TW201739832A - 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 = 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

Oxazine resin composition and its production method, prepreg, laminated board and cured product

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

In recent years, it has been used for copper-clad laminates for printed wiring boards, adhesives for multilayer wiring boards, semiconductor sealing materials, adhesives for semiconductor packaging, semiconductor mounting modules, or for automotive, aircraft, and building components. A curable material used for parts and the like requires a heat-resistant material excellent in stability under high temperature/high humidity or reliability. Further, in the field of energy, research and development progress of fuel cells, various secondary batteries, and the like have gradually required heat resistant materials. In particular, in a hybrid vehicle, an electric vehicle, or a distributed power source, a power device is often used centering on an inverter, and its power density is also drastically increased. Therefore, a tantalum carbide (SiC) device which operates at a high temperature of 200 ° C or higher is also expected. Further, an electronic control unit (ECU) using a normal semiconductor wafer is also mounted in an engine room from a vehicle interior, and therefore heat resistance that can withstand severe conditions is still required. In response to such a demand, a heat-resistant resin obtained by reacting a compound containing a benzoxazine ring structure with an epoxy resin has been studied (Patent Document 1, Patent Document 2, Non-Patent Document 1, etc.).

In addition, when a compound containing a benzoxazine ring structure and an epoxy resin such as bisphenol A diglycidyl ether are reacted in stoichiometric amounts, unreacted materials remain, which hinders formation of an ideal crosslink. Since the epoxy resin is made more than a stoichiometric amount, the cured resin provides a high glass transition point (Tg) (Non-Patent Document 2). However, the conventional resin and resin compositions have the following disadvantages: the glass transition temperature is about 160 ° C, and the properties are not sufficient in terms of heat resistance or flame retardancy, and in order to obtain good characteristics, a high hardening temperature and a long length are required. Hardening time, etc. In order to increase the glass transition temperature by industrial low-temperature hardening for a short period of time, a sulfazine resin obtained by using a polyfunctional phenol resin as a raw material can be used, but this method has a residual unhardened portion, although the glass transition temperature is increased. However, the dimensional stability is degraded.

Further, recently, as the thickness of the laminate is reduced, there is a problem of warpage of the laminate, and low warpage performance is required. Therefore, the resin to be used is required to be low in elasticity, but an oxazine resin composition satisfying the above characteristics cannot be obtained. [Prior Art Document] [Patent Literature]

[Patent Document 1] European Patent No. 2,304,852. [Non-patent literature]

[Non-Patent Document 1] "Forming Process", Vol. 19, No. 10, 634-640 (2007) [Non-Patent Document 2] "J. Appl. Polym. Sci.", Vol. .61, p1595 (1996)

[Problem to be Solved by the Invention] An object of the present invention is to provide an oxazine resin composition which can form heat resistance even under an industrially advantageous low-temperature short-time hardening condition, and a cured product thereof. A cured product excellent in properties and good in dimensional stability. [Means for solving problems]

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, it has been found that by using a polyfunctional oxazine resin having a specific molecular weight distribution, heat resistance is improved, and viscosity of the resin is also low, thereby being low temperature for a short period of time. The hardening is also easy under the conditions, and the elastic modulus of the hardened material is relatively low, thereby completing the present invention.

That is, the present invention is an oxazine resin composition containing an oxazine resin (A) and an epoxy resin (B), and the oxazine resin composition is characterized in that the oxazine resin (A) is represented by the following formula (1), and has the following molecular weight distribution in gel permeation chromatography (GPC) measurement: n=0 body content rate is 15% (area%) or less, n=1 body and n= The total content of the two bodies is 35% to 70%, the content of n=3 or more is 50% or less, and the number average molecular weight is 400 to 2,500 in terms of standard polystyrene.

[Chemical 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 these aromatic ring groups may have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to Any one of 6 alkoxy group, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 12 carbon atoms or aralkyloxy group having 7 to 12 carbon atoms; a substituent of an aromatic ring. Further, in the formula (1), A ₁ includes an adjacent two carbons in the aromatic ring and is integrated with a ring-constituting atom of -CNCO- 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. Further, in the present specification, the biphenyl ring as the aromatic ring group means -Ph-Ph- (here, Ph is a phenylene group), and the oxazine ring means a member of -CNCOCC-which is a ring-shaped member. Ring (hydrooxazine ring). X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or formula (1b). R ₁ each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 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, and an aralkyl group having 7 to 12 carbon atoms. m is 1 or 2, and n is the number of repeating units and represents an integer of 0 or more, and the average value thereof is 1 to 5.

[Chemical 2]

In the formula (1a), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (1b), R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 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 these aromatic ring groups may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 6 Any one of an aryl group of ～10, 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 is a substituent of the aromatic ring.

The oxazine resin composition may contain a curing agent (C) for an epoxy resin, or may contain 0.01 to 10 parts by mass of a hardening accelerator (D) per 100 parts by mass of the epoxy resin (B). . The hardener (C) for epoxy resin is preferably a phenolic hardener.

In the case of blending the hardener (C) for epoxy resin, it is preferred to use the active hydrogen (H) of the hardener (C) for epoxy resin and the oxazine ring (Z) of the oxazine resin (A). The molar ratio of H/Z = 0/10 to 9/1 is formulated.

Moreover, it is preferable to mix so that the sum of the oxazine ring (Z) and the active hydrogen (H) with respect to the epoxy group 1 mol of the epoxy resin (B) is 0.2 to 1.5 mol.

Further, the present invention is an oxazine resin composition comprising a oxazine resin (A) and an epoxy resin (B), and the oxazine resin composition is characterized in that the oxazine resin (A) is a novolac phenol. The compound (e), a monoamine compound represented by the following formula (21), and an aldehyde represented by the following formula (22), wherein the novolak phenol compound (e) is represented by the following formula (2) In addition, it has the following molecular weight distribution in the gel permeation chromatography measurement: the content of the k=0 body is 20% (area%) or less, and the total content of the k=1 body and the k=2 body is 50%. 95%, the content of the k=3 body is 15% or less, the content of the high molecular weight body of k=4 or more is 15% or less, and the number average molecular weight is 350 to 1500 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 aromatic group having 7 to 12 carbon atoms. alkyl)

[Chemical 3]

In the formula (2), A ₁ , X and m have the same meanings as A ₁ , X and m of the formula (1), respectively. k is the number of repeating units and represents an integer of 0 or more, and the average value thereof is 0.8 to 3.

Further, the present invention is a prepreg or laminate characterized in that the oxazine resin composition is used. Further, the present invention is a cured product obtained by curing the oxazine resin composition.

Further, the present invention provides a method for producing an oxazine resin, which comprises reacting a novolak phenol compound (e), a monoamine compound and an aldehyde to produce a oxazine resin, and the method for producing the oxazine resin is characterized in that: The novolak phenol compound (e) represented by the formula (2) is used as the novolak phenol compound (e).

Preferably, the monoamine compound is aniline and the aldehyde is formaldehyde. [Effects of the Invention]

The cured product obtained by curing the oxazine 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.

The oxazine resin composition of the present invention contains an oxazine resin (A) and an epoxy resin (B). The oxazine resin (A) used in the present invention is represented by the above formula (1), and the content of n = 0 is 15% or less, and 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 (Mn) is 400 to 2,500 in terms of standard polystyrene. The oxazine resin (A) is obtained from a novolak phenol compound (e) having a specific molecular weight distribution, a monoamine compound, and an aldehyde. Here, the content of n=1 body, n=2 body, n=3 body, k=1 body, k=2 body, k=3 body, etc. in the oxazine resin (A) and the novolak phenol compound (e) The rate is the area % obtained by GPC measurement. Further, the n=1 body means a component in which n is 1 in the formula (1), and the n=0 body means 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 any _one of a group containing a benzene ring, a naphthalene ring or a biphenyl ring which may have a substituent. The aromatic ring group may have a substituent on the aromatic ring, and the substituent 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, and a carbon number. Any of 6 to 10 aryloxy groups, 7 to 12 carbon atoms of aralkyl groups, or 7 to 12 carbon atoms of aralkyl groups. In the case of having a plurality of substituents, they may be the same or different. However, it is also possible that two carbons constituting a part of the hydrooxazine ring have no substituent, and one carbon adjacent to the two carbons does not have a substituent. Further, in the formulae (1) to (7), (21), and (22), the same reference numerals are used unless otherwise specified.

The alkyl group represents a linear, branched or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third butyl group. , pentyl, hexyl, cyclohexyl and the like. Among these groups, a branched or cyclic alkyl group tends to impart high heat resistance as compared with a linear one. 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. Preference is given to isopropyl, isobutyl, tert-butyl and cyclohexyl, more preferably to the third butyl or cyclohexyl group. Further, a methyl group is also preferable because the flame retardancy tends to be improved.

Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferred. The aralkyl group may, for example, be a benzyl group, a phenethyl group or a 1-phenylethyl group, and is preferably a benzyl group or a 1-phenylethyl group.

X is a divalent aliphatic cyclic hydrocarbon group or any one of the crosslinking groups represented by the above formula (1a) or the formula (1b). The carbon number of the divalent aliphatic cyclic hydrocarbon group is preferably 5 to 15, more preferably 5 to 10. Here, the divalent aliphatic cyclic hydrocarbon group may, for example, be dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, 5-vinylnorborn-2-ene, α-pinene, β a divalent aliphatic cyclic hydrocarbon group derived from an unsaturated cyclic aliphatic hydrocarbon compound such as limonene or limonene. Among these aliphatic cyclic hydrocarbon groups, a divalent hydrocarbon group derived from dicyclopentadiene is preferred from the viewpoint of heat resistance. Further, in the formulae (1a) and (1b), R ₃ , R ₄ , R ₅ and R ₆ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ₂ has the same meaning as A ₁ in the above formula (1) except that the valence is divalent.

R ₁ each 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, a benzyl group, etc. are mentioned, Preferably, a methyl group, a phenyl group, and a

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, etc. are mentioned, Preferably, a hydrogen atom, a methyl group, and a phenyl group are preferable.

m is 1 or 2 and corresponds to the number of hydroxyl groups of the raw novolac phenol compound.

n is a repeating unit and represents an integer of 0 or more, and its average value (number average) is 1 to 5, preferably 1.2 to 4.5, and more preferably 1.7 to 4. If it is in the above range, the effect of improving the hardenability becomes remarkable, and in this respect, it is preferable. Further, n in the above formula (1) can be obtained as follows.

