used, and a plurality of diisocyanate compounds can be reacted at the same time. Among them, diisocyanate compound (e) particularly excellent in flexibility and the like is phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate. , Isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or norbornane-diisocyanate methyl.

  As the carboxylic acid compound (f) having two hydroxyl groups in the molecule, any diol compound having both an alcoholic hydroxyl group or a phenolic hydroxyl group and a carboxyl group in the molecule can be used. Alcoholic hydroxyl groups having excellent properties are particularly preferred, and examples thereof include diol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid.

  As the arbitrary diol compound (g), any aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms can be used. Methylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-heptanediol, 1,9-nonanediol, 1,10-decane Diol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,4-dimethanol , Butadiene-acrylonitrile copolymer having a hydroxyl group at the end, water at the end Spiro glycol having a group, 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 having polystyrene in the side chain, and a polystyrene-acrylonitrile having a hydroxyl group at the terminal Examples thereof include diol compounds such as macromonomers having a copolymer in the side chain, or reaction products of these diol compounds with oxides such as ethylene oxide and propylene oxide.

  When the active energy ray-curable resin composition of the present invention is used as a solder resist application, the reactive compounds (B-1) and (B-2) have a solid content acid value of 50 to 150 mg · KOH / g. It is preferable to use what is. If the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and if patterning is performed, there is a possibility that it remains as a residue, or in the worst case, patterning cannot be performed. On the other hand, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high, and the photocured pattern may be peeled off.

  The reactive compound (B-1) is generally commercially available as acid-modified epoxy acrylates. Specifically, KAYARAD CCR-1159H (manufactured by Nippon Kayaku) as cresol novolac acid-modified epoxy acrylate, KAYARAD PCR-1169H (manufactured by Nippon Kayaku) as phenol novolac acid-modified epoxy acrylate, special bisphenol acid-modified epoxy acrylate KAYARAD ZAR-1559H (manufactured by Nippon Kayaku), KAYARAD ZFR-1540H (manufactured by Nippon Kayaku) and the like, and KAYARAD TCR-1310H (manufactured by Nippon Kayaku) as the trisphenolmethane acid-modified epoxy acrylate.

  In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various applications, other components may be added up to 70% by weight on an internal basis. Examples of other components include photopolymerization initiators, other additives, and coloring materials. The other component which can be used for the following is illustrated.

Examples of the radical 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-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthracones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.
One type of initiator can be used alone, or two or more types can be used in combination.

  In addition to this, a compound having a substituent capable of reacting with the epoxy group of the epoxy resin (A), which does not have an unsaturated double bond capable of reacting with active energy rays, is blended depending on the purpose of use. It is also preferable. Examples of the substituent capable of reacting with the epoxy group include a carboxyl group, an amino group, and a hydroxyl group. Among these, in view of the reactivity of the epoxy group, a carboxyl group or an amino group is preferable, and a carboxyl group is particularly preferable.

  Examples of such compounds include aliphatic carboxylic acids such as lauric acid, stearic acid, sebacic acid, tetra and hexahydrophthalic acid, aromatic carboxylic acids such as phthalic acid, and carboxyl groups such as (meth) acrylic acid. The radical copolymer etc. which copolymerized the containing monomer component are also mentioned.

  Other additives include thermosetting catalysts such as melamine, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and thixotropy such as aerosil. Agents, phthalocyanine blue, phthalocyanine green, titanium oxide, silicone, fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be used.

  Examples of pigment materials include organic pigments such as phthalocyanine, azo, and quinacridone, inorganic pigments such as titanium oxide, carbon black, bengara, zinc oxide, barium sulfate, and talc, known general coloring, and extender pigments. can do.

  In addition, resins that are not reactive with active energy rays and epoxy groups (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalates Resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range up to 40% by weight.

Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added in a range of 40% by weight, more preferably up to 20% by weight, based on the total weight of the composition.
Examples of volatile solvents that can be used include ketones such as acetone, ethyl methyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diester. Glycol ethers such as propylene 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, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl Ether acetate, dialkyl glutarate, dialkyl succinate, adipic acid dial And esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination. You may use together.

  In addition, an epoxy resin (A) may be mixed with an active energy ray hardening-type resin composition previously, and can also be mixed and used just before use. Of these, the above-mentioned main component solution (B) is blended into a two-component solution comprising a main agent solution containing an epoxy curing catalyst such as melamine and the like, and a curing agent solution mainly composed of an epoxy resin (A). It is also preferable to use a mixture of these.

  The energy ray curable resin composition of the present invention is cured only by irradiation with energy rays such as ultraviolet rays, but is heated at a temperature of 50 to 200 ° C., preferably 140 to 180 ° C. as necessary after irradiation with energy rays. By performing the treatment, the epoxy group can be thermally cured to obtain a hardened product in a short time. In addition, when using the composition of this invention for a resist use, this heat effect process is performed after the image development process after energy beam irradiation.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, unless otherwise specified, “parts” are parts by weight and “%” is% by weight. The softening point and epoxy equivalent were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JIS K-7236.
2) Hydroxyl equivalent: Obtained by measuring the epoxy equivalent of the corresponding epoxy resin and the epoxy group in the epoxy resin with an equivalent amount of acetic acid, ring-opening the epoxy group, and measuring according to JIS K 0070. It was calculated from the hydroxyl equivalent.
3) Softening point: measured by a method according to JIS K-7234
4) GPC measurement conditions are as follows.
Model: Shodex SYSTEM-21 Column: KF-804L + KF-803L (× 2) Linking eluent: THF (tetrahydrofuran); 1 ml / min. 40 ° C. Detector: UV (254 nm; UV-41)
Sample: About 0.4% THF solution (20 μl injection)
Calibration curve: Shodex standard polystyrene used

Synthesis Example 1: Synthesis of Epoxy Resin for Examples Phenol-biphenyl novolac type epoxy resin (Nipponization) as an epoxy resin of formula (2 ′) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirrer NC-3000H manufactured by Yakuhin Co., Ltd., epoxy equivalent 288 g / eq., Softening point 68 ° C., Ar ′ in formula (2 ′) is all formula (3 ′), R is all hydrogen atoms) 472.5 parts, formula (2) As a phenol aralkyl resin, 27.5 parts of phenol-biphenyl novolak resin (KAYAHARD GPH65 hydroxyl group equivalent 202 g / eq. Manufactured by Nippon Kayaku Co., Ltd., Ar in formula (2) is all represented by formula (3), and R is all hydrogen atoms) After adding 100 parts of methyl ethyl ketone and dissolving uniformly at 70 ° C., 1 part of triphenylphosphine was added and stirred at 100 ° C. for 40 hours. After completion of the reaction, oxygen purge was performed to oxidize triphenylphosphine, and then the solvent was distilled off to obtain 500 parts of the target epoxy resin (EP1). The epoxy equivalent of the epoxy resin (EP1) is 326 g / eq. The softening point was 80 ° C., the value of formula (α) was 648, and the melt viscosity (150 ° C.) was 0.86 Pa · s.

Synthesis Example 2: Synthesis of Epoxy Resin for Examples Phenol-biphenyl novolac epoxy resin (NC-3000H epoxy equivalent, manufactured by Nippon Kayaku Co., Ltd.) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirrer 288 g / eq., Softening point 68 ° C.) 477.5 parts, phenol-biphenyl novolak resin (KAYAHARD GPH65 hydroxyl group equivalent 202 g / eq.) Manufactured by Nippon Kayaku Co., Ltd. 22.5 parts, methyl ethyl ketone 50 parts are charged at 70 ° C. After uniformly dissolving, 0.5 part of triphenylphosphine was added and stirred at 105 ° C. for 30 hours. An epoxy resin varnish (VE1) was obtained by adding 169 parts of methyl ethyl ketone and adjusting the resin concentration to 70% by weight. When a part of the solvent was distilled off to obtain an epoxy resin (EP2) contained in the varnish, the epoxy equivalent was 312 g / eq. The softening point was 72 ° C., the value of the formula (α) was 880, and the melt viscosity (150 ° C.) was 0.51 Pa · s.

