TWI720125B - Oxazine resin composition and cured product thereof - Google Patents

Abstract

（這裡，A₁ 為選自苯環、萘環或聯苯環中的芳香族環基，X為二價交聯基，m為1或2，n為1～5）The present invention provides an oxazine resin composition and a cured product thereof. The oxazine resin composition forms a cured product having excellent heat resistance and good dimensional stability even under industrially low temperature and short-time curing conditions. The oxazine resin composition of the present invention contains an oxazine resin (A) and an epoxy resin (B). The oxazine resin (A) is represented by the following formula (1) and has the following molecular weight distribution in GPC measurement ：The content rate of n=0 body is 15% or less, the total content of n=1 body and n=2 body is 35% to 70%, the content rate of n=3 body or more is 50% or less, and the number average molecular weight is 400～2500. [化1]

(Here, A ₁ is an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, X is a divalent crosslinking group, m is 1 or 2, and n is 1 to 5)

Description

Oxazine resin composition and its manufacturing method, prepreg, laminated board and hardened product

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

In recent years, it has been used for copper clad laminates for printed wiring boards, adhesives for multilayer wiring boards, sealing materials for semiconductors, adhesives for semiconductor packaging, modules for mounting semiconductors, or for automobiles, airplanes, building components, etc. The hardenable materials used in the parts, etc. require heat-resistant materials that are excellent in stability or reliability under high temperature/high humidity. Furthermore, in the energy field, research and development of fuel cells, various secondary batteries, etc. have progressed, and heat-resistant materials have gradually been required. Particularly in hybrid vehicles, electric vehicles, and distributed power supplies, power devices are often used with inverters as the center, and their power density has also increased dramatically. Therefore, silicon carbide (SiC) devices that operate at high temperatures above 200°C are also expected. In addition, the Electronic Control Unit (ECU) that uses a normal semiconductor chip is also mounted from the cabin to the engine room where the environment is harsh. Therefore, heat resistance that can withstand harsh conditions is still required. In response to this demand, heat-resistant resins (Patent Document 1, Patent Document 2, Non-Patent Document 1, etc.) obtained by reacting a compound containing a benzoxazine ring structure with an epoxy resin are being studied.

It has also been reported that when a compound containing a benzoxazine ring structure is reacted with an epoxy resin such as bisphenol A diglycidyl ether in a stoichiometric amount, unreacted substances remain, which hinders the formation of ideal crosslinking Therefore, by making the epoxy resin more than the stoichiometric amount, the cured resin provides a high glass transition point (Tg) (Non-Patent Document 2). However, these previous resins and resin compositions have the following disadvantages: the glass transition temperature is about 160°C, and the characteristics of heat resistance or flame retardancy are not sufficient. In order to obtain good characteristics, a high curing temperature and a long curing temperature are required. Hardening time, etc. In order to increase the glass transition temperature by hardening at a low temperature and a short time in industry, an oxazine resin obtained by using a polyfunctional phenol resin as a raw material can be used. However, this method has residual uncured parts, although the glass transition temperature is increased. But the disadvantage of poor dimensional stability.

In addition, recently, with the thinning of the laminate plate, there is a problem of the warpage of the laminate plate, and low warpage performance is required. Therefore, low elasticity is required for the resin used, but an oxazine resin composition that satisfies the characteristics cannot be obtained. [Prior Art Document] [Patent Document]

[Patent Document 1] European Patent No. 2304852 specification. [Non-Patent Literature]

[Non-Patent Document 1] "Forming and Processing", Volume 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] The object of the present invention is to provide an oxazine resin composition and a cured product thereof, which can be heat-resistant even under the industrially favorable low-temperature and short-time curing conditions. Hardened product with excellent properties and good dimensional stability. [Means to Solve the Problem]

In order to achieve the above-mentioned object, the present inventors have conducted diligent studies and found that by using a polyfunctional oxazine resin with a specific molecular weight distribution, heat resistance is improved, and the viscosity of the resin is also low, so that it can be used in a short time at low temperature. It is easy to harden under the conditions of, and the elastic modulus of the hardened product is relatively low, thus 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 composed of the following formula (1) It has the following molecular weight distribution in Gel Permeation Chromatography (GPC) measurement: the content rate of n=0 body 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 bodies or more is 50% or less, and the number average molecular weight is 400 to 2500 in terms of standard polystyrene conversion values.

[化1]

In 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 6 Any one of 6 alkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7-12 aralkyl, or C 7-12 aralkyloxy Substituents on aromatic rings. In addition, in the formula (1), _{the two adjacent carbons in the aromatic ring of A 1} are integrated with the ring constituent atoms 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 a hydrogen, it becomes a structure having an N-phenyl-benzoxazine ring structure. In addition, in this specification, the biphenyl ring as the aromatic ring group refers to -Ph-Ph- (here, Ph is a phenylene group), and the oxazine ring refers to a six-membered ring formed by -CNCOCC- Ring (hydroxazine 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 carbons, an aryl group having 6 to 12 carbons, and an aralkyl group having 7 to 12 carbons. R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, and an aralkyl group having 7 to 12 carbons. m is 1 or 2, n is the number of repeating units and represents an integer of 0 or more, and its average value is 1-5.