The styrene-converted molecular weight (α0, α1, α2, α3) corresponding to each of the n=0 body, the n=1 body, the n=2 body, the n=3 body, and the n=4 body was determined by the GPC measurement. Ratio of theoretical molecular weight (β0, β1, β2, β3, β4) of α4) and n=0, n=1, n=2, n=3, and n=4 (β0/α0, Β1/α1, β2/α2, β3/α3, β4/α4), and the average value of these (β0/α0 to β4/α4) was obtained. The numerical value obtained by multiplying the styrene-converted molecular weight Mn obtained by GPC by the average value is defined as the average molecular weight Mn. Then, the theoretical molecular weight of the formula (1) is defined as the average molecular weight Mn to calculate the value of n.

For example, in the case of the oxazine resin of the first embodiment described later, the structural formula is the following formula (3), and the theoretical molecular weight thereof is 434 + 223 n = Mn'. Further, Mn was 754 based on the GPC measurement value, and the average value of (β0/α0 to β4/α4) was 1.147. Therefore, n = 1.9 can be obtained by calculation based on 434 + 223n = 754 × 1.147.

The oxazine resin (A) used in the present invention must have a specific molecular weight distribution, and it is important that the content of n=0 and n=3 or more is a specific amount or less, and the total of n=1 and n=2 The rate is within a certain amount range. When the content of the n=0 body exceeds 15% (area%), the heat resistance is improved (high Tg), but the cured portion is likely to be hard and brittle, and the elastic modulus may not be obtained. The content of the n=0 body is preferably 12% or less, more preferably 10% or less, still more preferably 5% or less. In addition, when the content ratio of n=3 or more exceeds 50%, the reactivity may be significantly deteriorated and the unhardened material may remain in a large amount. The content ratio of n=3 or more is preferably 45% or less, and more preferably 40% or less. When it is in the above range, when the content of the n=0 body is small, it is preferable that the content ratio of n=3 or more is small. Further, when the content ratio of the n=0 body is large, the content ratio of n=3 or more may be large. Therefore, the difference between the content ratio of n=0 body and the content rate of n=3 or more is preferably 30% to 40%. If a specific amount of n=1 body or n=2 body is present, the cured product has a high Tg and a low elastic modulus, and the reactivity is also improved. This tendency is caused by which of n = 1 or n = 2, and therefore it is preferable to manage the total content of n = 1 and n = 2. The total content of the n=1 body and the n=2 body is preferably 40% to 65%, more preferably 43% to 60%, still more preferably 45% to 55%.

Further, the number average molecular weight is 400 to 2,500, preferably 400 to 2,000, more preferably 450 to 1,500, still more preferably 450 to 1,000, in terms of standard polystyrene.

In addition, in the peak of n=2 or more in the GPC measurement, in addition to the oxazine resin (A) represented by the formula (1), the novolak phenol compound (e) is also included by the monoamine compound and the aldehyde. Although some of the compounds were self-polymerized, since these compounds could not be separated, the respective content ratios were determined by the area % included.

The oxazine resin (A) is preferably 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, and m=1; The oxazine resin indicated.

[Chemical 4]

As described above, the oxazine resin (A) is obtained from a novolak phenol compound (e) having a specific molecular weight distribution, a monoamine compound, and an aldehyde. R ₁ of the formula (1) is a substituent derived from a monoamine 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 formula (2). k is an integer of 0 or more and represents an integer of 0 or more, and its average value (number average) is 0.8 to 3, preferably 1.0 to 2.7, and more preferably 1.2 to 2.5. The GPC measurement has the following specific molecular weight distribution: the content of the k=0 body is 20% (area%) or less, and the total content of the k=1 body and the k=2 body is 50% to 95%, k=3. The content of the body is 15% or less, the content of the high molecular weight body having k = 4 or more is 15% or less, and the 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 cannot be obtained in good yield. The content of the k=0 body is preferably 15% or less, more preferably 12% or less, further preferably 10% or less, and most preferably 5% or less. Further, the content of the high molecular weight body having k = 4 or more is preferably 10% or less, and more preferably a high molecular weight body containing no more than k = 5 or more. The content of the k=3 body is preferably 10% to 15%. The total content of the k=1 body and the k=2 body is preferably 60% to 92%, more preferably 65% to 90%. In particular, the content of the k=1 body is preferably 35% to 65%, and the content of the k=2 body is preferably 15% to 30%. Further, 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 degree of dispersion (weight average molecular weight Mw/Mn) is preferably from 1.05 to 1.3, more preferably from 1.08 to 1.2, still more preferably from 1.1 to 1.15. Further, the measurement conditions of the GPC of the novolak phenol compound (e) are the same as those of the GPC of the oxazine resin (A).

Examples of the phenol used for obtaining the novolak phenol compound (e) include phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, and isophthalic acid. The phenol, naphthalenediol, and the like are not limited to these compounds, and these phenols may be used singly or in combination of two or more. Among these phenols, monophenols such as phenol or alkylphenol are preferred. The alkyl group in the case of an alkylphenol is preferably an alkyl group having 1 to 6 carbon atoms.

The crosslinking agent used to obtain the novolac phenol compound (e) may, for example, be an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde or benzaldehyde represented by the following formula (4), or the following a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or acetophenone represented by the formula (5), or a terephthalic acid or a terephthalic acid dimethyl ester represented by the following formula (6) Ether, p-xylylene dichloride, 4,4'-dimethoxymethylbiphenyl, 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, two a crosslinking agent such as chloromethyl naphthalene or a crosslinking agent such as divinylbenzene, divinylbiphenyl or divinylnaphthalene represented by the following formula (7), or cyclopentadiene or two The cycloalkyldiene such as cyclopentadiene is not limited to these compounds, and these crosslinking agents may be used singly or in combination of two or more. X of the formula (1) and the formula (2) is a divalent aliphatic cyclic hydrocarbon group when a cycloalkyldiene is used, and when a crosslinking agent of the formula (4) or the formula (5) is used, When the crosslinking group represented by the formula (6) or the formula (7) is used, the crosslinking group represented by the formula (1a) is a crosslinking group represented by the formula (1b). Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, dichloro-p-xylene, 4,4'-dichloromethylbiphenyl is preferred, and formaldehyde is particularly preferred. Preferred examples of the use of formaldehyde in the reaction include a formalin aqueous solution, paraformaldehyde, trioxane, and the like.

[Chemical 5]

In the formulae (4) and (5), R ₃ and R ₄ have the same meanings as R ₃ and R ₄ in the formula (1a). In the formula (6) and formula _{(7), R 5, R} 6 and A ₂ in the formula (1b), R _5, R ₆ and A ₂ are the same meaning, Y independently represents a hydroxyl group, an alkoxy group or a halogen atom .

Examples of the acidic catalyst used for obtaining the novolak phenol compound (e) include protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, and zinc chloride. And a Lewis acid such as ferric chloride, oxalic acid or monochloroacetic acid, but not limited thereto. These acidic catalysts may be used singly or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferred.

The novolac phenol compound (e) having a specific molecular weight distribution used in the present invention can be adjusted by adjusting the molar ratio of the phenol to the aldehyde and removing the low molecular weight component from the obtained novolak phenol compound (e). obtain. Further, such a novolac phenol compound (e) can be obtained by a production method as shown in JP-A-2002-194041 or JP-A-2007-126683.

The molar ratio of the phenol to the crosslinking agent is represented by a molar ratio (phenol/crosslinking agent) of the phenol to the crosslinking agent 1 mol, and the molar ratio is 1 or more. Manufacturing, in the case of a large molar ratio, a large number of k = 0 body, k = 1 body, and in the case of a small molar ratio, a large number of high molecular weight body of k = 3 or more, k = 0 body, k = 1 body reduction. Further, in order to have a specific molecular weight distribution of the oxazine resin, it is necessary to set the novolak phenol compound (e) to a specific molecular weight distribution. The molar ratio (phenol/crosslinking agent) of 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, in order to be in the above range. By reducing or removing the low molecular weight component by adjusting the novolac phenol compound (e) obtained by adjusting the molar ratio of the phenol and the crosslinking agent in this manner, a novolak phenol compound (e) having a specific molecular weight distribution can be obtained. In this case, a method of reducing or removing a low molecular weight component, particularly a k=0 body, may be a method of dissolving in an alkaline aqueous solution by a method in which solubility in various solvents is poor, and other well-known separation methods.

The monoamine-based compound used to obtain the oxazine resin is represented by the above formula (21), and the aldehyde is represented by the formula (22). In the formula (21), R ₁ has the same meaning as R ₁ of the formula (1). Specific examples thereof include: R ₁ is methyl methylamine, R ₁ is ethyl amine, R ₁ is propyl amine, R ₁ is butyl amine, R ₁ is phenyl aniline, R ₁ methylaniline as a tolyl, R ₁ is meta-xylene group-dimethylaniline, R ₁ is a benzyl group of the benzylamine and the like, but are not limited to these compounds. Among these monoamine-based compounds, aromatic monoamine compounds are preferred, and aniline and methylaniline are more preferred.

In the formula (22), R ₂ has the same meaning as R ₂ of the formula (1). The aldehyde is the same aldehyde as that used in order to obtain the novolak phenol compound (e). Among these aldehydes, formaldehyde, acetaldehyde, and benzaldehyde are preferred, and formaldehyde is particularly preferred. A preferred form of the case of using formaldehyde includes a formalin aqueous solution, paraformaldehyde, trioxane, and the like.

The amount of each raw material used is preferably 1 mol to 2 mol, more preferably 0.9 mol to 1.1 mol, per mol of the hydroxyl group of the novolak phenol compound (e). The aldehydes are preferably from 1.7 moles to 2.5 moles, more preferably from 1.8 moles to 2.2 moles. In particular, aldehydes may be added in a slight excess. Relative to the hydroxyl group of the novolac phenol compound, the theoretical amount is monoamine 1 mol, aldehyde 2 mol, but as a side reaction, the polymerization of the novolac phenol compound or only the monoamine compound and the aldehyde are produced. Reaction product. Further, the separable unreacted material is removed in the post-treatment step, so that the monoamine compound or the aldehyde may also remain. The total amount of these impurities is preferably 5% by mass or less. Further, in the case where the novolak phenol compound (e) has an average of m (k + 2) OH groups, it is calculated that the 1 mol of the novolak phenol compound has an OH group of m (k + 2) mol, and OH is The base 1 molar was calculated to be 1 equivalent.