Synthesis Example 3: Synthesis of Epoxy Resin for Examples Phenol-biphenyl novolac type epoxy resin (Nipponization) as an epoxy resin of formula (2 ′) while purging nitrogen in a flask equipped with a stirrer, a reflux condenser, and a stirrer NC-3000H manufactured by Yakuhin Co., Ltd., epoxy equivalent 288 g / eq., Softening point 68 ° C., Ar ′ in formula (2 ′) is all formula (3 ′), R is all hydrogen atoms) 450 parts, phenol of formula (2) As an aralkyl resin, 50 parts of phenol-biphenyl novolak resin (KAYAHARD GPH65 hydroxyl group equivalent: 202 g / eq. Manufactured by Nippon Kayaku Co., Ltd., Ar in formula (2) is all represented by formula (3), and R is all hydrogen atoms), 100 parts methyl ethyl ketone And uniformly dissolved at 70 ° C., 1 part of triphenylphosphine was added, and the mixture was stirred at 100 ° C. for 80 hours. After completion of the reaction, oxygen purge was performed to oxidize triphenylphosphine, and then the solvent was distilled off to obtain 500 parts of the target epoxy resin (EP3). The epoxy equivalent of the epoxy resin (EP3) is 376 g / eq. The softening point was 91 ° C., the value of formula (α) was 405, and the melt viscosity (150 ° C.) was 3.34 Pa · s.

Comparative Synthesis Example 1: Synthesis of Epoxy Resin for Examples 249 parts of phenol aralkyl resin (in accordance with the method described in Japanese Patent Application Laid-Open No. 2003-301031) while purging nitrogen gas into a flask equipped with a stirrer, thermometer and condenser. Hydroxyl group equivalent 240 g / eq, softening point 94 ° C., Ar in formula (2) is all formula (3), R is all hydrogen atoms, n = 4.9 (average value), epichlorohydrin 555 parts (Phenol aralkyl resin, about 6 moles relative to one hydroxyl group equivalent) and 55 parts of methanol were added, dissolved under stirring, and heated to 73 ° C. Next, 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing with 300 parts of water was carried out, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure, 301 parts of a comparative epoxy resin (EP4) was obtained. The epoxy equivalent of the obtained epoxy resin was 311 g / eq. The softening point was 75 ° C., the value of the formula (α) was 1295, and the melt viscosity (150 ° C.) was 0.52 Pa · s.

Synthesis Example 4: Synthesis of Epoxy, Urethane Complex Type Carboxylic Acid-Containing Active Energy Ray Curing Compound (B-2) Epoxy having two or more epoxy groups in the molecule in a 3L flask equipped with a stirrer and a reflux tube As compound (d), Nippon Kayaku RE-310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184.0 g / equivalent) 368.0 g, monocarboxylic acid having an ethylenically unsaturated group in the molecule 141.2 g of acrylic acid (molecular weight: 72.06) as a compound (b), 1.02 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor and 1.53 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. The solution is reacted until the acid value of the liquid becomes 0.5 mg · KOH / g or less, and an epoxycarboxylate compound (theoretical molecule) : 509.2) was obtained.
Next, 755.5 g of carbitol acetate as a solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.16) as a carboxylic acid compound (f) having two hydroxyl groups in the molecule 268.3 g, 1.08 g of 2-methylhydroquinone as a thermal polymerization inhibitor and 140.3 g of spiroglycol (molecular weight: 304.38) as a diol compound (g) were added, and the temperature was raised to 45 ° C. To this solution, 485.2 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) was gradually added dropwise as a diisocyanate compound (e) so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature is raised to 80 ° C., and the reaction is carried out for 6 hours until absorption near 2250 cm ⁻¹ disappears by infrared absorption spectroscopy, and a resin solution containing 65% by weight of an aqueous alkali-soluble resin (B-2) Got. When the acid value was measured, it was 52.0 mg · KOH / g (solid content acid value: 80.0 mg · KOH / g).

