KR20170095141A - Oxazine resin composition and cured product thereof - Google Patents

Abstract

The purpose of the present invention is to provide an oxazine resin composition which is excellent in heat resistance and has good dimensional stability even at industrial curing conditions of low temperature and short time, and a cured product the oxazine resin composition. The oxazine resin composition comprises an oxazine resin (A) and an epoxy resin (B), wherein the oxazine resin (A) is represented by the following formula (1). In gel permeation chromatography (GPC) measurement, the oxazine resin composition has 15% or less of a content for the body of n = 0, 35 to 70% of a total content for bodies of n = 1 and n = 2, 50% or less of a content for the body of n = 3 or higher, and a molecular weight distribution with a number average molecular weight of 400 to 2500. In chemical formula 1, A_1 is an aromatic ring group selected from a benzene ring, a naphthalene ring, and a biphenyl ring; X is a divalent cross-linking group; m is 1 or 2; and n is 1 to 5.

Description

TECHNICAL FIELD [0001] The present invention relates to an oxazine resin composition and a cured product thereof.

The present invention relates to an oxazine resin composition containing an oxazine resin and an epoxy resin, and a cured product obtained by heat-curing the composition.

Description of the Related Art [0002] In recent years, there has been a demand for a curable resin composition for use in a copper clad laminate for a printed wiring board, an adhesive for a multilayer wiring board, a sealing material for semiconductor, an adhesive for semiconductor mounting, a semiconductor mounting module, There is a demand for a heat-resistant material excellent in stability and reliability under high temperature and high humidity. In the field of energy, further research and development such as fuel cells and various secondary batteries have progressed, and heat resistant materials have become necessary. Particularly, in a hybrid, an electric vehicle, and a distributed power source, a power device is mainly used in an inverter, and its power density is also dramatically increasing. Accordingly, the emergence of silicon carbide (SiC) devices operating at high temperatures of 200 DEG C or higher is also expected. Further, since an electronic control unit (ECU) using a conventional semiconductor chip is also mounted in an engine room in an environment of a vehicle cabin, heat resistance that can withstand harsh conditions is also required. For such a demand, a heat-resistant resin obtained by reacting a benzoxazine ring structure-containing compound with an epoxy resin has been studied (Patent Documents 1 and 2, Non-Patent Document 1, etc.).

When a compound containing a benzooxazine ring structure and an epoxy resin such as bisphenol A diglycidyl ether are reacted in a stoichiometric amount, unreacted materials remain to inhibit the formation of an ideal crosslinked structure, It has been reported that the resin after curing gives a high glass transition point (Tg) by increasing the amount of the epoxy resin (Non-Patent Document 2). However, these conventional resins and resin compositions can not be said to have sufficient properties in terms of heat resistance and flame retardancy at a glass transition temperature of about 160 DEG C, and a high curing temperature and a long curing time are required to obtain good properties Had a drawback. In order to improve the glass transition temperature by industrial low-temperature short-time curing, it is possible to use an oxepine resin obtained by using a polyfunctional phenol resin as a raw material. In this method, however, uncured portions remain and the glass transition temperature becomes high, It had the drawback of being.

In addition, in recent years, there has been a problem of bending of the laminated board due to the thinning of the laminated board, and a low bending performance is required. For this reason, the resin to be used is required to be low in carbonization, but an acryl resin composition that satisfies these properties has not been obtained.

Japanese Patent Application Laid-Open No. 2003-147165 Japanese Laid-Open Patent Publication No. 2008-94961

 Molding Processing, Vol. 19, No. 10, 634-640 (2007)  J. Appl. Polym. Sci., Vol. 61, p1595 (1996)

An object of the present invention is to provide an oxpeg resin composition and a cured product thereof which can provide a cured product having excellent heat resistance and good dimensional stability even under curing conditions of industrially favorable low temperature and short time.

The present inventors have conducted intensive studies in order to achieve the above object. As a result, it has been found that by using a polyfunctional oxazine resin having a specific molecular weight distribution, the heat resistance is improved and the viscosity of the resin is low, And that the modulus of elasticity of the cured product is relatively low. Thus, the present invention has been completed.

That is, the present invention relates to an oxepine resin composition containing an oxepine resin (A) and an epoxy resin (B), wherein the oxepine resin (A) is represented by the following formula (1), and the gel permeation chromatography ), The content ratio of n = 0 body is 15% (area%) or less, the total content of n = 1 body and n = 2 body is 35 to 70%, the content ratio of n = 3 body or more is 50% And has a number average molecular weight of 400 to 2,500 in terms of standard polystyrene.

[Chemical Formula 1]

In the formula (1)

A ₁ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group may be an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms , An aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms may be substituted as a substituent of the aromatic ring. In formula (1), A ₁ is an integral part of a ring constituent atom comprising -CNCO- and two adjacent carbons in the aromatic ring to form an oxazine ring. For example, when A ₁ is a benzene ring, R ₁ is a phenyl group, and R ₂ is hydrogen, it has a structure having an N-phenyl-benzoxazine ring structure. In the present specification, the biphenyl ring as the aromatic ring group means -Ph-Ph- (where Ph denotes a phenylene group), and the oxazine ring denotes a -CNCOCC- group which is a cyclic 6-membered ring Jade photo ring).

X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or (1b).

Each R ₁ independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

m is 1 or 2, and n is an integer of 0 or more as the number of repeating units, and the average value thereof is 1 to 5.

(2)

In formula (1a), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

In formula (1b), R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms. A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An aryloxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms may be substituted as a substituent of the aromatic ring.

The above-mentioned jade photographic resin composition may contain a curing agent for epoxy resin (C), and the curing accelerator (D) may be contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the epoxy resin (B). As the curing agent (C) for an epoxy resin, a phenolic curing agent is preferred.

(H) of the curing agent (C) for an epoxy resin and the oxazine ring (Z) of the oxepine resin (A) in the case of mixing the curing agent for epoxy resin (C) / 1. ≪ / RTI >

It is preferable that the total amount of the oxazine ring (Z) and the active hydrogen (H) be 0.2 to 1.5 moles per mole of the epoxy group of the epoxy resin (B).

The present invention also provides an oxepine resin composition comprising an oxepine resin (A) and an epoxy resin (B), wherein the oxepine resin (A) Wherein the novolak phenol compound (e) is represented by the following formula (2) and the content of k = 0 in the gel permeation chromatography measurement is , The content ratio of the k = 1 substance and the k = 2 substance is 50 to 95%, the content ratio of the k = 3 substance is 15% Is 15% or less, and the number average molecular weight is 350 to 1,500 in terms of standard polystyrene.

R ₁ -NH ₂ (21)

R ₂ -CHO (22)

(R ₁ and R ₂ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms)

(3)

In the formula (2)

A _1, X and m is a A _1, X and m as defined with each of the formula (1).

k represents an integer of 0 or more as the number of repeating units, and the average value thereof is 0.8 to 3.

Further, the present invention is a prepreg or laminated plate characterized by using the above-mentioned jade photographic resin composition. Further, the present invention is a cured product obtained by curing the above-mentioned jade photographic resin composition.

The present invention also provides a method for producing an ophthalmic resin by reacting a novolak phenol compound (e) with a monoamino compound and an aldehyde, wherein the novolak phenol compound (e) is a novolak phenol compound represented by the formula (2) Phenol compound (e) is used.

It is preferable that the monoamino compound is aniline and the aldehyde is formaldehyde.

The cured product obtained by curing the jade photographic resin composition of the present invention is excellent in heat resistance, low thermal expansion coefficient and flame retardancy, and hardly generates volatile by-products during the curing reaction.

1 is a GPC chart of the jade photographic resin of the present invention.
2 is an FT-IR chart of the jade photographic resin of the present invention.
3 is a GPC chart of the raw novolak phenol compound.
4 is a GPC chart of an oxazine resin of Comparative Example 1. Fig.

The photoresist composition of the present invention contains an oxepine resin (A) and an epoxy resin (B). The content of the n = 0 form is 15% or less, the sum of the contents of n = 1 form and n = 2 form is 35 to 70 (% by mass) %, A content ratio of n = 3 or more is 50% or less, and a number average molecular weight (Mn) is 400 to 2500 in terms of standard polystyrene. Such an oxepine resin (A) is obtained from a novolak phenol compound (e) having a specific molecular weight distribution, a monoamino compound and an aldehyde. Here, n = 1, n = 2, n = 3, k = 1, k = 2, k = 3, etc. in the jade photographic resin (A) and the novolak phenol compound Is the area% obtained by GPC measurement. The n = 1 form refers to a component in which n is 1 in the formula (1), and the n = 0 form refers to a component in which n in the formula (1) is 0. Here, the GPC measurement conditions are in accordance with the conditions described in the examples.

In the formula (1), A ₁ is an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring which may have a substituent. The aromatic ring of the aromatic ring group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms , An aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different. However, it is preferable that the two carbons constituting part of the hydroxazine ring do not have a substituent, and one carbon adjacent to the two carbons does not have a substituent. In the formulas (1) to (7), (21) and (22), common symbols have the same meanings unless otherwise specified.

Examples of the alkyl group include a linear, branched, or cyclic alkyl group and include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- , Pentyl group, hexyl group, cyclohexyl group and the like. Among them, the branched chain or cyclic alkyl group tends to give higher heat resistance than the linear chain type. The number of carbon atoms is preferably 1 to 4 in the case of a chain alkyl group and 6 in the case of a cyclic alkyl group. And is preferably an isopropyl group, an isobutyl group, a tert-butyl group or a cyclohexyl group, more preferably a tert-butyl group or a cyclohexyl group. Further, a methyl group is also preferable because flame retardancy tends to be improved.