Regarding the manufacturing method, there is no special manufacturing method, and the usual manufacturing method can be utilized. A typical production method is a method in which a phenol novolak phenol compound (e) and a monoamine compound are heated and stirred in a solvent, and then an aldehyde is added and held at 70 to 120 ° C for 20 minutes to 24 hours. After the reaction, the product is subjected to a method of reprecipitation by introducing the product into a poor solvent having a low solubility in methanol or the like, or by a synthetic chemical method such as solvent extraction, and the mixture is condensed at a temperature of 120 ° C or lower. The volatile component such as water is reduced in pressure and dried to obtain the oxazine resin (A) used in the present invention.

When the reaction temperature is lower than 70 ° C, the formation reaction of the oxazine ring becomes very slow, and substantially no reaction proceeds. When the reaction temperature exceeds 120 ° C, the generated oxazine ring is opened, and a bonding reaction occurs in the vicinity of the other phenolic hydroxyl group, and the side reaction of the high molecular weight is promoted, and an insoluble gel is easily formed. In the reaction at a high temperature, it is easy to cause a ring-opening crosslinking reaction of the oxazine ring simultaneously with the formation reaction of the oxazine ring. In order to improve the oxazine ring formation reaction and reduce the generation of gel, the reaction temperature is preferably from 70 ° C to 110 ° C, more preferably from 80 ° C to 100 ° C. In addition, when the reaction time is 20 minutes or less, the formation of the oxazine ring is insufficient, and when it is 24 hours or more, the ring-opening crosslinking reaction of the produced oxazine ring is gradually caused. Therefore, in order to improve the oxazine ring formation reaction and reduce the generation of gel, the reaction time is preferably from 1 hour to 10 hours, more preferably from 1.5 hours to 6 hours.

Further, the step of removing the water generated by the reaction may be further included. By removing the water formed by the reaction, the synthesis reaction time of the oxazine resin can be shortened, and the efficiency of the reaction can be achieved. The method of removing the generated water is not particularly limited, and examples thereof include a method of azeotroping with a solvent in the reaction solution. Further, the generated water can be removed to the outside of the system by setting the inside of the reaction vessel to a reduced pressure in the reaction step.

By introducing a poor solvent such as methanol into the reaction mixture obtained in this manner, the resin is analyzed to obtain a oxazine resin. Alternatively, the oxazine resin can be obtained by removing the solvent, water, monoamine-based compound and aldehyde by performing a water washing or a hydrazine washing operation after completion of the reaction.

Next, the epoxy resin (B) formulated in the oxazine resin composition of the present invention will be described. The epoxy resin (B) is not particularly limited, and any epoxy resin can be used as long as it is a well-known epoxy resin. Examples of the epoxy resin (B) which can be used include a polyglycidyl ether compound, a polyglycidylamine compound, a polyglycidyl ester compound, an alicyclic epoxy compound, and other modified epoxy resins, but are not limited thereto. Epoxy resin, these epoxy resins may be used singly or in combination of two or more.

Specific examples of the polyglycidyl ether compound include bisphenol A type epoxy resin (for example, Epotohto (registered trademark) YD-127, Epotohto YD-128, and Epotohto YD. -8125, Epotohto YD-825GS (above), bisphenol F-type epoxy resin (Epotohto YDF-170, Albert) Epotohto) YDF-1500, Epotohto YDF-8170, Epotohto YDF-870GS (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), tetramethyl bisphenol F epoxy Resins (for example, YSLV-80XY, YSLV-70XY (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.), biphenol-based epoxy resin (for example, YX-4000 (manufactured by Mitsubishi Chemical Corporation), ZX-1251 ( Nippon Steel & Sumitomo Chemical Co., Ltd., etc.), hydroquinone-type epoxy resin (such as Epotohto YDC-1312, Epotohto ZX-1027 (above is Nippon Steel & Sumitomo Chemical) Co., Ltd.), bisphenol-based epoxy resin (example) ZX-1201 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), naphthalene diphenol type epoxy resin (for example, ZX-1355 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon HP-4032D) (Dai Aisheng (DIC) Co., Ltd.), etc., bisphenol S-type epoxy resin (such as TX-0710 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon EXA-1515 (Greater Japan) Chemical Industry Co., Ltd.), etc., diphenyl sulfide type epoxy resin (for example, YSLV-50TE, YSLV-120TE (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.), diphenyl ether type epoxy Resin (for example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.), resorcinol type epoxy resin (for example, Epotohto ZX-1684 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) , Denacol EX-201 (made by Nagase Chemtex Co., Ltd.), etc., phenol novolac type epoxy resin (for example, Epotohto YDPN-638 (Nippon Steel & Sumitomo Chemical Co., Ltd.) Limited stock Division Manufacturing), jER152, jER154 (above is manufactured by Mitsubishi Chemical Corporation), Epiclon N-740, Epiclon N-770, Epiclon N-775 (above Dessert (DIC) Co., Ltd.), cresol novolac type epoxy resin (for example, Epotohto YDCN-700 series (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Aibi Cologne (Epiclon) N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-695 (above is Di Ai Sheng ( DIC), EOCN-1020, EOCN-102S, EOCN-104S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., alkyl novolak type epoxy resin (for example, Epotohto ZX) -1071T, Epotohto ZX-1270, Epotohto ZX-1342 (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc., styrenated phenol novolac type epoxy resin (for example) Epotohto ZX-1247, Albert Epotohto) GK-5855, Epotohto TX-1210, Epotohto YDAN-1000 (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), bisphenol novolac type epoxy resin, Naphthol novolac type epoxy resin (for example, Epotohto ZX-1142L (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.), β-naphthol aralkyl type epoxy resin (for example, ESN-155, ESN-185V, ESN-175 (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), naphthalene diphenol aralkyl epoxy resin (for example, ESN-355 and ESN-375 of ESN-300 series (above) Nippon Steel & Sumitomo Chemical Co., Ltd.), α-naphthol aralkyl type epoxy resin (for example, ESN-475V and ESN-485 of ESN-400 series (the above is manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) )), a biphenyl aralkyl phenol type epoxy resin (for example, NC-3000, NC-3000H (above, manufactured by Nippon Kayaku Co., Ltd.), etc.), a trishydroxyphenylmethane type epoxy resin (for example, EPPN- 501, EPPN-502 (above is manufactured by Nippon Kayaku Co., Ltd.), etc.) Tetrahydroxyphenylethane type epoxy resin (for example, YDG-414 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.), dicyclopentadiene type epoxy resin (for example, Epiclon HP7200, Abby) Epiclon HP-7200H (above), alkanediol type epoxy resin (Epotohto PG-207, Epotohto PG-207GS) (The above is manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), SR-16H, SR-16HL, SR-PG, SR-4PG, SR-SBA, SR-EGM, SR-8EGS (above is Sakamoto Pharmaceutical Co., Ltd.) Manufactured, etc.), aliphatic cyclic epoxy resin (eg, Suntohto ST-3000, Epotohto ZX-1658, Epotohto ZX-1658GS, Epotohto) FX-318 (the above is manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), HBPA-DGE (manufactured by Maruzen Petrochemical Co., Ltd.), etc., but is not limited to these compounds.

Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resins (e.g., Epotohto YH-434, Epotohto YH-434GS (the above is Nippon Steel & Sumitomo Chemical Co., Ltd.) Manufacturing Co., Ltd.), ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), Araldite MY720, Araldite MY721, Araldite MY9512, Araldite MY9663 (above Manufactured by Huntsman Advanced Materials, etc.), m-xylene diamine type epoxy resin (for example, TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.), 1, 3 - a bisaminomethylcyclohexane type epoxy resin (for example, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.), an isocyanurate type epoxy resin (for example, Tebike ( TEPIC)-P (manufactured by Nissan Chemical Industry Co., Ltd.), aniline type epoxy resin (for example, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), etc.), and urethane-urea type epoxy resin (example) Y238 (manufactured by Huntsman Advanced Materials, etc.), aminophenol-based epoxy resin (for example, ELM120, ELM100 (above), manufactured by Sumitomo Chemical Co., Ltd.), jER630 (manufactured by Mitsubishi Chemical Corporation) , Araldite MY0510, Araldite MY0600, Araldite MY0610 (manufactured by Huntsman Advanced Materials, etc.), etc., but are not limited to these compounds.

Specific examples of the polyglycidyl ester compound include a dimer acid type epoxy resin (for example, Epotohto YD-171 (manufactured by Nippon Steel & Metal Co., Ltd.), jER871 (manufactured by Mitsubishi Chemical Corporation), and the like. ), a hexahydrophthalic acid type epoxy resin (for example, SR-HHPA (manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc.), but is not limited to these compounds.

Specific examples of the alicyclic epoxy compound include aliphatic cyclic epoxy resins (e.g., Celloxide 2021, Celloxide 2021A, Celloxide 2021P, Cerroside). (Celloxide) 3000 (the above is manufactured by Daicel Chemical Industry Co., Ltd.), DCPD-EP, MCPD-EP, TCPD-EP (above, Maruzen Petrochemical Co., Ltd.), etc., but is not limited to These compounds.

Specific examples of the modified epoxy resin include a urethane-modified epoxy resin (for example, AER4152 (manufactured by Asahi Kasei E-materials Co., Ltd.), etc.), and an oxazolidinone ring-containing one. Epoxy resin, epoxy modified polybutadiene rubber derivative (such as PB-3600 (made by Daicel Chemical Co., Ltd.), etc.), CTBN modified epoxy resin (such as YR-102, YR- 450 (above), phosphorus-containing epoxy resin (such as Epotohto FX-305, Epotohto FX-289B, Epotohto) FX-1225, Epotohto TX-1320A, Epotohto TX-1328 (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc., but are not limited to these compounds.

Further, in the oxazine resin composition of the present invention, a curing agent (C) for an epoxy resin may be used in combination as needed. The curing agent for epoxy resin (C) which can be used together is a curing agent for epoxy resins which are generally used, such as various phenol resins, acid anhydrides, amines, anthraquinones, and acidic polyesters. The curing agent may be used alone or in combination of two or more. Among these hardeners for epoxy resins, a phenolic curing agent is particularly preferred. The amount of the curing agent (C) for the epoxy resin to be used is 0 mol of the active hydrogen group of the curing agent (C) for the epoxy resin (C) with respect to the oxazine ring 1 mol of the oxazine resin (A). 9 moles, preferably 0 moles to 7 moles, more preferably 1 mole to 5 moles, still more preferably 2 moles to 4 moles. Further, since 1 mol of OH group was produced from the oxazine ring 1 mol, the oxazine ring 1 mol was also referred to as an oxazine ring 1 equivalent.