Example 1 and Comparative Example 1: Preparation of Resist Dry Film and Resist Bonding Substrate Synthesis Examples 1-3, Comparative Synthesis Example 1, and a commercially available epoxy resin (trade name NC-3000, Nippon Kayaku Co., Ltd., formula Ar ′ in (2 ′) is all formula (3 ′), R is all hydrogen atom, epoxy equivalent 273 g / eq., Hydroxyl equivalent 9583.7 g / eq, softening point 57 ° C., and the value of formula (α) is 2001 ) 20g of each phenol aralkyl type epoxy resin and 34.44g of the epoxy compound obtained in Synthesis Example 4 as the reactive compound (B) and the urethane complex type carboxylic acid-containing active energy ray-curable compound (B-2). , And KAYARAD HX-220 (trade name: Nippon Kayaku diacrylate monomer) 3.54 g, Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 4.72 g of Kyacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a viscosity adjusting solvent, and kneaded uniformly in a roll mill. The present invention for resist and an active energy ray-curable resin composition for comparison were obtained.
After the obtained composition is uniformly coated on a polyethylene terephthalate (PET) film as a support film by wire bar coating, and passed through a hot air drying oven at a temperature of 70 ° C., a resin layer having a thickness of 30 μm is formed. A polyethylene film serving as a protective film was pasted on this resin layer to obtain a dry film for resist. The obtained dry film was laminated on the entire surface of a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 40 ° C. while peeling off the protective film.
After lamination, the film was exposed to vertical ultraviolet rays of 500 mJ through a patterned mask, and then the PET film was peeled off to evaluate its peelability, and then developed with a 1% by weight sodium carbonate aqueous solution and washed with water. Thereafter, the epoxy resin was cured and reacted with a hot air dryer at 150 ° C. to obtain a film.

The obtained sample was evaluated according to the following evaluation items.
-Peelability evaluation The peelability from a PET film is shown. ○: peels cleanly, Δ: dry film tears unless carefully peeled, ×: cannot peel.
-Warpage evaluation The degree of warping of the film after curing at 150 ° C is shown. ○: Almost no warpage. Δ: Some warpage is observed, ×: Warpage is large.
・ Bending evaluation The film after curing at 150 ° C. is valley-folded and strongly folded with a nail, and further folded into the opposite side at the same position and further strongly nailed with a nail. Visual evaluation of the state of the cured film at the folded part. ◯: No crack peeling, Δ: Some cracks are observed, ×: Peeling and cracking.
-Heat resistance evaluation The film after 150 degreeC hardening was immersed in the solder bath of 260 degreeC for 1 minute, it cooled, and the cellophane tape peeling test was done. ○: No peeling, Δ: Slight peeling, ×: Peel off greatly.

The evaluation results are summarized in the following table.

  From the above results, the active energy ray-curable resin composition of the present invention using an epoxy resin having a specific structure is tougher than a resin composition using a commercially available epoxy resin having a similar skeleton. It can be seen that a film is formed.