Examples of the aryl group include a phenyl group and a naphthyl group, and preferably a phenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a 1-phenylethyl group and the like, preferably a benzyl group and a 1-phenylethyl group.

X is a divalent aliphatic cyclic hydrocarbon group, or a crosslinking group represented by the formula (1a) or the formula (1b). The divalent aliphatic cyclic hydrocarbon group preferably has 5 to 15 carbon atoms, more preferably 5 to 10 carbon atoms. Here, the divalent aliphatic cyclic hydrocarbon group is preferably an unsaturated ring such as dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorbornene-2-ene,? -Pinene,? -Pinene, And a divalent aliphatic cyclic hydrocarbon group derived from an aliphatic hydrocarbon-type aliphatic hydrocarbon compound. Of these aliphatic cyclic hydrocarbon groups, divalent hydrocarbon groups derived from dicyclopentadiene are particularly preferred from the viewpoint of heat resistance. In the formulas (1a) and (1b), R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms. A ₂ has the same meaning as A ₁ in the formula (1) except that the valence is divalent.

Each R ₁ independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. For example, a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a benzyl group are exemplified, and a methyl group, a phenyl group and a tolyl group are preferable.

R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. For example, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and the like, preferably a hydrogen atom, a methyl group and a phenyl group.

m is 1 or 2 and corresponds to the number of hydroxyl groups in the starting novolak phenol compound.

n represents an integer of 0 or more as a repeating unit, and the average value (number average) thereof is 1 to 5, preferably 1.2 to 4.5, and more preferably 1.7 to 4. This range is preferable in that the effect of improving the curability is remarkable. In the above formula (1), n can be obtained as follows.

The GPC measurement revealed that the styrene-reduced molecular weights (? 0,? 1,? 2,? 3,? 4) corresponding to n = 0, n = 1, n = 2, n = of the theoretical molecular weights (? 0,? 1,? 2,? 3,? 4) of n = 0, n = 1, n = 2, n = alpha 1, beta 2 / alpha 2, beta 3 / alpha 3, beta 4 / alpha 4) are obtained, and an average value of these (beta 0 / alpha 0 to beta 4 / alpha 4) is obtained. The numerical value obtained by multiplying the molecular weight Mn converted by styrene by the GPC and this average value is defined as an average molecular weight Mn '. Next, the value of n is calculated by taking the theoretical molecular weight of the formula (1) as the average molecular weight Mn '.

For example, in the case of the jade photographic resin of Example 1 described later, the structural formula becomes the formula (3) described later, and the theoretical molecular weight is 434 + 223n = Mn '. From the measured GPC values, Mn is 754 and the average value of (? 0 /? 0 to? 4 /? 4) is 1.147. Therefore, from 434 + 223 n = 754 x 1.147, n = 1.9 can be obtained by calculation.

The jade photographic resin (A) used in the present invention is required to have a specific molecular weight distribution, and the content ratio of n = 0 and n = 3 or more is not more than a specific amount, and n = 1 and n = It is important that the sum of the content ratios falls within a specific amount range.

When the content ratio of n = 0 is more than 15% (area%), the heat resistance is improved (high Tg), but the cured portion is hard and brittle and the low elastic modulus may not be improved. The content of n = 0 is preferably 12% or less, more preferably 10% or less, still more preferably 5% or less.

When the content ratio of n = 3 or more is more than 50%, the reactivity is remarkably deteriorated and there is a possibility that unrecorded substances are left much. The content ratio of n = 3 or more is preferably 45% or less, and more preferably 40% or less.

Within the above range, when the content ratio of n = 0 is small, it is preferable that the content ratio of n = 3 or more is also small. When the content ratio of n = 0 is large, the content ratio of n = 3 or more may be large. Therefore, the difference between the content ratio of n = 0 and the content ratio of n = 3 or more is preferably 30 to 40%.

When the n = 1 or n = 2 is a specific amount, the cured product has a high Tg and a low elastic modulus, and the reactivity is also improved. This tendency occurs even when n = 1 or n = 2, so it is preferable to control the inclusion ratio of n = 1 and n = 2. The sum of the contents of n = 1 and n = 2 is preferably 40 to 65%, more preferably 43 to 60%, and even more preferably 45 to 55%.

The number average molecular weight is 400 to 2,500 in terms of standard polystyrene, preferably 400 to 2000, more preferably 450 to 1,500, and even more preferably 450 to 1,000.

In addition, in addition to the jade photographic resin (A) represented by the above formula (1), at least two peaks of n = 2 or more in the GPC measurement, a compound obtained by subjecting the novolak phenol compound (e) to a self-polymerization with a monoamino compound and an aldehyde But since these compounds can not be separated, the respective content ratios were calculated as the area percentages contained.

An oxepine resin (A) represented by the following formula (3) derived from a phenol novolak resin in which A ₁ is a benzene ring, X is a methylene group, R ₁ is a phenyl group, R ₂ is a hydrogen atom, .

[Chemical Formula 4]

As described above, the jade photographic resin (A) is obtained from a novolak phenol compound (e) having a specific molecular weight distribution, a monoamino compound and an aldehyde. R ₁ in the formula (1) is a substituent derived from a monoamino compound, and R ₂ is a substituent derived from an aldehyde.

The novolak phenol compound (e) having a specific molecular weight distribution is represented by the above formula (2). k is an integer of 0 or more as the number of repeating units, and the average value (number average) thereof is 0.8 to 3, preferably 1.0 to 2.7, more preferably 1.2 to 2.5. The content ratio of k = 0 body is 20% (area%) or less in the GPC measurement, the content ratio of k = 1 body and k = 2 body is 50 to 95%, the content ratio of k = 3 body is 15% , The content of the high molecular weight component having k = 4 or more is 15% or less, and the specific gravity of Mn is 350 to 1,500 in terms of standard polystyrene. Without such a molecular weight distribution, the oxazine resin used in the present invention can not be obtained in a good yield.

The content of k = 0 is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, most preferably 5% or less. The content of the high-molecular-weight polymer having k = 4 or more is preferably 10% or less, and more preferably, no high-molecular-weight polymer having k = 5 or more is contained at all. The content ratio of k = 3 is preferably 10 to 15%. The sum of the content ratios of k = 1 and k = 2 is preferably 60 to 92%, and more preferably 65 to 90%. In particular, the content ratio of k = 1 is preferably 35 to 65%, and the content ratio of k = 2 is preferably 15 to 30%. The number average molecular weight Mn is preferably from 350 to 1,000, more preferably from 350 to 700, still more preferably from 400 to 550. The dispersion degree (weight average molecular weight Mw / Mn) is preferably 1.05 to 1.3, more preferably 1.08 to 1.2, and further preferably 1.1 to 1.15. The measurement conditions of the GPC of the novolak phenol compound (e) are the same as the measurement conditions of GPC of the jade photographic resin (A).

The phenols used to obtain the novolak phenol compound (e) include phenol, cresol, ethyl phenol, butyl phenol, styrenated phenol, cumyl phenol, naphthol, catechol, resorcinol, naphthalenediol, But these phenols may be used alone or in combination of two or more. Among these phenols, monophenols such as phenol and alkylphenol are preferable. As the alkyl group in the case of alkylphenol, an alkyl group having 1 to 6 carbon atoms is suitable.

Examples of the crosslinking agent for obtaining the novolac phenol compound (e) include aldehydes such as formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, amylaldehyde and benzaldehyde represented by the following formula (4) , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetophenone, p-xylylene glycol represented by the following formula (6), p-xylylene glycol dimethyl ether, p-xylylene dichloride, A crosslinking agent such as dimethoxymethylbiphenyl, 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalenes and dichloromethylnaphthalenes, or a crosslinking agent such as divinylbenzenes, divinylbiphenyls, di Vinyl naphthalenes and the like, and cycloalkyldienes such as cyclopentadiene and dicyclopentadiene. However, the present invention is not limited thereto, and these crosslinking agents may be used alone or in combination of two kinds It may be used in combination with more. X in the formulas (1) and (2) is a bivalent aliphatic cyclic hydrocarbon group when a cycloalkyldiene is used, and when a cross-linking agent of the formula (4) And when the crosslinking agent of the formula (6) or the formula (7) is used, the crosslinking group is represented by the formula (1b). Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-xylylene dichloride and 4,4'-dichloromethylbiphenyl are preferable, and formaldehyde is particularly preferable. Preferable forms when formaldehyde is used in the reaction include formalin aqueous solution, paraformaldehyde, and trioxane.

[Chemical Formula 5]

Equation (4) and in the formula (5), R ₃ and R ₄ are each as defined and R ₃ and R ₄ in formula (1a). In the formula (6) and Equation (7), R _5, R ₆ and A ₂ are each the same meaning as R _5, R ₆ and A ₂ in the formula (1b), Y is independently a hydroxyl group, an alkoxy group, or Halogen atom.

Examples of the acidic catalyst used for obtaining the novolak phenol compound (e) include proton acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid and toluenesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, tin chloride, , Oxalic acid, and monochloracetic acid. However, the present invention is not limited thereto. These acidic catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid and oxalic acid are preferable.

The novolac phenol compound (e) having a specific molecular weight distribution used in the present invention can be obtained by adjusting the molar ratio of the phenols and the aldehydes and removing the low molecular weight component from the obtained novolak phenol compound (e) have. The novolak phenol compound (e) may also be obtained by using a production method as disclosed in Japanese Patent Application Laid-Open No. 2002-194041 or Japanese Patent Application Laid-Open No. 2007-126683.