The molar amount (equivalent) of the oxazine ring of the oxazine resin (A) was determined by calculation according to the value of the total amine value by the method described in the examples.

In addition, the active hydrogen group referred to in the present specification is 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 due to hydrolysis or the like, or exhibits Specific examples of the functional group for hardening include an acid anhydride group, a carboxyl group, an amine group, or a phenolic hydroxyl group. Further, regarding the active hydrogen group, 1 mol of the carboxyl group (-COOH) or the phenolic hydroxyl group (-OH) is calculated as 1 equivalent (1 mol based on the active hydrogen group), and the amine group (-NH ₂ ) is used. 1 mole was calculated to be 2 equivalents (2 moles on an active hydrogen basis). Further, when the active hydrogen group is not clear, the molar number or equivalent of the active hydrogen group can be determined by measurement. For example, a single epoxy resin such as phenyl glycidyl ether having a known epoxy equivalent can be reacted with a curing agent having an unknown active hydrogen equivalent, and the amount of the monoepoxy resin consumed can be measured to determine the activity of the hardener. Hydrogen equivalent.

In the oxazine resin composition, the amount of the sulfazine resin (A) and the epoxy resin hardener (C) used is 1 mol of the epoxy group (B), and the oxazine resin (A). The sum of the molar numbers of the active hydrogen groups of the oxazine ring and the hardener (C) for epoxy resin is from 0.2 moles to 1.5 moles, preferably from 0.3 moles to 1.5 moles, more preferably from 0.5 moles to 1.5 moles. The ear is further preferably from 0.8 mol to 1.2 mol. In the case where the sum of the molar numbers of the oxime ring and the active hydrogen group with respect to the epoxy group 1 mol is less than 0.2 mol or more than 1.5 mol, the hardening may become incomplete and good hardenability may not be obtained. For example, in the case where the oxazine resin (A) and the epoxy resin (B) are not used without using the epoxy resin hardener (C), the epoxy group 1B can be used with respect to the epoxy group (B). The oxazine ring of the oxazine resin (A) is formulated in a manner of from 0.8 mol to 1.5 mol, preferably from 0.8 mol to 1.2 mol. In addition, when a phenolic curing agent or an amine curing agent is blended as the curing agent (C) for epoxy resin, the oxazine ring and ring of the oxazine resin (A) can be used with respect to the epoxy group 1 molar. The total number of moles of the active hydrogen group of the curing agent (C) for the oxygen resin is adjusted to be 0.8 mol to 1.5 mol, preferably 0.8 mol to 1.2 mol. In the case of formulating an acid anhydride-based curing agent as the curing agent (C) for an epoxy resin, the total amount thereof is from 0.4 mol to 1.5 mol, preferably from 0.5 mol to 1.2 mol, more preferably from 0.6 mol to 1.0 mol. Further, as a theoretical amount, 1 mole of the oxazine ring or OH group corresponds to 1 equivalent (mole) of the active hydrogen group, and epoxy group 1 mole 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, and tetramethyl bisphenol F. a bisphenol such as tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide or 4,4'-thiobis(3-methyl-6-tert-butylphenol); or Catechol, resorcinol, methyl resorcinol, hydroquinone, monomethyl hydroquinone, dimethyl hydroquinone, trimethyl hydroquinone, mono-third a dihydroxybenzene such as butyl hydroquinone or di-tert-butyl hydroquinone; or a hydroxy naphthalene such as dihydroxynaphthalene, dihydroxymethylnaphthalene or trihydroxynaphthalene, but is not limited thereto.

In addition, phenol novolac resin such as phenol novolak resin such as Shonol BRG-555 (manufactured by Showa Denko Co., Ltd.) and DC-5 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) may be mentioned. And phenols and/or naphthols and aldehydes such as trihydroxyphenylmethane novolak resin and naphthol novolak resin, such as Resitop TPM-100 (manufactured by Qunrong Chemical Industry Co., Ltd.) Condensate, condensate of phenol and/or naphthol and benzenedimethanol, such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), phenol and/or naphthol a condensate with isopropenylacetophenone, a reaction product of phenols and/or naphthols with dicyclopentadiene, a phenol compound such as a condensate of phenols and/or naphthols and a biphenyl crosslinking agent Etc., but not limited to these compounds. In this case, the phenols may, for example, be phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol or phenylphenol, and the naphthols may be mentioned. 1-naphthol, 2-naphthol, and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipaldehyde. Gimedialdehyde, phthalaldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, and the like. Examples of the biphenyl crosslinking agent include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, and bis(chloromethyl)biphenyl. However, it is not limited to these compounds.

In addition to the above, an acid anhydride-based curing agent, an amine-based curing agent, or another curing agent may be used as the curing agent (C) for the epoxy resin. Specific examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and pyromellitic anhydride. Phthalic anhydride, trimellitic anhydride, methyl nadic anhydride, maleic anhydride, and the like, but are not limited to these compounds.

Specific examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, m-xylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, and diamine. Diphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, as a condensate of an acid such as a dimer acid and a polyamine An amine-based compound such as a polyamide amine is not limited to these compounds.

Specific examples of the other hardener include a phosphine compound such as triphenylphosphine or a phosphonium salt such as tetraphenylphosphonium bromide, or 2-methylimidazole, 2-phenylimidazole or 2-ethyl-4-methyl. Imidazoles such as imidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, or imidazolium salts of salts of imidazoles and trimellitic acid, isocyanuric acid, boric acid, and the like Or a quaternary ammonium salt such as trimethylammonium chloride or a diazabicyclo compound, or a salt of a diazabicyclo compound and a phenol or a phenol novolak resin, or a boron trifluoride and an amine Further, a compound such as an ether compound or an aromatic phosphonium or an iodonium salt is not limited to these compounds.

In the oxazine resin composition, a hardening accelerator (D) can be used as needed. 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 complex salts. These hardening accelerators may be used singly or in combination of two or more.

The amount of the curing accelerator to be used is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5.0 parts by mass, per 100 parts by mass of the epoxy resin (B) in the oxazine resin composition. By using a hardening accelerator, the hardening temperature can be lowered, or the hardening time can be shortened. The curing conditions of the oxazine resin composition of the present invention are 200 ° C to 240 ° C for 2 hours to 5 hours without using a curing accelerator, and 170 ° C to 190 ° C when a curing accelerator is used. 0.5 hours to 5 hours.

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethyl An alkyl-substituted imidazole compound such as imidazole, 2-isopropylimidazole, 2,4-dimethylimidazole or 2-heptadecylimidazole, or 2-phenylimidazole or 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1 -(2'-Cyanoethyl)imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, etc., substituted with a hydrocarbyl group having a ring structure such as an aryl group or an aralkyl group Compounds and the like are not limited to these compounds. Among these imidazole derivatives, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole is preferred from the viewpoint of hardenability at a low temperature.

Examples of the tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, and 1,8-diaza-bicyclo [5.4]. .0] -1 - undecene (1,8-diaza-bicyclo [5.4.0]-7-undecene, DBU), etc., but is not limited to these compounds. Examples of the phosphines include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane. The metal compound may, for example, be tin octylate or the like, but is not limited to these compounds. Examples of the amine-missing salt include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, and boron trifluoride chlorophenyl group. The boron trifluoride complex such as an amine complex, a boron trifluoride benzylamine complex, a boron trifluoride aniline complex, or a mixture of these complexes is not limited to these compounds.

Among these curing accelerators, when used as a buildup material or a circuit board, it is preferably 2-dimethylamino group from the viewpoint of excellent heat resistance, dielectric properties, solder resistance, and the like. Pyridine, 4-dimethylaminopyridine or imidazoles. Moreover, when it is used as a semiconductor sealing material, triphenylphosphine or DBU is preferable from the viewpoint of excellent in hardenability, heat resistance, electrical properties, moisture resistance reliability, and the like. Further, when a boron trifluoride complex is used, it is preferred to cause ring opening of the oxazine resin, and the resulting phenol group reacts with the epoxy group to increase the crosslinking density and obtain higher heat resistance.

In the oxazine resin composition, an organic solvent or a reactive diluent can be used for adjusting the viscosity. The organic solvent is not particularly limited, and examples thereof include decylamines such as N,N-dimethylformamide and N,N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, or Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or methanol, ethanol, 1-methoxy-2-propanol, benzyl alcohol, butyl diglycol, pine oil ( Alcohols such as pine oil), or acetates such as butyl acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, or the like A carbitol such as a granule or a butyl carbitol, or an aromatic hydrocarbon such as benzene, toluene or xylene, or dimethyl hydrazine, acetonitrile or N-methylpyrrolidone, but is not limited thereto. Further, examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether and phenyl glycidyl ether, or resorcinol glycidyl ether and neopentyl Difunctional glycidyl ethers such as diol glycidyl ether and 1,6-hexanediol diglycidyl ether, or polyfunctional glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, etc. Glycidyl ethers are not limited to these compounds.

The organic solvent or the reactive diluent is preferably a mixture of one or more of them in an organic compound concentration of 90% by mass or less in the oxazine resin composition, and a suitable type or amount thereof is appropriately selected depending on the use. For example, in the use of a printed wiring board, a polar solvent having a boiling point of 160 ° C or less, such as methyl ethyl ketone, acetone or 1-methoxy-2-propanol, is preferably used, and the amount thereof is preferably 40% by mass based on the nonvolatile content. 80% by mass. Further, in the use of the adhesive film, for example, a ketone, an acetate, a carbitol, an aromatic hydrocarbon, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or the like is preferably used. The amount of use is preferably such that the concentration of the nonvolatile component is 30% by mass to 60% by mass.

In the oxazine resin composition, other thermosetting resin or thermoplastic resin can be blended in a range that does not impair the properties. Examples thereof include a phenol resin, an acrylic resin, a petroleum resin, an anthracene resin, a coumarone-indene resin, a phenoxy resin, a polyurethane resin, a polyester resin, and a polyamide resin. , polyimine resin, polyamidimide resin, polyether phthalimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether oxime resin, polyfluorene resin, polyether ether ketone resin, poly A phenylene sulfide resin or a polyvinyl formal resin is not limited to these resins.