[化2]

In formula (1a), R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. In formula (1b), R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group 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. These aromatic ring groups may have an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, and 6 carbons. Any one of an aryl group having a carbon number of to 10, an aryloxy group having 6 to 10 carbons, an aralkyl group having 7 to 12 carbons, or an aralkyloxy group having 7 to 12 carbons is a substituent of the aromatic ring.

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

When the hardener (C) for epoxy resin is formulated, it is preferable to use the active hydrogen (H) of the hardener (C) for epoxy resin and the oxazine ring (Z) of the oxazine resin (A) as H/Z=0/10～9/1 mol ratio.

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

In addition, the present invention is an oxazine resin composition containing oxazine resin (A) and epoxy resin (B), and the oxazine resin composition is characterized in that: the oxazine resin (A) is made of novolac Compound (e), a monoamine compound represented by the following formula (21), and an aldehyde represented by the following formula (22), and the novolac compound (e) is obtained by the following formula (2) It has the following molecular weight distribution in the gel permeation chromatography measurement: the content of k=0 body is 20% (area%) or less, and the total content of k=1 body and k=2 body is 50%～ 95%, the content rate of k=3 body is 15% or less, the content rate of high molecular weight body of k=4 body or more is 15% or less, and the number average molecular weight is 350 to 1500 in terms of standard polystyrene conversion value. R ₁ -NH ₂ (21) R ₂ -CHO (22) (R ₁ and R ₂ each independently represent an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an aryl group having 7 to 12 carbons. alkyl)

[化3]

In formula (2), A ₁ , X and m have the same meaning as _{A 1} , X and m in formula (1), respectively. k is the number of repeating units and represents an integer of 0 or more, and its average value is 0.8-3.

In addition, the present invention is a prepreg or laminated board characterized by using the oxazine resin composition. Furthermore, the present invention is a cured product obtained by curing the oxazine resin composition.

In addition, the present invention is a method for producing an oxazine resin, which reacts a novolac compound (e), a monoamine-based compound, and aldehydes to produce an oxazine resin, and the method for producing an oxazine resin is characterized by using The novolac compound (e) represented by the formula (2) is referred to as the novolac compound (e).

Preferably, the monoamine-based 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 rate, 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 formula (1), and the content of n=0 body is 15% or less, and the total content of n=1 body and n=2 body is 35 % To 70%, the content rate of n=3 or more is 50% or less, and the number average molecular weight (Mn) is 400 to 2500 in terms of standard polystyrene conversion value. The oxazine resin (A) is obtained from a novolac compound (e), a monoamine-based compound, and aldehydes having a specific molecular weight distribution. Here, the content of n=1 body, n=2 body, n=3 body, k=1 body, k=2 body, k=3 body, etc. in oxazine resin (A) and novolac compound (e) The rate is the area% measured by GPC. In addition, n=1 body refers to a component in which n is 1 in formula (1), and n=0 body refers to a component in which n is 0 in formula (1). 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 groups including a benzene ring, a naphthalene ring, or a biphenyl ring that may have a substituent. These aromatic ring groups may have substituents on the aromatic ring. The substituents are alkyl groups having 1 to 6 carbons, alkoxy groups having 1 to 6 carbons, aryl groups having 6 to 10 carbons, and Any of 6-10 aryloxy, 7-12 aralkyl, or 7-12 aralkyloxy. When it has a plurality of substituents, they may be the same or different. However, the two carbons constituting a part of the hydroxazine ring may not have a substituent, and the one carbon adjacent to the two carbons may not have a substituent. In addition, in formula (1) to formula (7), formula (21), and formula (22), common symbols have the same meaning unless otherwise specified.

Alkyl represents a linear, branched, or cyclic alkyl group, and examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tertiary butyl. , Pentyl, hexyl, cyclohexyl, etc. Among these groups, branched or cyclic alkyl groups tend to impart high heat resistance compared to linear ones. The carbon number is preferably 1 to 4 in the case of a chain alkyl group, and preferably 6 in the case of a cyclic alkyl group. Preferred are isopropyl, isobutyl, tertiary butyl, and cyclohexyl, and more preferred are tertiary butyl and cyclohexyl. In addition, methyl is also preferred because of the tendency for flame retardancy to improve.

Examples of the aryl group include a phenyl group, a naphthyl group, and the like, and a phenyl group is preferred. The aralkyl group includes, for example, a benzyl group, a phenethyl group, and a 1-phenylethyl group, and a benzyl group and a 1-phenylethyl group are preferable.

X is a divalent aliphatic cyclic hydrocarbon group or any one of the crosslinking groups represented by the formula (1a) or the formula (1b). The number of carbon atoms of the divalent aliphatic cyclic hydrocarbon group is preferably 5-15, and more preferably 5-10. Here, the divalent aliphatic cyclic hydrocarbon group includes dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborne-2-ene, α-pinene, β -A divalent aliphatic cyclic hydrocarbon group derived from an unsaturated cyclic aliphatic hydrocarbon compound such as pinene and limonene. Among these aliphatic cyclic hydrocarbon groups, divalent hydrocarbon groups derived from dicyclopentadiene are particularly preferred from the viewpoint of heat resistance. In addition, in formula (1a) and formula (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 formula (1) except that the valence is divalent.

R ₁ each independently represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 12 carbons. 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, and a methyl group, a phenyl group, and a tolyl group are preferable.