The molar ratio of the phenol and the crosslinking agent is represented by the molar ratio of the phenols to the one mole of the crosslinking agent (phenol / crosslinking agent), and the molar ratio thereof is 1 or more. When the molar ratio is large, k = 0 and k = . On the contrary, when the molar ratio is small, a large number of high molecular weight units having k = 3 or more are produced, and k = 0 and k = 1 are fewer. Further, in order for the oxazine resin to have a specific molecular weight distribution, the novolak phenol compound (e) needs to have a specific molecular weight distribution. In order to achieve the above range, the molar ratio (phenol / crosslinking agent) between the phenol and the crosslinking agent is preferably 3 or more and 6 or less, and more preferably 4 or more and 5 or less. The novolak phenol compound (e) having a specific molecular weight distribution can be obtained by reducing or eliminating the low molecular weight component of the novolak phenol compound (e) obtained by adjusting the molar ratio of the phenol and the crosslinking agent. In this case, as a method for reducing or eliminating a low molecular weight component, particularly k = 0, there may be mentioned a method using a difference in solubility of various solvents, a method of dissolving in an aqueous alkali solution, and other known separation methods.

The monoamino compound used to obtain the jade photographic resin is represented by the formula (21), and the aldehyde is represented by the formula (22).

In the formula (21), R ₁ is the same meaning as R ₁ in the formula (1). Specifically, it is preferable that R ₁ is methylamine of methyl group, ethylamine of ethyl group, propylamine of propyl group, butylamine of butyl group, aniline of phenyl group, methyl aniline of tolyl group, dimethylaniline of xylly group, benzyl amine of benzyl group , But the present invention is not limited thereto. Of these monoamino compounds, aromatic monoamine compounds are preferable, and aniline and methyl aniline are more preferable.

(22) of, R ₂ has the same meaning as R ₂ in the formula (1).

These aldehydes are the same as the aldehydes used for obtaining the novolac phenol compound (e). Of these aldehydes, formaldehyde, acetaldehyde and benzaldehyde are preferable, and formaldehyde is particularly preferable. Preferable forms when formaldehyde is used include formalin aqueous solution, paraformaldehyde, and trioxane.

The amount of each raw material to be used is preferably 1 to 2 moles, more preferably 0.9 to 1.1 moles, of the monoamino compound per 1 mole (equivalent) of the hydroxyl group of the novolak phenol compound (e). The aldehyde is preferably 1.7 to 2.5 moles, and more preferably 1.8 to 2.2 moles. Particularly, the aldehydes are preferably added in a slight excess. The theoretical amount is 1 mole of the monoamino compound and 2 moles of the aldehyde per 1 mole of the hydroxyl group of the novolak phenol compound, but as the side reaction, the polymerization of the novolac phenol compound and the reaction product of only the monoamino compound and the aldehyde are produced. Since the separable unreacted material is removed in the post-treatment step, the monoamino compound or the aldehyde may remain. The total amount of these impurities is preferably 5 mass% or less.

When the novolak phenol compound (e) has on average m (k + 2) OH groups, 1 mole of the novolak phenol compound is calculated to have m (k + 2) Moles are calculated as 1 equivalent.

As the manufacturing method, there is no special manufacturing method, and a commonly used manufacturing method can be used. As a general production method, a method in which a novolac phenol compound (e) and a monoamino compound are heated and stirred in a solvent, then an aldehyde is added, and the mixture is maintained at 70 to 120 ° C for 20 minutes to 24 hours. After the reaction, the product is isolated and purified by a method of reprecipitation by introducing the product into a poor solvent having a low dissolving power for a product such as methanol or by a synthetic chemical method such as solvent extraction to obtain a volatile component such as a condensate, The resin is dried under reduced pressure at a reduced pressure to obtain the oxazine resin (A) for use in the present invention.

When the reaction temperature is lower than 70 ° C, the reaction for producing an oxazine ring is very slow and the reaction does not proceed substantially. When the reaction temperature is higher than 120 ° C, the resulting oxazine ring is opened, and a side reaction which causes a binding reaction with other vicinal phenolic hydroxyl groups is promoted to increase the molecular weight, facilitating the formation of an insoluble gel. In the reaction at a high temperature, the ring opening crosslinking reaction of the oxazine ring is liable to occur in parallel with the oxazine ring ring forming reaction. The reaction temperature is preferably 70 to 110 占 폚, more preferably 80 to 100 占 폚 in order to improve the reaction of generating an oxazine ring and to reduce the generation of gel.

Regarding the reaction time, formation of an oxazine ring is not sufficient for 20 minutes or less, and ring opening crosslinking reaction of an oxazine ring formed gradually in parallel for 24 hours or more occurs. For this reason, the reaction time is preferably 1 to 10 hours, more preferably 1.5 to 6 hours, in order to improve the reaction of generating an oxazine ring and to reduce the generation of gel.

Further, it may further include a step of removing water generated by the reaction. By removing the water generated by the reaction, it is possible to shorten the synthesis reaction time of the oxazine resin, and the efficiency of the reaction can be improved. The method for removing water to be produced is not particularly limited, and a method of azeotropically making a reaction with a solvent in the reaction solution may be mentioned. Further, by reducing the pressure inside the reaction vessel during the reaction step, the produced water may be removed from the system.

By adding a poor solvent such as methanol into the reaction mixture thus obtained, the resin component is precipitated to obtain an oxazine resin. Alternatively, after the completion of the reaction, the solvent, water, monoamino compound, and aldehyde are removed by washing with water or alkaline washing as necessary, thereby obtaining an oxazine resin.

Next, the epoxy resin (B) to be blended with the jade photographic resin composition of the present invention will be described.

The epoxy resin (B) is not particularly limited, and various epoxy resins can be used as long as they are known epoxy resins. Examples of the epoxy resin (B) that can be used include polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone or in combination of two or more.

Specific examples of the polyglycidyl ether compound include bisphenol A type epoxy resins (for example, Epotot (registered trademark) YD-127, YD-128, YD-8125, YD-825GS (Manufactured by Sumitomo Chemical Co., Ltd.), bisphenol F type epoxy resin (such as Eptot YDF-170, YDF-1500, YDF-8170 and YDF-870GS (For example, YX-4000 (manufactured by Mitsubishi Chemical Corporation), ZX (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) -1251 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), hydroquinone type epoxy resins (such as Epitot YDC-1312 and ZX-1027 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)), bisphenol- (For example, ZX-1201 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)), (E.g., ZX-1355 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Epikron HP-4032D (manufactured by DIC Co., Ltd.)), bisphenol S type epoxy resin (for example, TX-0710 Epoxy resin (for example, YSLV-50TE, YSLV-120TE (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Epiclon EXA-1515 (manufactured by Dainippon Chemical Industry Co., Ltd.) (For example, YSLV-80DE (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) and the like), resorcinol-type epoxy resin (for example, Epotot ZX-1684 (Manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Denacol EX-201 (manufactured by Nagase ChemteX Corporation), phenol novolak type epoxy resin (for example, Epitot YDPN-638 ), jER152, jER154 (manufactured by Mitsubishi Chemical Corporation) (Manufactured by DIC Corporation), cresol novolak type epoxy resin (for example, Epothrin YDCN-700 series (manufactured by Shin-Tetsu Sumikin Chemical Co., Ltd.), Epikron N-740, N-770, EOCN-102S, EOCN-104S (manufactured by Nippon Yakusho Pharmaceutical Co., Ltd.), Nippon Yakusho Co., Ltd., (For example, EPOTOTE ZX-1071T, ZX-1270, ZX-1342 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)), styrenated phenol novolak type Epoxy resins such as Epotot ZX-1247, GK-5855, TX-1210, YDAN-1000 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), bisphenol novolak type epoxy resins, (For example, ESN-155, ESN-185V and ESN-175 (manufactured by Shin-Etsu Chemical Co., Ltd.)), epoxy resin (for example, Epotot ZX-1142L (For example, ESN-355 and ESN-375 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), etc.) of an ESN-300 series), naphthalene diol aralkyl type epoxy resins (for example, ESN-475V and ESN-485 of ESN-400 series, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), biphenylaralkylphenol type epoxy resins (For example, EPPN-501, EPPN-502 (manufactured by Nippon Yaku Pharmaceutical Co., Ltd.), etc.) and the like (for example, NC-3000 and NC-3000H ), A tetrahydroxyphenyl ethane type epoxy resin (for example, YDG-414 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) and the like), dicyclopentadiene type epoxy resin (for example, Epiclon HP7200, HP-7200H Manufactured by DIC Co., Ltd.)), an alkylene glycol type epoxy resin (Ephoto PG-207, SR-8GS (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), PG-207GS (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), SR-16H, SR-16HL, SR-PG, SR-4PG, SR- ), Aliphatic cyclic epoxy resins (e.g., Santot ST-3000, Eportot ZX-1658, ZX-1658GS, FX-318 (available from Shinnitetsu Sumikin Chemical Co., Ltd.), HBPA-DGE Manufactured by Maruzen Petrochemical Co., Ltd.)), and the like, but the present invention is not limited thereto.

Specific examples of the polyglycidylamine compound include a diaminodiphenylmethane type epoxy resin (for example, Ephotoat YH-434, YH-434GS (manufactured by Shin-Tetsu Sumikin Chemical Co., Ltd.), ELM434 (Manufactured by Sumitomo Chemical Co., Ltd.), Araldite MY720, MY721, MY9512 and MY9663 (manufactured by Huntsman Advanced Chemicals Co., Ltd.)), meta-xylene diamine type epoxy resin (for example, TETRAD- (For example, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like), isocyanurate type epoxy resin (for example, TEPIC- P (manufactured by Nissan Chemical Industries, Ltd.), an aniline type epoxy resin (for example, GAN, GOT (manufactured by Nippon Yakusho KK) and the like), a hidantoin epoxy resin (for example, Y238 Manufactured by Materialis Co.), etc.), aminophenol Epoxy resin (for example, ELM120, ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), jER630 (manufactured by Mitsubishi Chemical Corporation), Araldite MY0510, MY0600, MY0610 (manufactured by Huntsman Advanced Materials Company) But are not limited to these.