In the oxazine resin composition, in order to improve the flame retardancy of the obtained cured product, various well-known flame retardants can be used. Examples of the flame retardant that can be used include a halogen-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an anthrone-based flame retardant, an inorganic flame retardant, and an organic metal salt-based flame retardant. From the viewpoint of the environment, a halogen-free flame retardant is preferred, and a phosphorus-based flame retardant is particularly preferred. These flame retardants may be used singly or in combination of two or more.

Phosphorus-based flame retardants can be classified into a phosphorus-based flame retardant (phosphorus-containing additive) and a reactive phosphorus compound, and the reactive phosphorus compound can be further classified into a phosphorus-containing epoxy resin and a phosphorus-containing hardener. When the phosphorus-based flame retardant of the added system is compared with the reactive phosphorus compound, the reactive phosphorus compound has a flame retarding effect from the viewpoint of not bleeding out at the time of curing and good compatibility. Large, it is preferred to use a reactive phosphorus compound.

As the phosphorus-containing additive, any of an inorganic phosphorus-based compound and an organic phosphorus-based compound can be used. Examples of the inorganic phosphorus-based compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as guanamine phosphate, but are not limited thereto.

Further, it is preferable that the red phosphorus is subjected to surface treatment in order to prevent hydrolysis or the like, and examples of the surface treatment method include (1) using magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, cerium oxide, and hydric hydroxide. a method in which an inorganic compound such as cerium, cerium nitrate or a mixture thereof is subjected to coating treatment; and (2) a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide, and a thermosetting resin such as a phenol resin. (3) A method of performing a double coating treatment using a thermosetting resin such as a phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide, but is not limited thereto. These methods.

Examples of the organophosphorus compound include a phosphate compound [for example, a methyl acid phosphate, an ethyl acid phosphate, an isopropyl phosphate, a dibutyl phosphate, a monobutyl phosphate, Butoxyethyl acid phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl phosphate, lauryl phosphate, tridecane Acid phosphate, oleic acid phosphate, tetracosyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, butyl pyrophosphate, glycolic acid Phosphate ester, (2-hydroxyethyl) methacrylate acid phosphate, etc., condensed phosphates (for example, PX-200 (made by Daiha Chemical Industry Co., Ltd.), etc.), phosphonic acid compound, phosphinic acid Common organic phosphorus compounds such as acid compounds, phosphine oxide compounds [for example, diphenylphosphine oxide, triphenylphosphine oxide, etc.], phosphine compounds (for example, triphenyl (9H-fluorene-9-ylidene)phosphane, etc.] Or a nitrogen-containing organophosphorus compound [for example, SPS-100, SPB-100, SPE-100 (above, manufactured by Otsuka Chemical Co., Ltd.), etc.] Or phosphinate metal salts [eg EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, EXOLIT OP935 (above) Clariant (manufactured by Clariant), etc., in addition to phosphorus compounds having an active hydrogen group directly bonded to a phosphorus atom [for example, 9,10-dihydro-9-oxa-10- Phosphorene-10-oxide (hereinafter abbreviated as DOPO), diphenylphosphine oxide, etc. or a phosphorus-containing phenol compound [eg 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10 -phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-HQ), 10-(2,7-dihydroxy-1-naphthalenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxidation , 10-(1,4-dihydroxy-2-naphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-NQ), diphenylphosphinyl group Hydroquinone, diphenylphosphino-1,4-dioxynaphthalene, 1,4-cyclooctylphosphinyl-1,4-phenylene glycol, 1,5-cyclooctyleneoxyl An organic phosphorus-based compound such as phosphino-1,4-phenyl diol or the like, or a derivative obtained by reacting these organophosphorus compounds with a compound such as an epoxy resin or a phenol resin Or a phosphorus-containing epoxy resin hardener, but are not limited to these compounds.

Further, the reactive phosphorus compound used for the phosphorus-containing epoxy resin or the phosphorus-containing hardener is preferably a phosphorus compound or a phosphorus-containing phenol having an active hydrogen group directly bonded to a phosphorus atom, in terms of ease of acquisition. In view of this, DOPO, DOPO-HQ, DOPO-NQ, and the like are more preferable.

Examples of the phosphorus-containing epoxy resin include the above-mentioned Epotohto FX-305, Epotohto FX-289B, Epotohto FX-1225, and Epotohto TX-1320A. Epotohto TX-1328, etc., but is not limited to these compounds.

The phosphorus-containing epoxy resin may have an epoxy equivalent of from 200 to 800, preferably from 300 to 780, more preferably from 400 to 760. Further, the phosphorus-containing epoxy resin may have a phosphorus content of 0.5% by mass to 6% by mass, preferably 2% by mass to 5.5% by mass, and more preferably 3% by mass to 5% by mass.

The phosphorus-containing hardener may be reacted with, for example, DOPO, an aldehyde, and a phenol compound by a production method as shown in Japanese Patent Laid-Open Publication No. 2008-501063 or Japanese Patent No. 4548547, in addition to the phosphorus-containing phenol. Thus, a phosphorus-containing phenol compound was obtained. In this case, the phosphorus-based compound is condensed and added to the aromatic ring of the phenol compound via an aldehyde to be incorporated into the molecule. In addition, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by further reacting with an aromatic carboxylic acid by a production method as shown in Japanese Laid-Open Patent Publication No. 2013-185002. Further, a phosphorus-containing benzoxazine compound can be obtained by a production method as shown in Japanese Patent Laid-Open Publication No. WO2008/010429.

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

The amount of the phosphorus compound to be blended is appropriately selected depending on the kind of the phosphorus compound, the component of the epoxy resin composition, and the degree of flame retardancy required. In the case where the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing hardener, it is relative to the oxazine resin (A), the epoxy resin (B), the flame retardant, and other filler materials or The solid content (nonvolatile content) in the oxazine resin composition in which all the additives are blended, the phosphorus content is preferably 0.2% by mass to 6% by mass, more preferably 0.4% by mass to 4% by mass, even more preferably 0.5% by mass. 3.5% by mass, particularly preferably 0.6% by mass to 3% by mass. If the phosphorus content is small, it may be difficult to ensure flame retardancy, and if the phosphorus content is too large, the heat resistance may be adversely affected.

Here, the phosphorus-containing epoxy resin is treated as a compound corresponding to both the phosphorus compound and the epoxy resin (A). Similarly, the phosphorus-containing curing agent is treated as a compound corresponding to both the phosphorus compound and the curing agent (C). Therefore, in the case of using a phosphorus-containing hardener, it is sometimes unnecessary to use other hardeners or phosphorus compounds. Similarly, in the case of using a phosphorus-containing epoxy resin, it is sometimes unnecessary to use other epoxy resins or phosphorus compounds.

The blending amount of the flame retardant is appropriately selected depending on the type of the phosphorus-based flame retardant, the components of the oxazine resin composition, and the degree of flame retardancy required. For example, the phosphorus content in the organic component (excluding the organic solvent) in the oxazine resin composition is preferably 0.2% by mass to 4% by mass, more preferably 0.4% by mass to 3.5% by mass, even more preferably 0.6% by mass to 3% by mass. If the amount of phosphorus is small, it may be difficult to ensure flame retardancy, and if the amount of phosphorus is too large, it may adversely affect heat resistance.

Further, in the case of using a phosphorus-based flame retardant, for example, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, calcium carbonate, zinc molybdate or the like may be used in combination as a flame retardant auxiliary.

Examples of the nitrogen-based flame retardant include a triazine compound, a cyanuric acid compound, an isocyanuric acid compound, and a phenothiazine. A triazine compound, a cyanuric acid compound, and an isocyanuric acid compound are preferable. Examples of the triazine compound include melamine, acetamide, benzoguanamine, mellon [2,4,6-tris(cyanoamino)-1,3,5-triazine], honey. Melamine [4,4'-iminobis(1,3,5-triazine-2,6-diamine)], ethylene dimelamine, melamine polyphosphate, three Examples of the triguanamine and the like include, for example, guanyl melamine sulfate, melem sulfate, melamamine sulfate, and the like, and an amine group III. A benzene-modified phenol resin (for example, LA-7052 (manufactured by Di-Aisheng (DIC) Co., Ltd.), etc.), and further modified with an amine-based triazine-modified phenol resin using tung oil or isomerized linseed oil Compounds and the like are not limited to these compounds. Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate, but are not limited thereto. The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the epoxy resin composition, and the desired flame retardancy. For example, it is preferably a curable epoxy resin combination. In 100 parts by mass of the solid component (nonvolatile component) in the product, the compound is blended in an amount of from 0.05 part by mass to 10 parts by mass, and particularly preferably in an amount of from 0.1 part by mass to 5 parts by mass. Further, when a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound or the like can be used in combination.

The anthrone-based flame retardant is not particularly limited as long as it is an organic compound containing a halogen atom, and examples thereof include, but are not limited to, an anthrone, an anthrone rubber, an anthrone resin, and the like. The blending amount of the anthrone-based flame retardant is appropriately selected depending on the type of the anthrone-based flame retardant, other components of the epoxy resin composition, and the desired flame retardancy. For example, it is preferably a curable epoxy. In 100 parts by mass of the solid component (nonvolatile component) in the resin composition, it is blended in a range of 0.05 parts by mass to 20 parts by mass. Further, when an anthrone-based flame retardant is used, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass, but are not limited thereto. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide, zirconium hydroxide, and the like, but are not limited thereto. Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, cerium oxide, and oxidation. Chromium, nickel oxide, copper oxide, tungsten oxide, etc., but not limited to these compounds. Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate, but are not limited thereto. Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, rhodium, chromium, nickel, copper, tungsten, tin, and the like, but are not limited thereto. Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax, but are not limited thereto. Examples of the low-melting glass include hydrated glass, SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O ₅ -MgO system, and P ₂ O ₅ -B ₂ O ₃ -PbO- A glassy compound such as a MgO system, a P-Sn-OF system, a PbO-V ₂ O ₅ -TeO ₂ system, an Al ₂ O ₃ -H ₂ O system, or a lead borosilicate system, but is not limited to these glasses. The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the epoxy resin composition, and the degree of flame retardancy required. For example, it is preferred to use an epoxy resin (A). And 100 parts by mass of the solid content (nonvolatile content) in the epoxy resin composition in which the curing agent (B), the flame retardant, and other fillers or additives are blended, in an amount of 0.05 parts by mass to 20 parts by mass The blending is particularly preferably carried out in the range of 0.5 parts by mass to 15 parts by mass.