R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 12 carbons. 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, and 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 material novolac 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 the said range, the improvement effect of hardenability becomes remarkable, and it is preferable from this point. In addition, n in the above-mentioned formula (1) can be obtained as follows.

According to the GPC measurement, the styrene-converted molecular weight corresponding to each of n=0 body, n=1 body, n=2 body, n=3 body and n=4 body (α0, α1, α2, α3 , Α4) and the ratio of the theoretical molecular weight (β0, β1, β2, β3, β4) of n=0 body, n=1 body, n=2 body, n=3 body, n=4 body (β0/α0, β1/α1, β2/α2, β3/α3, β4/α4), and find the average value of these (β0/α0～β4/α4). The value obtained by multiplying the styrene-converted molecular weight Mn determined by GPC by the average value is defined as the average molecular weight Mn. Then, the theoretical molecular weight of the formula (1) is set to the average molecular weight Mn, and the value of n is calculated.

For example, in the case of the oxazine resin of Example 1 mentioned later, the structural formula becomes the formula (3) mentioned later, and its theoretical molecular weight becomes 434+223n=Mn'. In addition, according to the GPC measurement value, Mn was 754, 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. It is important that the content of n=0 body and n=3 body or more is below the specific amount, and the total content of n=1 body and n=2 body is The rate is in the range of a specific amount. If the content of the n=0 body exceeds 15% (area %), the heat resistance is improved (high Tg), but the hardened part tends to become hard and brittle, and it may not be possible to have a low elastic modulus. The content of the n=0 body is preferably 12% or less, more preferably 10% or less, and still more preferably 5% or less. In addition, if the content of n=3 or more exceeds 50%, the reactivity may be significantly deteriorated and a large amount of uncured materials may remain. The content rate of n=3 or more is preferably 45% or less, and more preferably 40% or less. If it is in the said range, when the content rate of n=0 body is small, it is preferable that the content rate of n=3 body or more is also small. In addition, when the content rate of n=0 body is large, it does not matter if the content rate of n=3 body or more is large. Therefore, the difference between the content rate of n=0 body and the content rate of n=3 body or more is preferably 30% to 40%. If there is a specific amount of n=1 body or n=2 body, the cured product has a high Tg and a low elastic modulus, and the reactivity is also improved. This tendency is caused regardless of whether there are more n=1 body or n=2 body. Therefore, it is preferable to manage the total content ratio of n=1 body and n=2 body. The total content of n=1 body and n=2 body is preferably 40% to 65%, more preferably 43% to 60%, and still more preferably 45% to 55%.

In addition, the number average molecular weight is 400 to 2500 in terms of standard polystyrene conversion value, preferably 400 to 2000, more preferably 450 to 1500, and still more preferably 450 to 1000.

In addition, in the GPC measurement peaks with n=2 or more, in addition to the oxazine resin (A) represented by the above formula (1), the novolak phenol compound (e) is also included by the monoamine compound and the aldehyde It is similar to several compounds formed by self-polymerization, but since these compounds cannot be separated, each content rate is calculated as the area% included.

The oxazine resin (A) is preferably derived from the following formula (3) 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 represented oxazine resin.

[化4]

As described above, the oxazine resin (A) is obtained from the novolac compound (e), monoamine-based compounds, and aldehydes having a specific molecular weight distribution. In the formula (1), R ₁ is a substituent derived from a monoamine compound, and R ₂ is a substituent derived from aldehydes.

The novolac compound (e) having a specific molecular weight distribution is represented by the formula (2). k is the number of repeating units 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. In GPC measurement, it has the following specific molecular weight distribution: the content of k=0 body is 20% (area%) or less, the total content of k=1 body and k=2 body is 50%-95%, k=3 The content rate of the body is 15% or less, the content rate of the high molecular weight body with k=4 body or more is 15% or less, and the Mn is 350 to 1500 in terms of standard polystyrene conversion value. If it does not have such a molecular weight distribution, the oxazine resin used in the present invention cannot be obtained with a good yield. The content of the k=0 body is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, and most preferably 5% or less. In addition, the content of the high-molecular-weight body with k=4 or more is preferably 10% or less, and it is more preferable that the high-molecular-weight body with k=5 or more is not contained at all. The content of k=3 bodies is preferably 10% to 15%. The total content of k=1 body and k=2 body is preferably 60% to 92%, and more preferably 65% to 90%. In particular, the content of k=1 body is preferably 35% to 65%, and the content of k=2 body is preferably 15% to 30%. In addition, the number average molecular weight Mn is preferably 350 to 1,000, more preferably 350 to 700, and still more preferably 400 to 550. The degree of dispersion (weight average molecular weight Mw/Mn) is preferably 1.05 to 1.3, more preferably 1.08 to 1.2, and still more preferably 1.1 to 1.15. In addition, the GPC measurement conditions of the novolac compound (e) are the same as the GPC measurement conditions of the oxazine resin (A).

The phenols used to obtain the novolac compound (e) include phenol, cresol, ethyl phenol, butyl phenol, styrenated phenol, cumyl phenol, naphthol, catechol, and resorcinol. Phenol, naphthalenediol, etc., but not limited to these compounds, and these phenols may be used alone or in combination of two or more. Among these phenols, monophenols such as phenol and alkylphenol are preferred. In the case of alkylphenol, the alkyl group is suitably an alkyl group having 1 to 6 carbon atoms.