Specific examples of the polyglycidyl ester compound include dimer acid type epoxy resins (such as EGPOTT YD-171 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), jER871 (manufactured by Mitsubishi Chemical Corporation), etc.), hexahydrophthalic acid (For example, SR-HHPA (manufactured by Sakamoto Pharmaceutical Co., Ltd.) and the like), and the like, but the present invention is not limited thereto.

Specific examples of the alicyclic epoxy compound include aliphatic cyclic epoxy resins (for example, Celloxides 2021, 2021A, 2021P, 3000 (manufactured by Daicel Chemical Industries, Ltd.), DCPD-EP, MCPD-EP, TCPD -EP (manufactured by Maruzen Petrochemical Co., Ltd.)), and the like, but the present invention is not limited thereto.

Specific examples of the modified epoxy resin include a urethane-modified epoxy resin (for example, AER4152 (manufactured by Asahi Kasei Materials), an epoxy resin containing an oxazolidone ring, an epoxy-modified polybutadiene rubber derivative (E.g., PB-3600 (manufactured by Daicel Chemical Industries, Ltd.) and the like), CTBN-modified epoxy resin (e.g., YR-102 and YR-450 (For example, EPOTOT FX-305, FX-289B, FX-1225, TX-1320A and TX-1328 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)) and the like. It is not.

The curing agent (C) for an epoxy resin may be used in combination with the oxepine resin composition of the present invention, if necessary. Examples of the curing agent (C) for an epoxy resin which can be used in combination include those commonly used such as various phenol resins, acid anhydrides, amines, hydrazides and acidic polyesters. These curing agents for epoxy resins include 1 Or may be used in combination of two or more. Of these, phenolic curing agents are particularly preferred. The amount of the curing agent (C) for epoxy resin which can be used in combination is preferably 0 to 9 mol, more preferably 0 to 10 mol, per mol of the oxazine ring of the oxazine resin (A) To 7 moles, more preferably 1 to 5 moles, and still more preferably 2 to 4 moles. Also, since 1 mole of OH group is produced in 1 mole of the oxazine ring, 1 mole of the oxazine ring is also referred to as 1 equivalent of the oxazine ring.

The molar amount (equivalent) of the oxazine ring of the jade photographic resin (A) is calculated from the value of the total amine value by the method described in the examples.

The term "active hydrogen group" as used herein means a functional group having an active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen which generates active hydrogen by hydrolysis or the like, or a functional group exhibiting an equivalent curing action) Specific examples thereof include an acid anhydride group, a carboxyl group, an amino group, and a phenolic hydroxyl group. 1 mole of the carboxyl group (-COOH) or the phenolic hydroxyl group (-OH) is 1 equivalent (1 mole as the active hydrogen group), 1 mole of the amino group (-NH ₂ ) is 2 equivalents 2 mol as a hydrogen group). When the active hydrogen group is not clear, the number of moles or equivalents of active hydrogen groups can be determined by measurement. For example, by reacting a monoepoxy resin, such as phenyl glycidyl ether, which has an epoxy equivalent already known, with a curing agent whose active hydrogen equivalent is unknown, and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the curing agent is Can be obtained.

The amount of the curing agent (C) for the epoxy resin (A) and the amount of the curing agent (C) for the epoxy resin in the epoxy resin (B) The total amount of moles of active hydrogen groups in the curing agent (C) is 0.2 to 1.5 moles, preferably 0.3 to 1.5 moles, more preferably 0.5 to 1.5 moles, and still more preferably 0.8 to 1.2 moles. When the total number of moles of the oxazine ring and the active hydrogen group is less than 0.2 mol or more than 1.5 mol per 1 mol of the epoxy group, the curing is incomplete and good curing properties may not be obtained.

For example, when an epoxy resin (A) and an epoxy resin (B) are used without using a curing agent (C) for an epoxy resin, the content of the oxazine resin (A) relative to 1 mol of the epoxy group of the epoxy resin (B) Is in the range of 0.8 to 1.5 moles, preferably 0.8 to 1.2 moles.

When a phenol-based curing agent or an amine-based curing agent is blended as the curing agent (C) for an epoxy resin, the amount of the curing agent (C) for the epoxy resin and the curing agent for the epoxy resin The sum of the number of moles of hydrogen groups is preferably 0.8 to 1.5 moles, and preferably 0.8 to 1.2 moles. When an acid anhydride-based curing agent is blended as the curing agent (C) for an epoxy resin, the total amount is 0.4 to 1.5 moles, preferably 0.5 to 1.2 moles, and more preferably 0.6 to 1.0 moles. As the theoretical amount, 1 mole of the oxazine ring or OH group corresponds to 1 equivalent (mole) of active hydrogen group, and 1 mole of epoxy group corresponds to 1 equivalent.

Specific examples of the phenol resin-based curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetramethyl bisphenol Z, Bisphenols such as 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like; Dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone and di-tert-butylhydroquinone; And hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene. However, the present invention is not limited thereto.

In addition, phenol novolac resins such as Shonol BRG-555 (manufactured by Showa Denko KK), cresol novolac resins such as DC-5 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), resin TPM-100 SN-395, and SN-485 (manufactured by Shin-Etsu Tetsu Sumi Co., Ltd.), phenols such as naphthol novolak resin and / or condensation products of naphthol and aldehyde such as tris (Manufactured by Kinko Chemical Co., Ltd.), condensates of naphthols and xylylene glycol, condensates of phenols and / or naphthols with isopropenyl acetophenone, reactants of phenols and / or naphthols and dicyclopentadiene , Phenol compounds such as condensates of phenols and / or naphthols and biphenyl-based cross-linking agents, and the like, but are not limited thereto.

Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol and phenylphenol. Naphthols include 1-naphthol, 2- Naphthol, and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, Aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. As the biphenyl-based crosslinking agent, bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl and the like can be cited .

As the curing agent (C) for an epoxy resin, an acid anhydride-based curing agent, an amine-based curing agent or other curing agent may be used in addition to the above. Specific examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous pyromellitic acid, phthalic anhydride, trimellitic anhydride, methylnadic anhydride , Maleic anhydride, and the like, but are not limited thereto.

Specific examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, meta-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, benzyldimethylamine , 2,4,6-tris (dimethylaminomethyl) phenol, dicyandiamide, dimer acid and the like, and amine compounds such as polyamide amine, which are condensates of polyamines, but are not limited thereto .

Specific examples of other curing agents include phosphine compounds such as triphenylphosphine and the like, and phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl- Imidazoles such as methylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-methylimidazole, imidazoles and salts with trimellitic acid, isocyanuric acid, boric acid and the like Diazide salts, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, diazabicyclo compounds and salts such as phenols and phenol novolac resins, complex compounds such as boron trifluoride and amines and ether compounds, Aromatic phosphonium, or an iodonium salt, but the present invention is not limited thereto.

A curing accelerator (D) may be used in the jade photographic resin composition, if necessary. Examples of the curing accelerator (D) include, but are not limited to, phosphorus compounds such as imidazole derivatives, tertiary amines and phosphines, metal compounds, Lewis acids, and amine complexes. These curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator to be used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5.0 parts by mass, per 100 parts by mass of the epoxy resin (B) in the photoresist composition. By using the curing accelerator, the curing temperature can be lowered or the curing time can be shortened. The curing conditions of the photocurable resin composition of the present invention are 200 to 240 ° C for 2 to 5 hours when a curing accelerator is not used and 170 to 190 ° C for 0.5 to 5 hours when a curing accelerator is used.

The imidazole derivative may be any compound having an imidazole skeleton, and is not particularly limited. Ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl- Alkyl substituted imidazole compounds such as 2-phenylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole and 2-heptadecylimidazole, Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2- phenylimidazole, benzimidazole, Substituted with a hydrocarbon group containing a cyclic structure such as an aryl group or an aralkyl group such as - (2'-cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [ Imidazole compounds, and the like, but are not limited thereto. Among these imidazole derivatives, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole is preferable in terms of curing at low temperature.

Examples of the tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo [5.4.0] (DBU), but the present invention is not limited thereto. Examples of the phosphine include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and the like. The metal compound includes, for example, tin octylate and the like, but is not limited thereto. Examples of the amine complex salt include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, boron trifluoride aniline complex, And boron trifluoride complexes such as a mixture thereof, but are not limited thereto.

Of these curing accelerators, when used as a build-up material application or a circuit board application, 2-dimethylaminopyridine, 4-dimethylaminopyridine and imidazoles are preferred because they are excellent in heat resistance, dielectric properties and solderability Do. When used as a semiconductor encapsulating material, triphenylphosphine and DBU are preferred because they are excellent in curability, heat resistance, electrical properties, moisture resistance and the like. In addition, when boron trifluoride adducts are used, the ring-opening of the oxazine resin takes priority and the resulting phenol group reacts with the epoxy group to increase the crosslinking density and obtain higher heat resistance.

As the jade photographic resin composition, an organic solvent or a reactive diluent may be used for viscosity adjustment.

Examples of the organic solvent include, but are not limited to, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, ethers such as ethylene glycol monomethyl ether, acetone, methyl ethyl Ketones such as methanol, ethanol, 1-methoxy-2-propanol, benzyl alcohol, butyl diglycol and pine oil, butyl acetate, cellosolve acetate, ethyl There may be mentioned acetic acid esters such as diglycol acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as benzene, toluene and xylene, dimethyl sulfoxide, acetonitrile , N-methylpyrrolidone, and the like, but are not limited thereto.

Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether and phenyl glycidyl ether, resorcinol glycidyl ether, neopentyl glycol glycidyl ether, Bifunctional glycidyl ethers such as diethyl ether, diethyl ether, and 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, and pentaerythritol polyglycidyl ether Polyfunctional glycidyl ethers, but are not limited thereto.

These organic solvents or reactive diluents are preferably used singly or in combination of plural kinds in an amount of not more than 90% by mass as the concentration of the organic compound in the photoresist composition, and the appropriate kinds and amounts thereof to be used are appropriately selected depending on the application . For example, in the case of a printed wiring board, it is preferably a polar solvent having a boiling point of 160 DEG C or less such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, and the amount thereof is 40 to 80 mass% desirable. It is preferable to use, for example, a ketone, an ester of an ester, a carbitol, an aromatic hydrocarbon, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., It is preferable that the non-volatile matter concentration is 30 to 60% by mass.

In the jade photographic resin composition, other thermosetting resin or thermoplastic resin may be blended to the extent that the properties are not impaired. Examples of the resin include phenol resin, acrylic resin, petroleum resin, indene resin, coumarone resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, But are not limited to, polyphenylene ether resins, modified polyphenylene ether resins, polyether sulfone resins, polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, and polyvinyl formal resins .

For the purpose of improving the flame retardancy of the resulting cured product, various known flame retardants may be used in the jade photographic resin composition. Examples of the flame retardant that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants. From the viewpoint of the environment, a halogen-free flame retardant is preferable, and a phosphorus flame retardant is particularly preferable. These flame retardants may be used alone or in combination of two or more.

Phosphorus flame retardants are classified into two types, phosphorus-based flame retardants (phosphorus-containing additives) and phosphorus compounds, which are reactive. Phosphorus compounds reactive with phosphorus are further divided into phosphorus-containing epoxy resins and phosphorus-containing curing agents. When the phosphorus-based flame retardant of the additive system and the phosphorus compound of the reactive phosphorus are compared with each other, the reactive phosphorus compound does not bleed out at the time of curing and has good flame retardant effect and the use of a reactive phosphorus compound .

As the phosphorus-containing additive, both an inorganic phosphorus compound and an organic phosphorus compound can be used. Examples of the inorganic phosphorus compound include inorganic phosphorus compounds such as ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium triphosphate, ammonium polyphosphate and the like, phosphoric acid amide and the like. It is not.

As the surface treatment method, for example, (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, oxides such as titanium oxide, A method of coating with an inorganic compound such as bismuth, bismuth hydroxide, bismuth nitrate, or a mixture thereof, (2) a method in which a mixture of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide and the like and a thermosetting resin such as phenol resin (3) a method in which a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide or the like is coated with a thermosetting resin such as phenol resin in a double coating manner, and the like. It is not.

Examples of the organophosphorus compound include phosphoric acid ester compounds such as methyl ester phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate , Bis (2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, butyl pyrophosphate (For example, PX-200 (manufactured by Dai-ichi Kagaku Kogyo Co., Ltd.)], phosphonic acid compounds, phosphonic acid compounds such as polyphosphoric acid compounds , Phosphine oxide A general organic phosphorus compound such as a compound (for example, diphenylphosphine oxide, triphenylphosphine oxide, etc.) and a phosphorane compound (for example, triphenyl (9H-fluorene-9-ylidene) (For example, EXOLIT OP1230, OP1240, OP930, OP935 (or more)), nitrogen-containing organic phosphorus compounds (for example, SPS-100, SPB-100 and SPE-100 (manufactured by Otsuka Chemical Co., (Manufactured by Clariant), etc.), a phosphorus compound having an active hydrogen group directly connected to a phosphorus atom (for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- (E.g., diphenylphosphine oxide), or phosphorus-containing phenol compounds (for example, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide 10-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dihydroxy- -D (Hereinafter abbreviated as DOPO-NQ), diphenylphosphinyl hydroquinone, diphenylphosphonyl-1-oxo-10-phosphaphenanthrene-10- Dioxinaphthalene, 1,4-cyclooctylenephenylphosphinyl-1,4-phenyldiol, 1,5-cyclooctylenepropinyl-1,4-phenyldiol, etc.), and organic phosphorus compounds Containing epoxy resin or phosphorus-containing curing agent, which are derivatives obtained by reacting an organic phosphorus compound with a compound such as an epoxy resin or a phenol resin, but the present invention is not limited thereto.

As the reactive compound used in the phosphorus-containing epoxy resin and the phosphorus-containing curing agent, phosphorus compounds or phosphorus-containing phenols having an active hydrogen group directly linked to the phosphorus atom are preferable. From the viewpoint of availability, DOPO, DOPO-HQ , DOPO-NQ and the like are more preferable.

Examples of the phosphorus-containing epoxy resin include Eptot FX-305, FX-289B, FX-1225, TX-1320A and TX-1328 described above, but are not limited thereto.

The epoxy equivalent of the phosphorus-containing epoxy resin is preferably 200 to 800, more preferably 300 to 780, and even more preferably 400 to 760. The phosphorus content of the phosphorus-containing epoxy resin is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, and still more preferably 3 to 5% by mass.

As the phosphorus-containing curing agent, in addition to the above-mentioned phosphorus-containing phenols, for example, by reacting a phenolic compound with DOPO and an aldehyde by a production method as disclosed in Japanese Patent Publication No. 2008-501063 or Japanese Patent No. 4548547, Compound can be obtained. In this case, the phosphorus compound is introduced into the molecule through the condensation of the aromatic ring of the phenol compound via aldehydes. In addition, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by further reacting it with an aromatic carboxylic acid by a production method as disclosed in JP-A-2013-185002. In addition, a phosphorus-containing benzoxazine photographic compound can be obtained by a production method as described in a re-publication patent publication WO2008 / 010429.

The phosphorus content of the phosphorus-containing curing agent is preferably 0.5 to 12% by mass, more preferably 2 to 11% by mass, and still more preferably 4 to 10% by mass.

The compounding amount of the phosphorus compound is appropriately selected depending on the kind of the phosphorus compound, the component of the epoxy resin composition, and the degree of desired flame retardancy. (A), an epoxy resin (B), a flame retardant, and other fillers and additives in the case of a phosphorus compound containing a phosphorus compound, that is, a phosphorus containing epoxy resin or phosphorus containing curing agent The content of phosphorus is preferably 0.2 to 6% by mass, more preferably 0.4 to 4% by mass, still more preferably 0.5 to 3.5% by mass, particularly preferably 0.6 to 3% by mass, relative to the solid content (nonvolatile content) desirable. When the phosphorus content is low, there is a fear that the flame retardancy can not be ensured. If the phosphorus content is too much, the heat resistance may be adversely affected.

Here, the phosphorus-containing epoxy resin is regarded to correspond to both the phosphorus compound and the epoxy resin (A). Similarly, the phosphorus-containing curing agent is deemed to correspond to both the phosphorus compound and the curing agent (C). Therefore, when a phosphorus-containing curing agent is used, the use of other curing agent or phosphorus compound may be unnecessary. Similarly, when a phosphorus-containing epoxy resin is used, the use of other epoxy resin or phosphorus compound may be unnecessary.

The blending amount of the flame retardant is appropriately selected according to the kind of the phosphorus-based flame retardant, the component of the photoresist composition, and the degree of desired flame retardancy. For example, the content of phosphorus in the organic component (excluding the organic solvent) in the photoresist composition is preferably 0.2 to 4% by mass, more preferably 0.4 to 3.5% by mass, and still more preferably 0.6 to 3% Mass%. When the phosphorus content is low, there is a fear that the flame retardancy can not be ensured, and if it is too much, the heat resistance may be adversely affected.

When a phosphorus flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, calcium carbonate, zinc molybdate, or the like may be used in combination as a flame retardant aid.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable Do.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon [2,4,6-tris (cyanoamino) -1,3,5-triazine], melam [ For example, guanyl sulfamate, melamine sulfate, melamine sulfate, melamine sulfate, and the like, in addition to ethylenediamine, ethylenediamine, diethyleneglycolmethylenetetramine, iminobis (1,3,5-triazine-2,6- diamine) (For example, LA-7052 (manufactured by DIC Co., Ltd.)), and aminotriazine-modified phenol resin are additionally modified with tung oil and isophthalic linseed oil , But the present invention is not limited thereto.

The cyanuric acid compound includes, for example, cyanuric acid, melamine cyanuric acid and the like, but is not limited thereto.

The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the kind of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. Among 100 parts by mass of the solid content (nonvolatile content) in the curable epoxy resin composition, It is preferably blended in the range of 0.05 to 10 parts by mass, particularly preferably in the range of 0.1 to 5 parts by mass. When a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound or the like may be used in combination.

As the silicon-based flame retardant, any organic compound containing silicon atoms can be used without particular limitation, and examples thereof include silicone oil, silicone rubber, and silicone resin, but are not limited thereto.

The blending amount of the silicon-based flame retardant is appropriately selected according to the kind of the silicon-based flame retardant, the other components of the epoxy resin composition and the degree of desired flame retardancy. For example, in 100 parts by mass of the solid content (nonvolatile content) in the curable epoxy resin composition, By mass to 20 parts by mass. When a silicone flame retardant is used, a molybdenum compound or alumina may be used in combination.

Examples of the inorganic flame retardant include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glass, and the like.

Examples of the metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide and zirconium hydroxide.

Examples of the metal oxide include metal oxides such as zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, , Nickel oxide, copper oxide, tungsten oxide, and the like, but are not limited thereto.

Examples of the metal carbonate compound include, but are not limited to, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate and titanium carbonate. Examples of the metal powder include, but are not limited to, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten and tin.