Examples of the organic metal salt-based flame retardant include ferrocene, an ethyl acetonide metal complex, an organometallic carbonyl compound, an organic cobalt salt compound, an organic sulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound. A compound obtained by an ionic bond or a coordinate bond is not limited to these compounds. The amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, the other components of the epoxy resin composition, and the degree of flame retardancy required. For example, it is preferred to 0.005 parts by mass of 100 parts by mass of the solid component (nonvolatile component) in the epoxy resin composition in which the oxygen resin (A), the curing agent (B), the flame retardant, and other fillers or additives are blended It is formulated in a range of ~10 parts by mass.

The halogen-based flame retardant may be a bromine compound or a chlorine compound, and the chlorine compound is poor in terms of toxicity. Examples of the bromine compound include p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecbromo-p-diphenoxybenzene, decabromodiphenyl ether, and tetrabromobisphenol A. Hexabromocyclododecane, hexabromobenzene, 2,2'-ethylenebis(4,5,6,7-tetrabromoisoindoline-1,3-dione) [eg Scitech ( SAYTEXBT)-93 (made by Albemarle), ethane-1,2-bis(pentabromophenyl) [such as SAYTEX 8010 (made by Albemarle)] Or a brominated epoxy oligomer [for example, SR-T1000, SR-T2000 (above, manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc.), but is not limited to these compounds. The blending amount of the halogen-based flame retardant is appropriately selected depending on the type of the halogen-based flame retardant, other components of the epoxy resin composition, and the desired flame retardancy. For example, the epoxy resin (A), The solid content (nonvolatile content) in the epoxy resin composition in which all of the curing agent (B), the flame retardant, and other fillers or additives are blended is preferably 5% by mass to 15% by mass. Further, in the case where a halogen-based flame retardant is used as the flame retardant, the following compounds may be used in combination as a flame retardant: for example, an antimony compound such as antimony trioxide, antimony tetroxide or antimony pentoxide, tin oxide or tin hydroxide; a tin-based compound, a molybdenum compound such as molybdenum oxide or ammonium molybdate, a zirconium compound such as zirconium oxide or zirconium hydroxide, a boron compound such as zinc borate or barium metaborate, an anthrone oil, a decane coupling agent, or a high molecular weight fluorenone. Isocyanic compounds, chlorinated polyethylene, and the like.

A filler material can be used as needed in the oxazine resin composition. Specific examples thereof include molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium citrate, Calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, cerium oxide alumina fiber, strontium carbide fiber, polyester fiber, cellulose fiber, aromatic poly Amidoxime fiber, ceramic fiber, microparticle rubber, thermoplastic elastomer, pigment, and the like. The reason why the filler is usually used is an effect of improving impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite or magnesium hydroxide is used, it functions as a flame retardant auxiliary as described above, and has an effect of improving flame retardancy. The amount of the filler to be added is preferably 1 part by mass to 150 parts by mass based on 100 parts by mass of the solid component (excluding the solvent, including the resin, the curing agent, and the curing accelerator) excluding the filler in the oxazine resin composition. The part is more preferably 10 parts by mass to 70 parts by mass. If the amount of the compound is large, the adhesiveness required for the use of the laminate may be lowered, and the cured product may be brittle and sufficient mechanical properties may not be obtained. Further, if the amount of the mixture is small, there is no possibility that the impact resistance of the cured material such as the impact resistance of the cured product is improved.

In the oxazine resin composition, various additives such as a decane coupling agent, an antioxidant, a releasing agent, an antifoaming agent, an emulsifier, a thixotropic imparting agent, a smoothing agent, a flame retardant, and a pigment may be optionally added. The amount of these additives is preferably 0.01% by mass to 20% by mass based on the oxazine resin composition.

When the oxazine resin composition is formed into a plate-like substrate or the like, a fibrous filler is preferably used as a filler from the viewpoints of dimensional stability, bending strength, and the like. More preferably, a glass fiber board in which glass fibers are formed into a mesh shape is mentioned.

The oxazine resin composition can be prepared by impregnating a fibrous substrate to prepare a prepreg used in a printed wiring board or the like. As the fibrous base material, an inorganic fiber such as glass or a polyester resin, a woven fabric or a nonwoven fabric of an organic fiber such as a polyamine resin, a polyacrylic resin, a polyimide resin, or an aromatic polyamide resin may be used, but Limited to this. The method for producing the prepreg from the oxazine resin composition is not particularly limited. For example, it is immersed in a resin varnish prepared by adjusting the viscosity of the oxazine resin composition with a solvent, and then impregnated, and then dried by heating to make the resin component half. The prepreg is obtained by hardening (B-stage), and for example, it can be heated and dried at 100 ° C to 200 ° C for 1 minute to 40 minutes. Here, the amount of the resin in the prepreg is preferably 30% by mass to 80% by mass based on the resin component.

Further, when the prepreg is cured, a method of curing the laminate used in the usual production of a printed wiring board can be used, but it is not limited thereto. For example, when a prepreg is used to form a laminate, one or more prepregs are laminated, and a metal foil is placed on one side or both sides to form a laminate, and the laminate is heated and pressurized to be laminated. Chemical. Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like can be used. Further, the prepreg can be cured by pressurizing and heating the produced laminate to obtain a laminate. In this case, it is preferable to set the heating temperature to 160 ° C to 220 ° C, the pressing pressure to 50 N/cm ² to 500 N/cm ² , and the heating and pressing time to 40 minutes to 240 minutes. The target hardened material is obtained. If the heating temperature is low, the hardening reaction may not proceed sufficiently, and if the heating temperature is high, the oxazine resin composition may start to decompose. Further, when the pressure is low, bubbles may remain in the inside of the obtained laminate, and electrical characteristics may be lowered. If the pressure is high, the resin may flow before curing, and a cured product having a desired thickness may not be obtained. Further, when the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if the heating and pressing time is long, thermal decomposition of the oxazine resin composition in the prepreg may occur, which is disadvantageous.

The oxazine resin composition can be obtained by hardening using the same method as the well-known oxazine resin composition to obtain an epoxy resin cured product. The method for obtaining a cured product can be carried out in the same manner as the well-known oxazine resin composition, and can be suitably used: injection molding, injection, potting, dipping, drip coating, transfer forming, compression. A method of forming a laminate or the like by laminating a resin sheet, a resin-coated copper foil, or a prepreg, and heating and press-hardening to form a laminate. The curing temperature at this time is usually in the range of 100 ° C to 300 ° C, and the curing time is usually about 1 hour to 5 hours.

The cured product of the oxazine resin of the present invention may take the form of a laminate, a molded article, a binder, a coating film, a film or the like.

The oxazine resin composition of the present invention can be used in the form of a sheet or a film. In this case, it may be tableted or filmed by a conventionally known method, and an example of a suitable molding method is a method in which the oxazine resin composition is dissolved in a solvent and obtained by a conventionally known method. The resin solution is applied onto a substrate such as a metal foil, a polyester film, or a polyimide film which has been subjected to release treatment, and then dried and peeled off from the substrate to form an insulating sheet, an insulating film, an adhesive sheet or Adhesive film.

The method for producing the adhesive sheet is not particularly limited. For example, on a carrier film which is not dissolved in the epoxy resin composition such as a polyester film or a polyimide film, the thickness of the present invention is preferably 5 μm to 100 μm. After the epoxy resin composition, it is heated and dried at 100 ° C to 200 ° C for 1 minute to 40 minutes to form a sheet. The resin sheet is formed by a method generally called a casting method. At this time, if the sheet to which the epoxy resin composition is to be applied is subjected to surface treatment with a release agent in advance, the formed adhesive sheet can be easily peeled off. Here, the thickness of the adhesive sheet is desirably formed to be 5 μm to 80 μm. The adhesive sheet obtained in this manner is usually an insulating insulating sheet, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles in the epoxy resin composition.

Next, a method of manufacturing a laminated board using the prepreg or the insulating bonding sheet of the present invention will be described. When a prepreg is used to form a laminate, one or a plurality of prepregs are laminated, and a metal foil is placed on one side or both sides to form a laminate, and the laminate is heated and pressurized to be laminated and integrated. . Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like can be used. The conditions for heating and pressurizing the laminate may be appropriately adjusted and heated and pressurized under the conditions in which the epoxy resin composition is cured. If the pressure is too low, the inside of the obtained laminate may remain. Since bubbles have a low electrical property, it is desirable to pressurize under conditions satisfying moldability. For example, the temperature can be set to 160 ° C to 220 ° C, the pressure is set to 49.0 N / cm ² to 490.3 N / cm ² (5 kgf / cm ² ~ 50 kgf / cm ² ), and the heating time is set to 40 minutes ~ 240 minutes. Further, a single-layer laminated plate obtained in this manner can be used as an inner layer material to produce a multilayer board. In this case, first, the laminated board is subjected to circuit formation by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to carry out a blackening treatment to obtain an inner layer. An insulating layer is formed on the circuit forming surface on one or both sides of the inner layer by a prepreg or an insulating bonding sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

When an insulating layer is formed using an insulating adhesive sheet, an insulating adhesive sheet is placed on a circuit forming surface of a plurality of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. The laminate is then heat-pressed and integrally molded, thereby forming a cured product of the insulating bonding sheet as an insulating layer, and forming a multilayer of the inner layer. Alternatively, a cured product of an insulating bonding sheet is formed as an insulating layer between the inner layer material and the metal foil as the conductor layer. Here, the metal foil may use the same metal foil as that used in the laminated board used as the inner layer. Further, the heat and pressure forming can be carried out under the same conditions as the molding of the inner layer. When the epoxy resin composition is applied onto the laminate to form an insulating layer, the epoxy resin composition is applied to the circuit-forming surface resin of the outermost layer of the inner layer at a thickness of preferably 5 μm to 100 μm. The film is heated and dried at 100 ° C to 200 ° C for 1 minute to 90 minutes to form a sheet. It is formed by a method generally called a casting method. The thickness after drying is desirably formed to be 5 μm to 80 μm. Further, a via hole or a circuit can be formed on the surface of the multilayer laminated plate formed in this manner by an addition method or a subtractive method to form a printed wiring board. Further, the printed wiring board can be further used as an inner layer material to repeat the above-described method, thereby further forming a multilayer laminated board.