The crosslinking agent used to obtain the novolac compound (e) may include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and benzaldehyde represented by the following formula (4), or the following Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone represented by the formula (5), or terephthalic alcohol and terephthalic methanol represented by the following formula (6) Ether, p-xylylene dichloride, 4,4'-dimethoxymethyl biphenyl, 4,4'-dichloromethyl biphenyl, dimethoxymethyl naphthalene, two Crosslinking agents such as chloromethyl naphthalenes, or crosslinking agents such as divinylbenzenes, divinyl biphenyls, and divinyl naphthalenes represented by the following formula (7), or cyclopentadiene or divinyl naphthalenes Cycloalkyldienes such as cyclopentadiene are not limited to these compounds. These crosslinking agents may be used alone or in combination of two or more. X in formulas (1) and (2) becomes a divalent aliphatic cyclic hydrocarbon group when cycloalkyldienes are used, and when a crosslinking agent of formula (4) or formula (5) is used, it becomes The crosslinking group represented by the formula (1a) becomes the crosslinking group represented by the formula (1b) when the crosslinking agent of the formula (6) or the formula (7) is used. Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, dichlorop-xylene, 4,4'-dichloromethylbiphenyl are preferred, and formaldehyde is particularly preferred. In the case of using formaldehyde in the reaction, preferred forms include aqueous formalin, paraformaldehyde, trioxane, and the like.

[化5]

In formula (4) and formula (5), _{R 3} and R ₄ have the same meaning as _{R 3} and R ₄ in formula (1a), respectively. 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 .

The acid catalyst used to obtain the novolac compound (e) includes protic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, and zinc chloride. , Lewis acids such as ferric chloride, oxalic acid, monochloroacetic acid, etc., but not limited to these compounds. These acid catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferred.

The novolac compound (e) having a specific molecular weight distribution used in the present invention can be obtained by adjusting the molar ratio of phenols and aldehydes and removing low molecular weight components from the obtained novolac compound (e). obtain. In addition, such a novolac compound (e) can also be obtained by a manufacturing method as shown in Japanese Patent Laid-Open No. 2002-194041 or Japanese Patent Laid-Open No. 2007-126683.

The molar ratio of phenols to crosslinking agent is expressed as the molar ratio of phenols to 1 mol of crosslinking agent (phenols/crosslinking agent), and the molar ratio is 1 or more. For manufacturing, when the molar ratio is large, a large amount of k=0 body and k=1 body are produced. On the contrary, when the molar ratio is small, a large amount of high molecular weight bodies with k=3 body or more are produced, and k=0 body, k=1 body reduction. In addition, in order for the oxazine resin to have a specific molecular weight distribution, the novolac compound (e) must be set to a specific molecular weight distribution. In order to set it so that it may become the said range, the molar ratio of a phenol and a crosslinking agent (phenols/crosslinking agent) is preferably 3 or more and 6 or less, More preferably, it is 4 or more and 5 or less. By reducing or removing low molecular weight components from the novolac compound (e) obtained by adjusting the molar ratio of the phenols and the crosslinking agent in this way, a novolac compound (e) having a specific molecular weight distribution can be obtained. In this case, methods for reducing or removing low-molecular-weight components, particularly k=0 bodies, include methods using poor solubility in various solvents, methods of dissolving in alkaline aqueous solutions, and other well-known separation methods.

The monoamine-based compound used to obtain the oxazine resin is represented by the formula (21), and the aldehydes are represented by the formula (22). In formula (21), _{R 1} has the same meaning as _{R 1} in 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 compounds, aromatic monoamine compounds are preferred, and aniline and methylaniline are more preferred.

In formula (22), _{R 2} has the same meaning as _{R 2} in formula (1). The aldehydes are the same aldehydes used to obtain the novolac compound (e). Among these aldehydes, formaldehyde, acetaldehyde, and benzaldehyde are preferred, and formaldehyde is particularly preferred. Preferred forms when using formaldehyde include formalin aqueous solution, paraformaldehyde, trioxane, and the like.

Regarding the amount of each raw material used, the monoamine-based compound is preferably 1 mol to 2 mol, and more preferably 0.9 mol to 1.1 mol relative to 1 mol (equivalent) of the hydroxyl group of the novolac compound (e). The aldehydes are preferably 1.7 mol to 2.5 mol, more preferably 1.8 mol to 2.2 mol. In particular, aldehydes can be added in a slight excess. Relative to the hydroxyl group of the novolac phenol compound, the theoretical amount is 1 mol of monoamine compound and 2 mol of aldehydes, but polymerization of novolac compounds or only monoamine compound and aldehydes occurs as a side reaction The reaction product. In addition, unreacted substances that can be separated are removed in the post-treatment step, so monoamine-based compounds or aldehydes may also remain. The total amount of these impurities is preferably 5% by mass or less. In addition, when the novolac compound (e) has m(k+2) OH groups on average, the novolac compound calculated as 1 mol has m(k+2) OH groups, and the OH group The base 1 mole is calculated as 1 equivalent.