Examples of the boron compound include, but are not limited to, zinc borate, zinc metaborate, barium metaborate, boric acid, borax and the like.

Examples of the low melting point glass include hydrated glass, SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ -based, ZnO-P ₂ O ₅ -MgO-based, P ₂ O ₅ -B ₂ O ₃ - Glassy compounds such as PbO-MgO, P-Sn-OF, PbO-V ₂ O ₅ -TeO ₂ , Al ₂ O ₃ -H ₂ O and borosilicate lead. .

The blending amount of the inorganic flame retardant is appropriately selected according to the kind of the inorganic flame retardant, the other components of the epoxy resin composition and the degree of the desired flame retardancy. For example, the epoxy resin (A), the curing agent (B), the flame retardant and other fillers It is preferable to blend in an amount of 0.05 to 20 parts by mass, particularly preferably 0.5 to 15 parts by mass, based on 100 parts by mass of a solid content (non-volatile matter) in the epoxy resin composition in which all of the additives are added.

Examples of the organometallic salt-based flame retardant include compounds having an ionic bond or coordination bond between a metal atom and an aromatic compound or a heterocyclic compound, such as ferrocene, an acetylacetonate metal complex, an organic metal carbonyl compound, an organic cobalt salt compound, , But the present invention is not limited thereto.

The blending amount of the organometallic salt-based flame retardant is appropriately selected according to the kind of the organic metal salt-based flame retardant, the other components of the epoxy resin composition, and the degree of desired flame retardancy. For example, the epoxy resin (A), the curing agent (B) (Nonvolatile matter) in the epoxy resin composition in which all of the other fillers, additives, and the like are blended in an amount of 0.005 to 10 parts by mass.

Examples of the halogen-based flame retardant include a bromine compound and a chlorine compound, but a chlorine compound is not preferable in view of toxicity. Examples of the bromine compound include p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, 2,2'-ethylenebis (4,5,6,7-tetrabromoisocyanine-1,3-dione) (for example, SAYTEX BT-93 (For example, SR-T1000, SR-T2000 (manufactured by Nippon Shokubai Co., Ltd.) or the like], ethane-1,2-bis (pentabromophenyl) [for example, SAYTEX 8010 (Manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)], and the like, but the present invention is not limited thereto.

The blending amount of the halogen-based flame retardant is appropriately selected according to the kind of the halogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. Examples thereof include epoxy resin (A), curing agent (B) The halogen content is preferably 5 to 15% by mass based on the solid content (non-volatile matter) in the epoxy resin composition containing all of the filler and the additive. When a halogen-based flame retardant is used as the flame retardant, antimony compounds such as antimony trioxide, antimony trioxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum oxide, A zirconium compound such as zirconium oxide or zirconium hydroxide, a boron compound such as zinc borate or barium metaborate, a silicon oil, a silane coupling agent, a silicon-based compound such as high molecular weight silicon, chlorinated polyethylene, Or may be used in combination.

A filler may be optionally added to the jade photographic resin composition. Specific examples of the filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, A fiber, a glass fiber, an alumina fiber, a silica alumina fiber, a silicon carbide fiber, a polyester fiber, a cellulose fiber, an aramid fiber, a ceramic fiber, a particulate rubber, a thermoplastic elastomer and a pigment. Generally, the reason for using the filler is to improve the impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant adjuvant as described above and has an effect of improving flame retardancy.

The blending amount of these fillers is preferably from 1 to 150 parts by mass, more preferably from 10 to 70 parts by mass per 100 parts by mass of the solid content (excluding the solvent, the resin, the curing agent and the curing accelerator) desirable. If the blending amount is large, there is a fear that the adhesiveness required for laminated board applications is lowered, and further, the cured product is disengaged and sufficient mechanical properties may not be obtained. If the compounding amount is too small, there is a possibility that the effect of compounding the filler, such as the improvement of the impact resistance of the cured product, may not be exhibited.

Various additives such as a silane coupling agent, an antioxidant, a releasing agent, a defoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment may be further added to the jade photographic resin composition. The blending amount of these additives is preferably 0.01 to 20% by mass with respect to the jade photographic resin composition.

When the jade photographic resin composition is a plate-like substrate or the like, it is preferable that it is fibrous in terms of dimensional stability and bending strength. More preferably, a glass fiber substrate in which glass fibers are woven in the form of a mesh is exemplified.

The jade photographic resin composition can impregnate a fibrous substrate to prepare a prepreg for use in a printed wiring board or the like. As the fibrous substrate, inorganic fibers such as glass, woven or nonwoven fabric of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin can be used, but the present invention is not limited thereto. The method for producing the prepreg from the photocurable resin composition is not particularly limited. For example, the photocurable resin composition is impregnated with a resin varnish prepared by adjusting the viscosity of the photocurable resin composition with a solvent, (B-staged), and can be heated and dried, for example, at 100 to 200 ° C for 1 to 40 minutes. Here, the resin amount in the prepreg is preferably 30 to 80% by mass of the resin component.

In order to harden the prepreg, a curing method of a laminated board generally used for producing a printed wiring board can be used, but the present invention is not limited thereto. For example, when a laminate is formed using a prepreg, a laminate is formed by laminating one prepreg or a plurality of prepregs and arranging a metal foil on one side or both sides of the prepreg, and heating and pressing the laminate to form a laminate do.

As the metal foil, copper, aluminum, brass, nickel, etc. alone, an alloy, and a composite metal foil can be used. Then, the produced laminate is heated under pressure to cure the prepreg to obtain a laminate. At this time, it is preferable to set the heating temperature to 160 to 220 占 폚, the pressing pressure to 50 to 500 N / cm2, and the heating and pressurizing time to 40 to 240 minutes, and the desired cured product can be obtained. If the heating temperature is low, the curing reaction does not sufficiently proceed, and if it is high, decomposition of the oxazine resin composition may start. If the pressing pressure is low, bubbles may remain in the laminate to be obtained and electrical properties may be deteriorated. If the pressing pressure is high, the resin may flow before being cured, and a cured product having a desired thickness may not be obtained. Further, if the heating and pressurizing time is short, there is a fear that the curing reaction will not proceed sufficiently, and if it is long, pyrolysis of the oxazine resin composition in the prepreg may occur.

An epoxy resin cured product can be obtained by curing the same in the same manner as in the case of the known jade photographic resin composition. As a method for obtaining the cured product, the same method as the known jade photographic resin composition can be employed. The method of obtaining the cured product may be a method such as molding, injection, potting, dipping, drip coating, transfer molding, compression molding, Or the like, followed by heating and pressure-curing to form a laminated board. The curing temperature at that time is usually in the range of 100 to 300 占 폚, and the curing time is usually about 1 to 5 hours.

The cured product of the photocurable resin of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film and the like.

The jade photographic resin composition of the present invention can be molded into a sheet or a film. In this case, it is possible to make a sheet or film using a conventionally known method, but an example of a preferable molding method is a method in which the above-mentioned jade photographic resin composition is dissolved in a solvent and the obtained resin solution is applied to a surface- An insulating film, an adhesive sheet or an adhesive film by coating on a base material such as a polyester film or a polyimide film by a conventionally known method, followed by drying and peeling from the substrate.

The method for producing the adhesive sheet is not particularly limited. For example, the epoxy resin composition of the present invention is preferably applied to a carrier film which is not dissolved in an epoxy resin composition such as a polyester film or a polyimide film, To 100 탆, and then heated and dried at 100 to 200 캜 for 1 to 40 minutes to form a sheet. Generally, a resin sheet is formed by a method called a casting method. At this time, if the surface of the sheet to which the epoxy resin composition is applied is surface-treated in advance with a release agent, the formed adhesive sheet can be easily peeled off. The thickness of the adhesive sheet is preferably 5 to 80 占 퐉. The thus obtained adhesive sheet is usually an insulating adhesive sheet having an insulating property, but a conductive adhesive sheet can be obtained by mixing a metal having conductivity or a metal-coated fine particle with the epoxy resin composition.

Next, a method of manufacturing a laminated board using the prepreg or insulating adhesive sheet of the present invention will be described. When a laminate is formed by using a prepreg, a laminate is formed by laminating one or plural prepregs and a metal foil on one or both sides, and the laminate is heated and pressed to be laminated and integrated. As the metal foil, copper, aluminum, brass, nickel, etc. alone, an alloy, and a composite metal foil can be used. The conditions under which the laminate is heated and pressed can be appropriately adjusted under the condition that the epoxy resin composition is cured and then heated and pressed. However, if the amount of pressure applied is too low, bubbles remain in the resulting laminate, It is preferable to pressurize under the condition that the moldability is satisfied. For example, the temperature can be set to 160 to 220 ° C, the pressure to 49.0 to 490.3 N / cm 2 (5 to 50 kgf / cm 2), and the heating time to 40 to 240 minutes. Furthermore, a multi-layered plate can be produced using the thus obtained single-layered laminate as an inner layer material. In this case, circuit formation is first performed on the laminate by the additive method or the subtractive method, and the surface of the formed circuit is treated with an acid solution to be blackened to obtain an inner layer material. An insulating layer is formed of a prepreg or an insulating adhesive sheet on one surface or both circuit forming surfaces of the inner layer material and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

In the case of forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is disposed on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally formed, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Or the cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil as the conductor layer. Here, as the metal foil, the same materials as those used for the laminate used as the inner layer material can be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material. When the epoxy resin composition is applied to the laminate to form the insulating layer, the circuit forming surface resin of the outermost layer of the inner layer material is coated with the above epoxy resin composition preferably at a thickness of 5 to 100 탆, For 1 to 90 minutes to form a sheet. It is usually formed by a method called casting method. The thickness after drying is preferably 5 to 80 탆. A printed wiring board can be formed by performing a via hole formation or a circuit formation on the surface of the multilayered laminate thus formed by the additive method or the subtractive method. Further, by repeating the above method using the printed wiring board as an inner layer material, a multilayer laminate can be further formed.