Example 2 and Comparative Example 2: Preparation of Alkali-Developable Liquid Solder Resist and Resist Evaluation 10 g of the epoxy resin synthesized in Synthesis Example 1 (Example) or a commercially available epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.) As reactive compounds (B-1), KAYARAD CCR-1159H (Example 2-1 and Comparative Example 2), KAYARAD ZAR-1559H (Example 2-2), and KAYARAD ZCR-1361 (Example 2-3) 30 g of each, 20 g of dipentaerythritol hexaacrylate as the other curable compound, 3 g of Irgacure 907 as an ultraviolet reactive initiator, and 0.5 g of DETX-S were mixed. Further, 30 g of barium sulfate powder was added and mixed by a three roll mill to prepare an alkali developing resist composition.
Further, this was coated on a copper-clad laminate with a hand applicator so as to have a film thickness of 20 μm at the time of drying, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, a multilayer material was obtained by irradiating and curing ultraviolet rays with an irradiation dose of 1000 mJ using an ultraviolet vertical exposure apparatus (Oak Seisakusho) equipped with a high-pressure mercury lamp. Similarly, a mask pattern was covered from the top of the coated product after drying, and then vertically exposed in the same manner to obtain a patterned multilayer material.
Moreover, what was covered and exposed with the mask pattern sprayed 1 weight% sodium carbonate aqueous solution with the spray, and melt | dissolved and developed the unexposed part.
The multilayer material after the ultraviolet irradiation was heat-treated at 150 ° C. for 60 minutes to react with the epoxy resin, and then the physical properties of the cured product were evaluated according to the following. The evaluation results are shown in the table below.

-Development property evaluation The time (seconds) until the development was completed was shown as the development time.
-Adhesive evaluation The adhesiveness to the base material of the board | substrate after 150 degreeC hardening was evaluated by the cross-cut cellophane tape peeling test (JISK5600-5-6: 1999). ○: No crack peeling 100/100, Δ: 99/100 or more where some cracks are observed, x: less than 99/100 with peeling.
・ Heat resistance evaluation Apply rosin-based flux to the substrate after curing at 150 ° C, then immerse in a solder bath at 260 ° C for 1 minute, cool, and perform a cross-cut cellophane tape peel test (JIS K5600-5-6: 1999). It was. ○: No crack peeling 100/100, Δ: 99/100 or more where some cracks are observed, x: less than 99/100 with peeling.

Example 3 and Comparative Example 3: Preparation of Molded Dry Film and Preparation of Resin Molding Material 10 g of epoxy resin synthesized in Synthesis Example 1 or commercially available epoxy resin (NC-3000, manufactured by Nippon Kayaku), reactive compound (B ), 20 g of tripropylene glycol diacrylate, 20 g of (meth) acrylic acid copolymer (Dainal BR-77 manufactured by Mitsubishi Rayon) as other additive material, and Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 4.72 g and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) 0.47 g, 1.05 g of melamine as a thermosetting catalyst and 5 g of methyl ethyl ketone as a viscosity adjusting solvent, kneaded with a mixer, uniformly dispersed, and a book for molding material An active energy ray-curable resin composition for invention and comparison was obtained.
The obtained composition is uniformly coated on a polyimide film as a substrate film by wire bar coating, passed through a hot air drying furnace at a temperature of 50 ° C., and a resin layer having a thickness of 50 μm is formed. A polyethylene film serving as a protective film was attached to the film to obtain a dry film for molding material.
The dry film was processed to be uneven and laminated on a polytetrafluoroethylene plate through a hot roll at 80 ° C., and then exposed to 1000 mJ ultraviolet rays from the PET film side.
After curing with ultraviolet rays, the film was peeled off from the concavo-convex processed polytetrafluoroethylene plate and further heated at 150 ° C. for 1 hour. The obtained samples were evaluated according to the following. The evaluation results are shown in the table below.

  The molded surface was bent outward at 180 degrees, and the molded product was visually observed. ○: No crack peeling, ×: Some cracks are observed.

  From the above results, the active energy ray-curable resin composition of the present invention using an epoxy resin having a specific structure is tougher than a resin composition using a commercially available epoxy resin having a similar skeleton. It can be seen that a molded product can be obtained.

  The active energy ray-curable resin composition of the present invention has shown use as a resist material capable of alkali development and as a molding material, but as another molding material and film-forming material as an application that makes use of this characteristic. Specifically, it can be suitably used for optical parts such as lenses, paints, films and the like.