Regarding the manufacturing method, there is no special manufacturing method, and a commonly used manufacturing method can be used. A general production method includes a method of heating and stirring the novolak phenol compound (e) and the monoamine compound in a solvent, adding aldehydes, and maintaining the novolac compound (e) at 70°C to 120°C for 20 minutes to 24 hours. After the reaction, the product is separated and purified by reprecipitation by throwing it into a poor solvent such as methanol, which has low solubility for the product, or by synthetic chemical methods such as solvent extraction, and condensed at a temperature below 120°C Volatile components such as water are removed under reduced 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 the reaction does not substantially proceed. If the reaction temperature exceeds 120° C., the generated oxazine ring will open, and a bonding reaction will occur with other phenolic hydroxyl groups. This promotes high molecular weight side reactions and tends to form insoluble gels. In the reaction at high temperature, it is easy to cause the ring-opening and 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 70°C to 110°C, more preferably 80°C to 100°C. In addition, with regard to the reaction time, if the reaction time is 20 minutes or less, the formation of the oxazine ring is insufficient, and if it is 24 hours or more, the ring-opening and crosslinking reaction of the generated oxazine ring is gradually caused at the same time. Therefore, in order to improve the oxazine ring formation reaction and reduce the generation of gel, the reaction time is preferably 1 hour to 10 hours, more preferably 1.5 hours to 6 hours.

In addition, it may further include a step of removing water generated by the reaction. By removing the water generated 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 a method of azeotroping with the solvent in the reaction solution and the like can be mentioned. In addition, by setting the inside of the reaction vessel to a reduced pressure in the reaction step, the generated water can also be removed out of the system.

An oxazine resin is obtained by adding a poor solvent such as methanol to the reaction mixture obtained in this way to analyze the composition of the resin. Alternatively, the oxazine resin can be obtained by removing the solvent, water, monoamine-based compound, and aldehydes by performing water washing or washing operation as necessary after the reaction is completed.

Next, the epoxy resin (B) blended in the oxazine resin composition of the present invention will be described. The epoxy resin (B) is not particularly limited, and various epoxy resins can be applied as long as it is a well-known epoxy resin. Usable epoxy resins (B) include polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins, but are not limited to these Epoxy resins, these epoxy resins may be used alone, or two or more of them may be used in combination.

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

Specific examples of polyglycidylamine compounds include: diaminodiphenylmethane type epoxy resins (for example, Epotohto YH-434, Epotohto YH-434GS (the above are Nippon Steel & Sumikin Chemicals) Co., Ltd.), ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), Araldite MY720, Araldite MY721, Araldite MY9512, Araldite MY9663 (the above are Huntsman Advanced Chemicals (Huntsman Advanced Materials), etc.), meta-xylene diamine epoxy resin (such as TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.), 1,3 -Bisaminomethyl cyclohexane type epoxy resin (such as TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.), isocyanurate type epoxy resin (such as Terbic ( TEPIC)-P (manufactured by Nissan Chemical Industry Co., Ltd.), aniline epoxy resin (such as GAN, GOT (the above are manufactured by Nippon Kayaku Co., Ltd.), etc.), hydantoin-type epoxy resin (such as Y238 (manufactured by Huntsman Advanced Materials), etc.), aminophenol epoxy resin (such as ELM120, ELM100 (manufactured by Sumitomo Chemical Co., Ltd. above), jER630 (manufactured by Mitsubishi Chemical Co., Ltd.) , Araldite MY0510, Araldite MY0600, Araldite MY0610 (manufactured by Huntsman Advanced Materials), etc., but not limited to these compounds.

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

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

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

Moreover, in the oxazine resin composition of this invention, the hardener (C) for epoxy resins may be used together as needed. The hardeners (C) for epoxy resins that can be used in combination include various phenol resins, acid anhydrides, amines, hydrazines, acid polyesters, and other commonly used hardeners for epoxy resins. These epoxy resins Only one type of hardener may be used in combination, or two or more types may be used in combination. Among these hardeners for epoxy resins, phenolic hardeners are particularly preferred. The compounding amount of the epoxy resin hardener (C) that can be used in combination is 1 mol relative to the oxazine ring of the oxazine resin (A), and the active hydrogen group of the epoxy resin hardener (C) is 0 mol~ The amount is 9 mol, preferably 0 mol to 7 mol, more preferably 1 mol to 5 mol, and still more preferably 2 mol to 4 mol. In addition, since 1 mol of oxazine ring generates 1 mol of OH group, 1 mol of oxazine ring is also referred to as 1 equivalent of oxazine ring.

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

In addition, the active hydrogen group in this specification refers to a functional group having active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen that generates active hydrogen due to hydrolysis or the like, or a functional group showing The functional group with equivalent curing action), specifically, an acid anhydride group, a carboxyl group, an amino group, or a phenolic hydroxyl group can be mentioned. In addition, regarding the active hydrogen group, 1 mol of the carboxyl group (-COOH) or phenolic hydroxyl group (-OH) is calculated as 1 equivalent (1 mol as the active hydrogen group), and the amine group (-NH ₂ ) 1 mol is calculated as 2 equivalents (2 mol based on active hydrogen base). In addition, 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 mono-epoxy resin such as phenyl glycidyl ether with a known epoxy equivalent can be reacted with a hardener with an unknown active hydrogen equivalent, and the amount of mono-epoxy resin consumed can be measured to determine the activity of the hardener Hydrogen equivalent.