In the case of forming the insulating layer with the prepreg, one prepreg or a plurality of prepregs are stacked on the circuit formation surface of the inner layer material, and a metal foil is arranged on the outer side thereof to form a laminate. Then, the laminate is heated and pressed to integrally form a cured product of the prepreg as an insulating layer, and the metal foil on the outside of the prepreg is formed as a conductor layer. Here, as the metal foil, the same material as used for the laminate used as the inner laminate may be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material. A printed wiring board can be formed by performing a via hole formation or a circuit formation on the surface of the multilayer laminate thus formed by the additive method or the subtractive method. Further, by repeating the above method using the printed wiring board as an inner layer material, it is possible to further form a multilayered multilayered plate.

As the encapsulant obtained by using the jade photographic resin composition, a tape-encapsulating material of a semiconductor chip, a potting liquid encapsulant, an underfill resin, and an interlayer insulating film of a semiconductor are easily used.

In order to prepare the jade photographic resin composition for a semiconductor encapsulating material, it is preferable that the jade photographic resin composition is preliminarily mixed with additives such as other coupling agents, releasing agents, and inorganic fillers, , And the mixture is sufficiently mixed until homogeneous. When used as a tape-encapsulating agent, the resin composition obtained by the above-mentioned technique is heated to produce a semi-cured sheet, and the encapsulating tape is placed on a semiconductor chip, Followed by softening and molding, followed by complete curing at 170 to 250 ° C. When used as a potting liquid encapsulant, the resin composition obtained by the above-mentioned technique may be dissolved in a solvent if necessary, and then applied to semiconductor chips or electronic parts and directly cured.

The cured product was evaluated by heat curing. As a result, it was found that a cured product of the cured product was obtained by mixing a novolak phenol compound (e) having a specific molecular weight distribution with an oxepine resin (A) having a specific molecular weight distribution obtained from a monoamino compound and an aldehyde ) Has a lower viscosity than that of an oxazine resin other than the oxazine resin (A), so that the resin tends to undergo curing even at a low temperature for a short period of time. The cured product is excellent in heat resistance and dimensional stability, It is possible to combine high heat resistance and good dimensional stability, and is particularly useful for thin-film laminates.

Example

EXAMPLES The present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited thereto unless they depart from the gist thereof. Unless otherwise stated, " part " represents the mass part, and "% "

The analysis method and the measurement method are shown below. In addition, the unit of equivalents is "g / eq.".

Epoxy equivalent: measured according to JIS K7236 standard.

Softening point: Measured according to JIS K7234 standard, ring method. Specifically, an automatic softening point device (ASP-MG4, manufactured by Meitec Co., Ltd.) was used.

Joint Photographic Ring Equivalent: The molar number (equivalent) Z of the photochemical ring of the jade photographic resin (A) was calculated from the value of the total amine value (Y) by the following equation. The total amine value was measured in accordance with JIS K7237 standard, but chloroform was used instead of ortho-nitrotoluene used in a mixed solvent.

Z = 56110 / Y

(Mw) and dispersity (Mw / Mn): GPC measurement (number average molecular weight, number average molecular weight, number average molecular weight . Specifically, use in that it includes a main body column (Toso Co., Ltd., TSKgelG4000H _{XL, XL} TSKgelG3000H, TSKgelG2000H _XL) to (Toso Co., Ltd., HLC-8220GPC) in series, column temperature was set to 40 ℃. Further, THF was used as the eluent, the flow rate was 1 ml / min, and a differential refractive index detector was used as the detector. The measurement sample was prepared by dissolving 0.05 g of the sample in 10 ml of THF and filtering with a microfilter. For the data processing, GPC-8020 model II version 6.00 manufactured by Toso Co., Ltd. was used. Mn, Mw, and Mw / Mn were determined from standardized monodisperse polystyrene (manufactured by Tosoh Corporation, A (trade name), manufactured by Tosoh Corporation), n = 0 content, n = 1 content, n = 2 content, F-10, F-20, F-40, F-80, F-128) obtained from the A-5000, A-1000, A-2500, A-5000, F-1, F-2, F- Respectively. The measurement of k = 0 to 4 form of phenol novolac resin, Mn and the like is also the same.

Tg and? Tg: Measured with a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.) in accordance with IPC-TM-6502.4.25.c and Tgm (middle of the transition curve for the tangent line between the glass state and the rubber state) Temperature) was defined as the glass transition temperature (Tg). The temperature was raised to 275 占 폚 at a rate of 10 占 폚 / min, held for 10 minutes, cooled to 20 占 폚 at 100 占 폚 / min, held for 20 minutes, and then heated to 275 占 폚 at 20 占 폚 / min. Tg (1st) at the first temperature rise was taken as Tg (1st), Tgm at the second temperature rise was taken as Tg (2nd) and ΔTg was calculated as Tg (2nd) - Tg (1st).

Elastic modulus: The value of E 'at 50 ° C when the measurement was carried out at a temperature increase rate of 5 ° C / min with a dynamic viscoelasticity measuring apparatus (EXTAR 6000 DMA6100, manufactured by Hitachi Hitech Science Co., Ltd.) was taken as an elastic modulus (50 ° C) The elastic modulus (220 deg. C) of E 'was determined.

IR: The absorbance at a wave number of 650 to 4000 cm ^-1 was measured by a total internal reflection method (ATR method) of a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X).

Flammability: Evaluated according to the UL94 standard by the vertical method.

Specific dielectric constant and dielectric loss tangent: The specific dielectric constant and dielectric loss tangent at a frequency of 1 GHz were evaluated by a capacitance method using a material analyzer (AGILENT Technologies) according to the IPC-TM-6502.5.5.9 standard.

Copper peel strength and interlaminar adhesion: Measured according to JIS C6481 standard, and the interlaminar adhesive strength was peeled off between the 7th and 8th layers.

Synthesis Example 1 (Synthesis of phenol novolak resin)

2500 parts of phenol and 7.5 parts of oxalic acid dihydrate were charged into a glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, a cooling tube and a dropping device, stirred while injecting nitrogen gas, And the temperature was raised. Next, while stirring at 80 캜, 474.1 parts of 37.4% formalin was added dropwise over 30 minutes to react. The reaction was continued for 3 hours while maintaining the reaction temperature at 92 占 폚. The temperature was raised, and the temperature was raised to 110 캜 while removing the reaction product water from the system. The residual phenol was recovered under reduced pressure at 160 캜, the temperature was further raised to 250 캜, and a part of k = 0 was recovered to obtain phenol novolak resin (e-1). The phenol novolac resin (e-1) thus obtained had a hydroxyl group equivalent of 105, a content of k = 0, a content of k = 1, an content of k of 1, 3-isomer content: 11%, content of k = 4 or more, content: 10%, Mn: 529, Mw: A GPC measurement chart is shown in Fig. In the figure, a peak represented by (a ₀ ) represents k = 0, a peak group represented by (b ₀ ) represents k = 1 and k = 2, and a peak represented by (c ₀ ) , And a peak group represented by (d ₀ ) represents k = 4 or more.

Synthesis Example 2 (Synthesis of phenol novolak resin)

A phenol novolak resin (e-2) was obtained in the same manner as in Synthesis Example 1 except that the recovery temperature at 250 占 폚 was changed to 240 占 폚. The phenol novolak resin (e-2) thus obtained had a hydroxyl group equivalent of 105, a content of k = 0, a content of k = 0, a content of k = 1, 10%, content of k = 4 or more substances: 9%, Mn: 510, and Mw: 567.

The abbreviations used in Examples and Comparative Examples are as follows.

[Novolac phenol compound]

(e-1): The phenol novolak resin of Synthesis Example 1

(e-2): The phenol novolak resin of Synthesis Example 2

BRG-555: phenol novolak resin (Showon BRG-555, hydroxyl equivalent: 105, k = 0 content: 25% by area, k = 1 content: 18% Content: 14 area%, k = 3 content: 10 area%, k = 4 area or higher content: 33 area%, Mn: 353, Mw: 547)

[Epoxy resin]

YDPN-638: phenol novolak type epoxy resin (Epitote YDPN-638, epoxy equivalent: 176, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

YD-128: Bisphenol A type liquid epoxy resin (Epotot YD-128, epoxy equivalent: 186, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

FX-1225: Phosphorus-containing epoxy resin (Epotot FX-1225, epoxy equivalent: 320, phosphorus content: 2.5%, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

[Curing agent]

BRG-557: Phenol novolak resin (Shawon BRG-557, softening point: 80 占 폚, hydroxyl equivalent: 105, manufactured by Showa Denko KK)

GK-5855P: An aromatic modified novolac resin (GK-5855P, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd., hydroxyl equivalent: 230)

GDP9140: dicyclopentadiene / phenol cocondensation resin (GDP9140, manufactured by KANEI Chemical Co., Ltd., hydroxyl equivalent: 196)

[Curing accelerator]

TBZ: 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (Kyuzol TM TBZ manufactured by Shikoku Kasei Kogyo Co.,

[Flame Retardant]

PX-200: aromatic condensed phosphoric acid ester (PX-200, phosphorus content: 9%, manufactured by Daihachi Chemical Industry Co., Ltd.)