Claims (9)

Structure and formula (1) in which at least glycidoxybenzenes or glycidoxynaphthalenes are bonded with an aralkyl group as a linking group

An active energy ray-curable resin composition containing a phenol aralkyl type epoxy resin (A) having the structure shown in FIG. 5 and a compound (B) having an unsaturated double bond capable of reacting with an active energy ray, An active energy ray-curable resin composition characterized by satisfying the following condition .
Conditions <br/> The hydroxyl equivalent of the phenol aralkyl type epoxy resin X (g / eq.), The error epoxy equivalent Y (g / eq.), The respective relationships softening point when the Z (° C.) The following formula (α)
100 ≦ (X / Y) × Z ≦ 1100... (Α)
The filling,
The phenol aralkyl type epoxy resin (A) is represented by the following formula (2):

(In the formulas (2) to (4), m represents the number of substituents R and represents an integer of 1 to 3, n represents an average value of the number of repetitions of 1 to 10, and R represents a hydrogen atom, a halogen atom, It represents any of a hydrocarbon group having 1 to 15 carbon atoms, a trifluoromethyl group, an allyl group or an aryl group, and each R may be the same as or different from each other, and Ar may be the same or different. If they are different, the groups of formulas (3) and (4) shall be arranged in any order.)
And a phenol aralkyl resin having the structure shown below and the following formula (2 ′)

(In the formulas (2 ′) to (4 ′), m and R have the same meaning as in the formulas (2) to (4), and n ′ represents an average value of the number of repetitions of 1 to 10. Ar 'May be the same or different, and when they are different, the groups of formulas (3') and (4 ') are arranged in any order.)
It was obtained by reacting with a phenol aralkyl type epoxy resin having the structure shown in
The compound (B) having an unsaturated double bond that can react with the active energy ray is an unsaturated compound that can react with the epoxy compound (a) having two or more epoxy groups in the molecule by the active energy ray. Compound (B-1) which is a reaction product obtained by reacting a polybasic acid anhydride (c) with an epoxycarboxylate compound obtained by reacting a monocarboxylic acid compound (b) having a double bond Or an epoxy carboxylate compound obtained by reacting an epoxy compound (d) having two epoxy groups in the molecule with a monocarboxylic acid (b) having an ethylenically unsaturated group in the molecule, and a diisocyanate compound ( e) Reaction with a carboxylic acid compound (f) having two hydroxyl groups in the molecule, an arbitrary diol compound (g), and an arbitrary polybasic acid anhydride (c) A more resulting compound (B-2), and
When the nonvolatile content of the active energy ray-curable resin composition is 100% by weight, the blending ratio of the phenol aralkyl type epoxy resin (A) is 2 to 75% by weight and can be reacted by the active energy ray. The compounding ratio of the compound (B) having an unsaturated double bond is 15 to 98% by weight. 2. The active energy ray-curable resin composition according to claim 1 , wherein all R of the phenol aralkyl type epoxy resin (A) is a hydrogen atom. All Ar phenol aralkyl type epoxy resin (A) is a structure of formula (3), the structure and the active energy ray curable resin according to claim 1 or 2, all the Ar 'has the formula (3') Composition. The active energy ray-curable compound (B) has the same molecule as a substituent selected from a carboxyl group, amino group or hydroxyl group capable of reacting with the epoxy resin (A) and an unsaturated double bond capable of reacting with the active energy ray. The active energy ray-curable resin composition according to any one of claims 1 to 3 , which is a compound contained in the inside. The active energy ray-curable resin composition according to any one of claims 1 to 4 , which is a molding material. The active energy ray-curable resin composition according to any one of claims 1 to 4 , which is a film forming material. It is a resist material composition, The active energy ray hardening-type resin composition as described in any one of Claims 1-4 . Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 1-4 . A multilayer material having a layer of the cured product according to claim 8 .