In the oxazine resin composition, the usage amount of the oxazine resin (A) and the curing agent for epoxy resin (C) is 1 mol of the epoxy group of the epoxy resin (B), and the oxazine resin (A) The total number of moles of the active hydrogen groups of the oxazine ring and the hardener for epoxy resin (C) is 0.2 mol to 1.5 mol, preferably 0.3 mol to 1.5 mol, more preferably 0.5 mol to 1.5 mol Ears, more preferably 0.8 mol to 1.2 mol. When the total number of moles of the oxazine ring and the active hydrogen group is less than 0.2 mol or more than 1.5 mol relative to 1 mol of the epoxy group, the hardening may become incomplete and good hardening physical properties may not be obtained. For example, in the case of using oxazine resin (A) and epoxy resin (B) without using the hardener (C) for epoxy resin, it can be compared with 1 mol of epoxy group of epoxy resin (B). The oxazine ring of the oxazine resin (A) is formulated so that it becomes 0.8 mol to 1.5 mol, preferably 0.8 mol to 1.2 mol. In addition, when a phenol-based curing agent or an amine-based curing agent is formulated as the epoxy resin curing agent (C), the oxazine ring and the ring of the oxazine resin (A) can be used with respect to 1 mol of the epoxy group. The curing agent for oxygen resin (C) is blended so that the total number of moles of active hydrogen groups becomes 0.8 mol to 1.5 mol, preferably 0.8 mol to 1.2 mol. When an acid anhydride-based hardener is formulated as the hardener (C) for epoxy resins, the total amount is 0.4 mol to 1.5 mol, preferably 0.5 mol to 1.2 mol, and more preferably 0.6 mol to 1.0 mol. In addition, as a theoretical amount, 1 mole of oxazine ring or OH group corresponds to 1 equivalent of active hydrogen group (mole), and 1 mole of epoxy group corresponds to 1 equivalent.

Regarding the phenol resin curing agent, specific examples include: bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F , Tetramethyl bisphenol S, tetramethyl bisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6-tertiary butylphenol) and other bisphenols; or Catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-third Dihydroxybenzenes such as butyl hydroquinone and di-tert-butyl hydroquinone; or hydroxy naphthalenes such as dihydroxy naphthalene, dihydroxy methyl naphthalene, and trihydroxy naphthalene, but are not limited to these compounds.

In addition, phenol novolac resins such as Shonol BRG-555 (manufactured by Showa Denko Co., Ltd.), and cresol novolac resins such as DC-5 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) , Resitop (Resitop) TPM-100 (manufactured by Qunrong Chemical Industry Co., Ltd.) and other phenols and/or naphthols and aldehydes such as trihydroxyphenylmethane type novolac resins, naphthol novolac resins Condensates, SN-160, SN-395, SN-485 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and other phenols and/or naphthols and benzenedimethanol, phenols and/or naphthols Condensates with isopropenyl acetophenone, phenols and/or naphthols and dicyclopentadiene reactants, phenols and/or naphthols and biphenyl crosslinking agents and other phenolic compounds Etc., but not limited to these compounds. In this case, the phenols may include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc., and naphthols may include Produce 1-naphthol, 2-naphthol and so on. The aldehydes can be exemplified by formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, Pimelic aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, etc. Biphenyl-based crosslinking agents include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, etc. However, it is not limited to these compounds.

In addition to the above, the hardener (C) for epoxy resin can be an acid anhydride hardener, an amine hardener, or other hardeners. Specific examples of acid anhydride hardeners include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, Phthalic anhydride, trimellitic anhydride, methyl nadic anhydride, maleic anhydride, etc., but not limited to these compounds.

Specific examples of amine hardeners include diethylenetriamine, triethylenetetramine, m-xylene diamine, isophorone diamine, diamino diphenyl methane, diamino diphenyl sulfide, and diamino diamine. Diphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamine, as a polycondensate of dimer acid and other acids and polyamines Amine-based compounds such as polyamide amines are not limited to these compounds.

Specific examples of other hardeners include phosphine compounds such as triphenylphosphine, or phosphonium salts such as tetraphenylphosphonium bromide, or 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazoles such as oxyimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, or imidazole salts as salts of imidazoles with trimellitic acid, isocyanuric acid, boric acid, etc. , Or quaternary ammonium salts such as trimethylammonium chloride, or diazabicyclic compounds, or salts of diazabicyclic compounds and phenols or phenol novolac resins, or boron trifluoride and amines Or complex compounds such as ether compounds, or aromatic phosphonium, or iodonium salts, but are not limited to these compounds.

In the oxazine resin composition, a hardening accelerator (D) can be used as needed. Examples of the hardening accelerator (D) include phosphorus compounds such as imidazole derivatives, tertiary amines, and phosphines, metal compounds, lewis acids, and amine complex salts, but are not limited to these compounds. These hardening accelerators may be used alone or in combination of two or more kinds.

The amount of the hardening accelerator used is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.05 parts by mass to 5.0 parts by mass relative to 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. Regarding the curing conditions of the oxazine resin composition of the present invention, when a curing accelerator is not used, it is 200°C to 240°C for 2 hours to 5 hours, and when a curing accelerator is used, it is 170°C to 190°C, 0.5 hour to 5 hours.

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. Examples include: 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethyl Alkyl substituted imidazole compounds such as imidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, or 2-phenylimidazole, 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 and other imidazoles substituted by aryl or aralkyl and other hydrocarbon groups containing a ring structure Compounds etc. are not limited to these compounds. Among these imidazole derivatives, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole is preferable from the viewpoint of hardenability at low temperature.