Further, when the insulating layer is formed by the prepreg, a laminate of a prepreg or a plurality of prepregs is disposed on the circuit forming surface of the inner layer, and a metal foil is disposed on the outer side to form a laminate. . Then, the laminate is heat-pressed and integrally molded, whereby a cured product of the prepreg is formed as an insulating layer, and a metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal foil as that used in the laminated board used as the inner layer board can also be used. Further, the heat and pressure forming can be carried out under the same conditions as the molding of the inner layer. Further, the surface of the multilayer laminated plate formed as described above may be subjected to via formation or circuit formation by an addition method or a subtractive method, and the printed wiring board may be molded. Further, the printed wiring board can be further used as an inner layer material to repeat the above-described method, thereby further forming a multilayered multilayer board.

The sealing material obtained by using the oxazine resin composition is used for a strip-shaped sealing material for a semiconductor wafer, a potting-type liquid sealant, an underfill resin, and an interlayer insulating film for a semiconductor, and can be suitably used for these purposes.

In order to prepare the oxazine resin composition into a semiconductor sealing material, a method in which an additive such as another coupling agent or a releasing agent or an inorganic filler which is optionally blended in the oxazine resin composition is preliminarily mixed is used. Mix well using an extruder, kneader, roll, etc. until it becomes uniform. In the case of being used as a tape-like sealant, a method of heating a resin composition obtained by the above-described method to prepare a semi-cured sheet to form a sealant tape, and then applying the sealant may be mentioned. The tape is placed on a semiconductor wafer, heated to 100 ° C to 150 ° C to soften and form, and is completely cured at 170 ° C to 250 ° C. Further, in the case of being used as a potting-type liquid sealant, the resin composition obtained by the above-described method is dissolved in a solvent as needed, and then applied to a semiconductor wafer or an electronic component to directly harden. Just fine.

The oxazine resin composition is produced and the cured product is evaluated by heat hardening, and as a result, the oxazine resin having a specific molecular weight distribution obtained from the novolak phenol compound (e) having a specific molecular weight distribution, the monoamine compound, and the aldehyde is obtained ( A) The viscosity of the resin is lower than that of the oxazine resin other than the oxazine resin (A), so that it is easily cured even under a low temperature for a short period of time, and the cured product is excellent in heat resistance and dimensional stability. The modulus of elasticity is also relatively low, and the workability is good, not only that, but also high heat resistance and good dimensional stability, especially for a film laminate. [Examples]

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to these examples as long as the gist of the invention is not exceeded. Unless otherwise indicated, "parts" means parts by mass, and "%" means mass%.

The analysis method or measurement method is shown below. In addition, the unit of the equivalent is "g/eq.".

Epoxy equivalent: measured according to Japanese Industrial Standard (JIS) K7236 standard.

Softening point: Measured according to the JISK7234 standard and the ring and ball method. Specifically, an automatic softening point device (manufactured by Meitech Co., Ltd., ASP-MG4) was used.

Oxazine ring equivalent: The molar number (equivalent) Z of the oxazine ring of the oxazine resin (A) is calculated from the following formula based on the value of the total amine value (Y). Further, the total amine value was measured in accordance with the JIS K7237 standard, but chloroform was used instead of o-nitrotoluene for the mixed solvent. Z=56110/Y

n=0 body content rate, n=1 body content rate, n=2 body content rate, n=3 body or more content ratio, number average molecular weight (Mn), weight average molecular weight (Mw), and dispersion degree (Mw/Mn) : Determined by GPC measurement. Specifically, the main body (manufactured by Tosoh Co., Ltd., HLC-8220GPC) uses a device having a series of pipe strings (manufactured by Tosoh Co., Ltd., TSKgel G4000H _XL , TSKgel G3000H _XL , TSKgel G2000H _XL ), and a tube. The column temperature was set to 40 °C. Further, the eluent was used in tetrahydrofuran (THF), the flow rate was set to 1 mL/min, and the detector used a differential refractive index detector. The measurement sample was obtained by using 50 μL of a 0.05 g sample dissolved in 10 mL of THF and filtering using a microfilter. The data processing was performed using GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation. n=0 body content rate, n=1 body content rate, n=2 body content rate, and n=3 body or more content ratio are converted according to the area % of the peak, and Mn, Mw, and Mw/Mn are based on the standard single Dispersed polystyrene (manufactured by Tosoh Co., Ltd., A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20 , F-40, F-80, F-128) The calibration curve obtained is converted. The measurement of k=0 to 4 body, Mn, and the like of the phenol novolak resin is also the same.

Tg and ΔTg: measured according to IPC-TM-6502.4.25.c using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., DSC7000X), and Tgm (relative to the state of glass) The temperature at the intermediate temperature of the tangential curve of the tangent to the rubber state is taken as the glass transition temperature (Tg). With respect to the measurement conditions, the temperature was raised to 275 ° C at a rate of 10 ° C / min and held for 10 minutes, and then cooled to 20 ° C at 100 ° C / min for 20 minutes, and then raised to 275 ° C at 20 ° C / min. Tgm in the first temperature rise was taken as Tg (1st), Tgm in the second temperature rise was taken as Tg (2nd), and ΔTg was calculated from Tg(2nd)-Tg(1st).

Modulus of elasticity: 50 ° C at a temperature of 5 ° C / min using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Co., Ltd., EXTAR 6000 DMA6100) The value of E' was taken as the elastic modulus (50 ° C), and the value of E' at 220 ° C was taken as the elastic modulus (220 ° C).

Infrared (IR): Total reflection measurement by Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) The method (Attenuated Total Reflection (ATR) method) is used to measure the absorbance at a wave number of 650 cm ^-1 to 4000 cm ^-1 .

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

Relative permittivity and dielectric loss tangent: According to the IPC-TM-6502.5.5.9 standard, the relative value at 1 GHz is obtained by a capacitance method using a material analyzer (manufactured by AGILENT Technologies). The dielectric constant and the dielectric loss tangent were evaluated.

Copper foil peel strength and interlayer adhesion: measured according to JIS C6481 standard, and the interlayer adhesion was peeled off between the seventh layer and the eighth layer and measured.

Synthesis Example 1 (Synthesis of Phenolic Novolak Resin) In a glass separable flask equipped with a stirring device, a thermometer, a nitrogen gas introduction device, a condenser tube, and a dropping device, 2,500 parts of phenol and 7.5 parts of oxalic acid dihydrate were added. The mixture was stirred while injecting nitrogen gas, and heated to increase the temperature. Then, while stirring at 80 ° C, 474.1 parts of 37.4% of fumarin was added dropwise over 30 minutes and allowed to react. Further, the reaction temperature was maintained at 92 ° C and the reaction was carried out for 3 hours. When the temperature was raised, the reaction product water was removed to the outside of the system, and the temperature was raised to 110 °C. The residual phenol was recovered under reduced pressure at 160 ° C, and the temperature was raised to 250 ° C to recover a part of the k = 0 body to obtain a phenol novolak resin (e-1). The obtained phenol novolak resin (e-1), hydroxyl equivalent: 105, k=0 body content: 10% (area%), k=1 body content: 46%, k=2 body content: 23 %, k = 3 body content: 11%, k = 4 or more contents: 10%, Mn: 529, Mw: 587. The GPC assay spectrum is shown in Figure 3. In the figure, the peak indicated by (a ₀ ) represents k=0, the group of peaks indicated by (b ₀ ) represents k=1 and k=2, and the peak represented by (c ₀ ) represents k=3. The group of peaks represented by (d ₀ ) represents k=4 or more.

Synthesis Example 2 (Synthesis of Phenolic Novolak) A phenol novolak resin (e-2) was obtained in the same manner as in Synthesis Example 1, except that the recovery temperature at 250 ° C was changed to 240 ° C. Regarding the obtained phenol novolak resin (e-2), hydroxyl equivalent: 105, k = 0 body content: 19%, k = 1 body content: 42%, k = 2 body content: 20%, k = 3 body content rate: 10%, k=4 or more content rate: 9%, Mn: 510, Mw: 567.

The abbreviations used in the examples and comparative examples are as follows.

[Novolak phenol compound] (e-1): phenol novolak resin (e-2) of Synthesis Example 1: phenol novolak resin BRG-555 of Synthesis Example 2: phenol novolac resin (manufactured by Showa Denko Co., Ltd., Shonol BRG-555, hydroxyl equivalent: 105, k=0 body content: 25 area%, k=1 body content: 18 area%, k=2 body content: 14 area%, k=3 Body content: 10 area%, k=4 or more content: 33 area%, Mn: 353, Mw: 547)

[Epoxy Resin] YDPN-638: Phenolic novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto YDPN-638, epoxy equivalent: 176) YD-128: Bisphenol A Liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto YD-128, epoxy equivalent: 186) FX-1225: phosphorus-containing epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. Made by the company, Epotohto FX-1225, epoxy equivalent: 320, phosphorus content: 2.5%)

[Hardener] BRG-557: Phenolic novolac resin (manufactured by Showa Denko Co., Ltd., Shonol BRG-557, softening point: 80 ° C, hydroxyl equivalent: 105) GK-5855P: Aromatic modified novolac Resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., GK-5855P, hydroxyl equivalent: 230) GDP9140: Dicyclopentadiene/phenol co-condensation resin (manufactured by Qunrong Chemical Industry Co., Ltd., GDP 9140, hydroxyl equivalent: 196)

[hardening accelerator] TBZ: 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezole (registered trademark) TBZ)

[Flame retardant] PX-200: Aromatic condensed phosphate ester (manufactured by Daiba Chemical Industry Co., Ltd., PX-200, phosphorus content: 9%)

[Others] Comparative resin 2: bisphenol F-aniline type benzoxazine resin (manufactured by Shikoku Chemical Industry Co., Ltd., oxazine ring equivalent: 217) Comparative resin 3: bisphenol A-aniline type benzoxazine resin (Manufactured by Zibo Kerrben Polymer New Material Co., Ltd., Kb-31, oxazide ring equivalent: 246)

Example 1 200 parts of the phenol novolak resin (e-1) obtained in Synthesis Example 1 as a novolak phenol compound (e), 189 parts of aniline, and 256 parts of toluene were added in the same apparatus as in Synthesis Example 1. The mixture was stirred while injecting nitrogen gas, and heated to increase the temperature. Then, while stirring at 50 ° C, 134 parts of 92% paraformaldehyde was added over 1 hour, and 13 parts of water was added dropwise. Further, the temperature was maintained at 85 ° C and the reaction was carried out for 2 hours. When the temperature was raised, the reaction product water was removed to the outside of the system and the temperature was raised to 120 °C. The residual aniline and toluene were recovered under reduced pressure at 120 ° C to obtain a oxazine resin (resin 1). The GPC measurement spectrum of the obtained resin 1 is shown in Fig. 1 . In the figure, the peak shown in (a) represents n = 0, the peak group shown in (b) represents n = 1 and n = 2, and the peak group shown in (c) represents n = 3 the above. The FT-IR measurement spectrum is shown in Figure 2.