[Other]

Comparative resin 2: bisphenol F-aniline type benzoxazine resin (manufactured by Shikoku Chemical Co., Ltd., oxazine ring equivalent: 217)

Comparative resin 3: Bisphenol A-aniline type benzoxazine resin (Kb-31, manufactured by Zibo Kerrben Polymer New Material Co., Ltd., Jaffak ring equivalent: 246)

Example 1

200 parts of the phenol novolak resin (e-1) obtained in Synthesis Example 1, 189 parts of aniline, and 256 parts of toluene were injected as the novolak phenol compound (e) as the novolak phenol compound (e) Followed by stirring, and heating was performed to raise the temperature. Next, 134 parts of 92% paraformaldehyde was poured over 1 hour while stirring at 50 占 폚, and then 13 parts of water was added dropwise. The reaction was continued at 85 캜 for 2 hours. The temperature was raised, and the temperature was raised to 120 캜 while removing the reaction product water from the system. The remaining aniline and toluene were recovered under reduced pressure while being maintained at 120 DEG C to obtain an oxepine resin (resin 1).

A GPC measurement chart of the obtained Resin 1 is shown in Fig. In the figure, the peak represented by (a) represents n = 0, the peak group represented by (b) represents n = 1 and n = 2, and the peak group represented by (c) . An FT-IR measurement chart is shown in Fig.

Example 2

Resin 2 was obtained in the same manner as in Example 1 except that 200 parts of the phenol novolak resin (e-2) was used as the novolak phenol compound (e).

Example 3

Resin 3 was obtained in the same manner as in Example 1 except that 180 parts of aniline and 128 parts of 92% paraformaldehyde were used.

Reference Example 1

Comparative resin 1 was obtained in the same manner as in Example 1 except that 200 parts of BRG-555 was used as the novolak phenol compound (e). A GPC measurement chart of the obtained Comparative Resin 1 is shown in Fig. In the figure, the peak represented by (a) represents n = 0, the peak group represented by (b) represents n = 1 and n = 2, and the peak group represented by (c) .

The n = 0 content ratio, n = 1 content ratio, n = 2 content ratio, n = 3 copolymers in the Resins 1 to 3 and Comparative Resin 1 obtained in Examples 1 to 3 and Reference Resin 1 and Comparative Resins 2 to 3 Table 1 shows the results of measurement of the abnormal contents, Mn, Mw, the equivalent of the oxazine ring, and the softening point.

Example 4

70 parts of Resin 1, 100 parts of YDPN-638 and 30 parts of BRG-557 were mixed on a 120 占 폚 hot plate and mixed with 2.0 ml of TBZ varnish adjusted to 0.05 g / ml with methyl ethyl ketone (MEK) Respectively. After sufficiently cooling, the resulting solid ground product was cured in a vacuum press at 130 캜 for 15 minutes and at 190 캜 for 80 minutes. Tg (1st), Tg (2nd), and Tg of the cured product were measured. The results are shown in Table 2.

Examples 5 to 7 and Comparative Examples 1 to 4

(Parts) of the formulation shown in Table 2, and a cured product was obtained in the same manner as in Example 4. The same tests as in Example 4 were carried out, and the results are shown in Table 2. (H) / (Z) in the table represents the equivalence ratio (molar ratio) of the active hydrogen (H) to the oxazine ring (Z) (Molar ratio) of the sum of the hydrogen (H) and the oxazine ring (Z).

From Table 2, a cured product having a small? Tg was obtained by using the resin of the examples. The small? Tg means that the unreacted portion is small, and the cured product or the laminated plate using the resin of the examples can be said to have good dimensional stability. The cured product using the conventional multifunctional jade photographic resin has the drawback that the Tg is increased, but the unhardened portion remains to deteriorate the dimensional stability, that is,? Tg becomes large. However, since the cured product of the example has a Tg equivalent to that of the conventional multifunctional oxazine photographic resin and has a small? Tg, the trade-off of the conventional technique can be solved.

Example 8

(Solid content: 180 parts), MEK varnish (NV.75%) of FX-1225 (solid content: 180 parts), MEK varnish of the BRG-557 (MEK varnish , 77 parts of varnish (NV.65%) (solid content: 50 parts) and 2.0 ml of MEK varnish (0.05 g / ml) of TBZ were mixed and compounded in the formulations shown in Table 3 to prepare a mixed solvent of MEK and propylene glycol monomethyl ether (Mass ratio = 1/1) to obtain a resin varnish of NV of 50%.

The obtained resin varnish was impregnated in a glass cloth WEA 628 XS13 (0.18 mm thick, manufactured by Nitto Denki Co., Ltd.). The impregnated glass cloth was dried in a hot air circulation furnace at 150 캜 for 9 minutes to obtain a prepreg. 8 sheets of the obtained prepregs were superposed, and a copper foil (3EC manufactured by Mitsui Mining & Mining Co., Ltd.) was superimposed on the upper and lower sides and heated and pressed at 130 占 폚 for 15 minutes and 190 占 폚 for 20 kg / . The elastic modulus (50 캜) and the elastic modulus (220 캜) of the laminate were measured. The results are shown in Table 3.

Examples 9 to 10 and Comparative Examples 5 to 7

(Part) of the formulation shown in Table 3, and a laminated board was obtained in the same manner as in Example 8. [ The same tests as in Example 8 were carried out, and the results are shown in Table 3. < tb > < TABLE >

From Table 3, it was found that when the resin of Examples was used, the elastic modulus was low even at a temperature exceeding the glass transition temperature, and the elasticity was low. In recent years, there has been a problem of bending of the laminated board due to the thinning of the laminated board, and a resin to be used for improving it is required to have a low elastic modulus, but the conventional art does not provide a jade photographic resin composition satisfying the characteristics. However, since the resin of the example is low elasticity even at a temperature exceeding the glass temperature than the conventional jade photographic resin, the bending problem of the laminated board can be further improved.

Examples 11 to 13 and Comparative Examples 8 to 9

(Parts) of the prescription of Table 4, and a laminated board was obtained in the same manner as in Example 8. [ Flame retardancy, relative dielectric constant, dielectric tangent, copper peel strength, and interlaminar bond strength were measured, and the results are shown in Table 4.

Claims (12)

An oxepine resin composition comprising an oxepine resin (A) and an epoxy resin (B), wherein the oxepine resin (A) is represented by the following formula (1), and in the gel permeation chromatography measurement, Wherein the total content of n = 1 and n = 2 is 35 to 70%, the content of n = 3 or more is 50% or less, and the number average molecular weight is a standard polystyrene reduced value By weight based on the total weight of the composition.
[Chemical Formula 1]

(Wherein A ₁ is each independently an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as substituents of the aromatic ring.
X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or (1b).
Each R ₁ independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
m is 1 or 2;
n is an average value of 1 to 5.)
(2)

(Wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms.
A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent of the aromatic ring. The method according to claim 1,
Further, an oxazine resin composition comprising a curing agent (C) for an epoxy resin. 3. The method of claim 2,
(H / Z) of the active hydrogen (H) of the curing agent for epoxy resin (C) to the oxazine ring (Z) of the oxazine resin (A) was adjusted to 0/10 to 9/1 by using a curing agent for epoxy resin C). ≪ / RTI > The method according to claim 2 or 3,
(C) for an epoxy resin so that the sum of the number of moles of active hydrogens of the curing agent for epoxy resin (C) is 0.2 to 1.5 moles per mole of the epoxy group of the epoxy resin (B) By weight. 5. The method according to any one of claims 1 to 4,
Wherein the curing agent (C) for an epoxy resin is a phenolic curing agent. 6. The method according to any one of claims 1 to 5,
Further, the curing accelerator (D) is incorporated in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the epoxy resin (B). A prepreg characterized by using the jade photographic resin composition according to any one of claims 1 to 6. A laminate characterized by using the jade photographic resin composition according to any one of claims 1 to 6. A cured product obtained by curing the oxazine resin composition according to any one of claims 1 to 6. An ophthalmic resin composition comprising an oxepine resin (A) and an epoxy resin (B), wherein the oxepine resin (A) comprises a novolak phenol compound (e), a monoamino compound represented by the following formula (21) Wherein the novolak phenol compound (e) is obtained from an aldehyde represented by the following formula (22), wherein the novolak phenol compound (e) is represented by the following formula (2) the total content of k = 1 and k = 2 is 50 to 95%, the content of k = 3 is 15% or less, the content of k = 4 or higher is 15% Wherein the number average molecular weight is 350 to 1,500 in terms of standard polystyrene.
(3)

(Wherein A ₁ is each independently an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as substituents of the aromatic ring.
X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or (1b).
m is 1 or 2;
k is an average value of 0.8 to 3.)
[Chemical Formula 4]

(Wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms.
A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent of the aromatic ring.
R ₁ -NH ₂ (21)
R ₂ -CHO (22)
(R ₁ and R ₂ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms) A process for producing an ophthalmic resin by reacting a novolak phenol compound (e) with a monoamino compound represented by the following formula (21) and an aldehyde represented by the following formula (22), wherein the novolak phenol compound (e) Wherein the content ratio of k = 0 is 20% or less, the sum of contents of k = 1 and k = 2 is 50 to 95% by area, and k = 3 parts by mass or less, 15% by area or less, k = 4 or more high molecular weight fractions of 15% by area or less, and a number average molecular weight of 350 to 1,500 in terms of standard polystyrene, Method of manufacturing photographic resin.
[Chemical Formula 5]

(Wherein A ₁ is each independently an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms may be substituted as a substituent of the aromatic ring.
X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or (1b).
m is 1 or 2;
k is an average value of 0.8 to 3.)
[Chemical Formula 6]

(Wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms.
A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and the aromatic ring group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An aryloxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms may be substituted as a substituent of the aromatic ring.
R ₁ -NH ₂ (21)
R ₂ -CHO (22)
(R ₁ and R ₂ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms) 12. The method of claim 11,
Wherein the monoamino compound is aniline and the aldehyde is formaldehyde.

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