Tertiary amines include, for example, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4 .0]-7-undecene (1,8-diaza-bicyclo[5.4.0]-7-undecene, DBU) etc., but not limited to these compounds. The phosphines include, for example, triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, but are not limited to these compounds. Examples of the metal compound include tin octoate, but are not limited to these compounds. Amine complex salts include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenyl Boron trifluoride complexes such as amine complexes, boron trifluoride benzylamine complexes, boron trifluoride aniline complexes, or mixtures of these complexes, etc., but are not limited to these compounds.

Among these hardening accelerators, when used as buildup materials or circuit board applications, in terms of excellent heat resistance, dielectric properties, solder resistance, etc., 2-dimethylamino group is preferred. Pyridine, 4-dimethylaminopyridine or imidazoles. In addition, when used as a semiconductor sealing material, triphenylphosphine or DBU is preferred from the viewpoint of excellent curability, heat resistance, electrical properties, and humidity resistance reliability. In addition, if boron trifluoride complexes are used, the ring opening of the oxazine resin is preferentially caused, and the generated phenol group reacts with the epoxy group to increase the crosslink density and obtain higher heat resistance, which is preferable.

In the oxazine resin composition, an organic solvent or a reactive diluent can be used to adjust the viscosity. The organic solvent is not specifically defined. For example, amines such as N,N-dimethylformamide and N,N-dimethylacetamide, or ethers such as ethylene glycol monomethyl ether, or Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, or methanol, ethanol, 1-methoxy-2-propanol, benzyl alcohol, butyl diethylene glycol, pine oil ( pine oil) and other alcohols, or butyl acetate, cellosolve acetate, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other acetates, or soluble Cellulose, carbitols such as butyl carbitol, aromatic hydrocarbons such as benzene, toluene, and xylene, or dimethyl sulfene, acetonitrile, N-methylpyrrolidone, etc., but are not limited to these compounds. In addition, reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, or resorcinol glycidyl ether, neopentyl ether Difunctional glycidyl ethers such as glycol glycidyl ether and 1,6-hexanediol diglycidyl ether, or multifunctional such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and pentaerythritol polyglycidyl ether Glycidyl ethers are not limited to these compounds.

These organic solvents or reactive diluents are preferably used singly or as a mixture of more than 90% by mass of the organic compound in the oxazine resin composition, and the appropriate type or amount of use is appropriately selected according to the application. For example, in printed wiring board applications, polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160° C. or less are preferred, and the amount used is preferably 40% by mass to non-volatile content. 80% by mass. In addition, for adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used. The use amount thereof is preferably such an amount that the concentration of the non-volatile content becomes 30% by mass to 60% by mass.

In the oxazine resin composition, other thermosetting resins and thermoplastic resins can be blended within a range that does not impair the characteristics. Examples include phenol resins, acrylic resins, petroleum resins, indene resins, coumarone-indene resins, phenoxy resins, polyurethane resins, polyester resins, and polyamide resins. , Polyimide resin, polyimide imide resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether turbid resin, poly turbid resin, polyether ether ketone resin, poly Phenyl sulfide resin, polyvinyl formal (polyvinyl formal) resin, etc., but 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. Usable flame retardants include, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like. From the viewpoint of the environment, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone or in combination of two or more kinds.

Phosphorus-based flame retardants can be divided into two types: additive-based phosphorus-based flame retardants (phosphorus-containing additives) and reactive phosphorus compounds. Reactive phosphorus compounds can be further divided into phosphorus-containing epoxy resins and phosphorus-containing hardeners. In the case of comparing an additive-based phosphorus-based flame retardant with a reactive phosphorus compound, the reactive phosphorus compound does not bleed out during curing and has good compatibility. The flame retardant effect is better. Large, it is preferable to use a reactive phosphorus compound.

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

In addition, red phosphorus is preferably surface-treated to prevent hydrolysis. Examples of surface treatment methods include: (1) The use of magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, and hydroxide A method of coating with inorganic compounds such as bismuth, bismuth nitrate, or a mixture of these; (2) Using a mixture of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and thermosetting resins such as phenol resin The method of coating treatment; (3) The method of double coating treatment with thermosetting resin such as phenol resin on the film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc., but not limited to These methods.

Regarding organophosphorus compounds, for example, phosphate compounds [such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, Butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecane Base acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, butyl pyrophosphate, glycolic acid Phosphate, (2-hydroxyethyl) methacrylate acid phosphate, etc.], condensed phosphate esters [such as PX-200 (manufactured by Dahachi Chemical Industry Co., Ltd.), etc.], phosphonic acid compounds, phosphines Acid compounds, phosphine oxide compounds [e.g. diphenyl phosphine oxide, triphenyl phosphine oxide, etc.], phosphine compounds [e.g. triphenyl (9H-fluorene-9-ylidene) phosphane, etc.] and other general-purpose organophosphorus compounds , Or nitrogen-containing organic phosphorus compounds [such as SPS-100, SPB-100, SPE-100 (the above are manufactured by Otsuka Chemical Co., Ltd.), etc.], or phosphinic acid metal salts [such as EXOLIT (EXOLIT) OP1230, EXOLIT OP1240, EXOLIT OP930, EXOLIT OP935 (the above are made by Clariant), etc.], in addition to Examples include: phosphorus compounds with active hydrogen groups directly bonded to phosphorus atoms [for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO), two Phenyl phosphine oxide, etc.] or phosphorus-containing phenol compounds [such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-HQ) ), 10-(2,7-dihydroxy-1-naphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl) )-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-NQ), diphenylphosphinyl hydroquinone, diphenylphosphino-1,4-di Oxynaphthalene, 1,4-cyclooctylphosphinyl-1,4-phenyldiol, 1,5-cyclooctylphosphinyl-1,4-phenyldiol, etc.] and other organic phosphorus It is not limited to these compounds, or phosphorus-containing epoxy resins or phosphorus-containing curing agents, which are derivatives obtained by reacting these organophosphorus-based compounds with compounds such as epoxy resins or phenol resins.