Example 2 Resin 2 was obtained in the same manner as in Example 1 except that 200 parts of 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). The GPC measurement spectrum of the obtained comparative resin 1 is shown in Fig. 4 . In the figure, the peak shown in (a) represents n = 0, the peak group shown in (b) represents n = 1 and n = 2, and the peak group shown in (c) represents n = 3 the above.

The resin No. 1 to Resin 3 and Comparative Resin 1 obtained in Examples 1 to 3 and Reference Example 1 and the comparative resin 2 to Comparative resin 3 had n=0 body content ratio, n=1 body content ratio, and n=2 body. The measurement results of the content rate, the content of n=3 or more, the Mn, Mw, the oxazine ring equivalent, and the softening point are shown in Table 1.

[Table 1]

Example 4 70 parts of resin 1, 100 parts of YDPN-638, and 30 parts of BRG-557 were mixed on a hot plate at 120 ° C, and adjusted to 0.05 g/mL with 2.0 mL of methyl ethyl ketone (MEK). TBZ varnish is mixed. After sufficiently cooling, the formulated solid pulverized product was vacuum-pressed at 130 ° C for 15 minutes and hardened at 190 ° C for 80 minutes. Tg (1st), Tg (2nd), and ΔTg of the cured product were measured. The results are shown in Table 2.

Each of Examples 5 to 7 and Comparative Examples 1 to 4 was prepared by blending the amount (parts) of the formulation of Table 2, and a cured product was obtained in the same manner as in Example 4. The same test as in Example 4 was carried out, and the results are shown in Table 2. Further, (H)/(Z) in the table represents the equivalent ratio (molar ratio) of active hydrogen (H) to oxazine ring (Z), and (H+Z)/(E) represents active hydrogen (H) and The equivalent ratio of the sum of the oxazin ring (Z) to the epoxy group (E) (mol ratio).

[Table 2]

According to Table 2, when the resin of the example was used, a cured product having a small ΔTg was obtained. The small ΔTg means that the unreacted portion is small, and the cured product or the laminated plate of the resin of the example can be said to have good dimensional stability. Although the cured product of the conventional polyfunctional oxazine resin is used, although the Tg is increased, there is a disadvantage that the unhardened portion remains and the dimensional stability is deteriorated, that is, ΔTg is increased. However, the cured product of the example has the same Tg as the conventional polyfunctional oxazine resin, and the ΔTg is small, so that the trade-off of the prior art can be eliminated.

Example 8 28 parts (solid content: 21 parts) of MEK varnish (nonvolatile content (NV.) 75%) and 240 parts (solid content: 180 parts) of FX-1225 MEK varnish (NV. 75%), 77 parts (solid content: 50 parts) of BRG-557 MEK varnish (NV.65%) and 2.0 mL of TBZ MEK varnish (0.05 g/mL) were mixed and formulated in Table 3 to A mixed solvent of MEK and propylene glycol monomethyl ether (mass ratio = 1/1) was dissolved to obtain a NV.50% resin varnish.

The obtained resin varnish was impregnated in a glass cloth WEA628XS13 (manufactured by Nitto Textile Co., Ltd., 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C for 9 minutes to obtain a prepreg. The obtained prepreg was superposed on eight sheets, and copper foil (manufactured by Mitsui Mining & Mining Co., Ltd., 3EC) was superposed on top and bottom, and heated at 130 ° C, 15 minutes, 190 ° C, 20 kg/cm ² , and 80 minutes. Pressurize to obtain a laminate. The elastic modulus (50 ° C) and the elastic modulus (220 ° C) of the laminate were measured. The results are shown in Table 3.

Example 9 to Example 10 and Comparative Example 5 to Comparative Example 7 The blending amount was obtained in the same manner as in Example 8 except that the blending amount (parts) of the formulation of Table 3 was adjusted. The same test as in Example 8 was carried out, and the results are shown in Table 3.

[table 3]

According to Table 3, when the resin of the example was used, the elastic modulus was small even at a temperature exceeding the glass transition temperature, and the elasticity was low. Recently, the problem of warpage of the laminated sheet has been caused by the reduction in the thickness of the laminated sheet, and the resin used to improve the above problem is expected to have a low elastic modulus. However, the prior art cannot obtain an oxazine resin composition satisfying the characteristics. However, the resin of the example is also less elastic than the conventional oxazine resin at a temperature exceeding the glass temperature, so that the problem of warpage of the laminated plate can be further improved.

Example 11 to Example 13 and Comparative Example 8 to Comparative Example 9 The compounding amount (parts) of the formulation of Table 4 was adjusted, and a laminate was obtained in the same manner as in Example 8. Each test of flame retardancy, relative dielectric constant, dielectric loss tangent, copper foil peel strength, and interlayer adhesion was carried out, and the results are shown in Table 4.

[Table 4]

no

Figure 1 is a GPC chart of the oxazine resin of the present invention. 2 is a Fourier Transform Infrared Spectroscopy (FT-IR) spectrum of the oxazine resin of the present invention. Fig. 3 is a GPC chart of a raw material novolak phenol compound. 4 is a GPC chart of the oxazine resin of Comparative Example 1.

Claims (12)

An oxazine resin composition containing a oxazine resin (A) and an epoxy resin (B), and the oxazine resin composition is characterized in that the oxazine resin (A) is represented by the following formula (1) In the gel permeation chromatography measurement, the content of the n=0 body is 15% by area or less, and the total content of the n=1 body and the n=2 body is 35% by area to 70% by area, and n=3 or more. The content of the content is 50% by area or less, and the number average molecular weight is 400 to 2500 in terms of standard polystyrene; (wherein 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 have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 6 An alkoxy group, 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 an aromatic ring a substituent; X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or the following formula (1b); and R ₁ each 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; and 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 a carbon number of 7 ～12 aralkyl; m is 1 or 2; n is an average of 1 to 5); (wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; and A ₂ represents an aromatic cyclic group selected from a benzene ring, a naphthalene ring or a biphenyl ring; The aromatic ring group may have 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, and a carbon number of 7 An aralkyl group of ～12 or an aralkyloxy group having 7 to 12 carbon atoms is a substituent of the aromatic ring). The oxazine resin composition according to claim 1, wherein the epoxy resin hardener (C) is further prepared. The oxazine resin composition according to claim 2, wherein the active hydrogen (H) of the epoxy resin hardener (C) and the oxazine ring (Z) of the oxazine resin (A) are used. The hardener (C) for epoxy resin is blended in such a manner that the molar ratio (H/Z) is from 0/10 to 9/1. The oxazine resin composition according to claim 2, wherein the oxazine ring of the oxime resin (A) with respect to the epoxy group of the epoxy resin (B) The epoxy resin hardener (C) is blended in such a manner that the molar ratio of the active hydrogen of the epoxy resin hardener (C) is from 0.2 mol to 1.5 mol. The oxazine resin composition according to Item 2 or 3, wherein the epoxy resin hardener (C) is a phenolic curing agent. The oxazine resin composition according to any one of the items 1 to 3, wherein the epoxy resin (B) is further blended in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the epoxy resin (B). Agent (D). A prepreg characterized by using the oxazine resin composition according to any one of claims 1 to 6. A laminated board characterized by using the oxazine resin composition according to any one of claims 1 to 6. A cured product obtained by hardening an oxazine resin composition according to any one of claims 1 to 6. An oxazine resin composition comprising an oxazine resin (A) and an epoxy resin (B), and the oxazine resin composition is characterized in that the oxazine resin (A) is a phenolic phenol compound (e), The monoamine compound represented by the following formula (21) and the aldehyde represented by the following formula (22) are obtained, and the novolak phenol compound (e) is represented by the following formula (2), and In the gel permeation chromatography measurement, the content of the k=0 body is 20% by area or less, and the total content of the k=1 body and the k=2 body is 50% by area to 95% by area, and the content ratio of the k=3 body is 15% by area or less, the content of the high molecular weight body of k=4 or more is 15% by area or less, and the number average molecular weight is 350 to 1500 in terms of standard polystyrene; (wherein 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 have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 6 An alkoxy group, 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 an aromatic ring a substituent; X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or the following formula (1b); m is 1 or 2; k is 0.8 to an average value Number of 3); (wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; and A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring; The aromatic ring group may have 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, and a carbon number of 7 ～12 aralkyl or aralkyloxy having 7 to 12 carbon atoms as a substituent of an aromatic ring); R ₁ —NH ₂ (21) R ₂ —CHO (22) (R ₁ and R ₂ are each independently The ground 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. A method for producing a oxazine resin, which comprises reacting a novolak phenol compound (e), a monoamine compound represented by the following formula (21), and an aldehyde represented by the following formula (22) to produce a oxazine resin, and The method for producing the oxazine resin is characterized in that the novolak phenol compound (e) is represented by the following formula (2), and has the following molecular weight distribution in gel permeation chromatography measurement: k=0 body content The rate is 20% by area or less, the total content of the k=1 body and the k=2 body is 50% by area to 95% by area, the content of the k=3 body is 15% by area or less, and the high molecular weight of k=4 or more. The content of the body is 15% by area or less, and the number average molecular weight is 350 to 1500 in terms of standard polystyrene; (wherein 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 have an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 6 Any one of an alkoxy group, 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 a fragrance a substituent of a group ring; X each independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by the following formula (1a) or the following formula (1b); m is 1 or 2; k is an average value a number of 0.8 to 3); (wherein R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; and A ₂ represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring; The aromatic ring group may have 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, and a carbon number of 7 Any of aralkyl groups of ～12 or aralkyloxy groups having 7 to 12 carbon atoms as a substituent of an aromatic ring; R ₁ —NH ₂ (21) R ₂ —CHO (22) (R ₁ , R ₂ each 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. The method for producing an oxazine resin according to claim 11, wherein the monoamine compound is aniline and the aldehyde is formaldehyde.