In addition, the reactive phosphorus compound used in the phosphorus-containing epoxy resin or the phosphorus-containing hardener is preferably the phosphorus compound or phosphorus-containing phenol having an active hydrogen group directly bonded to the phosphorus atom, in terms of ease of obtaining From a viewpoint, DOPO, DOPO-HQ, DOPO-NQ, etc. are more preferable.

Phosphorus-containing epoxy resins include, for example, the above-mentioned Albert (Epotohto) FX-305, Albert (Epotohto) FX-289B, Albert (Epotohto) FX-1225, and Albert (Epotohto) TX-1320A. , Epotohto TX-1328, etc., but not limited to these compounds.

The epoxy equivalent of the phosphorus-containing epoxy resin may be 200-800, preferably 300-780, and more preferably 400-760. In addition, the phosphorus content of the phosphorus-containing epoxy resin may be 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.

In addition to the above-mentioned phosphorus-containing phenols, the phosphorus-containing hardener can be produced by a manufacturing method as shown in Japanese Patent Publication No. 2008-501063 or Japanese Patent No. 4548547 to react, for example, DOPO, aldehydes, and phenol compounds. Thus, a phosphorus-containing phenol compound is obtained. In this case, the phosphorus-based compound is condensed and added to the aromatic ring of the phenol compound via aldehydes to be incorporated into the molecule. In addition, the production method shown in JP 2013-185002 A can be used to further react with aromatic carboxylic acids to obtain a phosphorus-containing active ester compound from a phosphorus-containing phenol compound. In addition, the phosphorus-containing benzoxazine compound can be obtained by the production method shown in Japanese Patent Publication No. WO2008/010429.

The phosphorus content of the phosphorus-containing hardener 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 compounding amount of the phosphorus compound is appropriately selected according to the kind of the phosphorus compound, the components of the epoxy resin composition, and the degree of flame retardancy required. When the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing hardener, compared to the oxazine resin (A), epoxy resin (B), flame retardant and other filler materials or The solid content (non-volatile content) in the oxazine resin composition prepared by all additives, etc., and the phosphorus content are preferably 0.2% by mass to 6% by mass, more preferably 0.4% by mass to 4% by mass, and still more preferably 0.5% by mass to 3.5% by mass, particularly preferably 0.6% by mass to 3% by mass. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if the phosphorus content is too high, it may adversely affect the heat resistance.

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 hardener is treated as a compound corresponding to both the phosphorus compound and the hardener (C). Therefore, in the case of using a phosphorus-containing hardening agent, it is sometimes unnecessary to use other hardening agents or phosphorus compounds. Similarly, in the case of using phosphorus-containing epoxy resin, sometimes it is not necessary to use other epoxy resins or phosphorus compounds.

The blending amount of the flame retardant is appropriately selected according to the kind of the phosphorus flame retardant, the components of the oxazine resin composition, and the degree of required flame retardancy. 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, and still more 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, it may adversely affect the heat resistance.

In addition, when a phosphorus-based flame retardant is used, for example, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, calcium carbonate, zinc molybdate, etc. can be used in combination as a flame retardant auxiliary.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like. Triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred. Examples of triazine compounds include melamine, acetguanamine, benzoguanamine, mellon [2,4,6-tris(cyanoamino)-1,3,5-triazine], honey White amine (melam) [4,4'-imino bis (1,3,5-triazine-2,6-diamine)], ethylene dimelamine (ethylene dimelamine), polyphosphate melamine, three Guanylamine (triguanamine), etc., in addition to these, for example, guanyl melamine sulfate, melem sulfate, melam sulfate and other triazine sulfate compounds, amino triazine Aminotriazine-modified phenol resin [such as LA-7052 (manufactured by DIC) Co., Ltd.), and further modified by tung oil, isomerized linseed oil, etc. Compounds etc. are not limited to these compounds. The cyanuric acid compound includes, for example, cyanuric acid, melamine cyanurate, etc., but is not limited to these compounds. The amount of the nitrogen-based flame retardant is appropriately selected according to the type of nitrogen-based flame retardant, the other components of the epoxy resin composition, and the degree of flame retardancy required. For example, it is preferable to use a curable epoxy resin composition. The solid content (non-volatile content) in 100 parts by mass is blended in the range of 0.05 part by mass to 10 parts by mass, and it is particularly preferably blended in the range of 0.1 part by mass to 5 parts by mass. In addition, when a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, etc. may be used in combination.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. Examples include silicone oil, silicone rubber, and silicone resin, but are not limited to these compounds. The blending amount of the silicone flame retardant is appropriately selected according to the type of silicone flame retardant, other components of the epoxy resin composition, and the degree of flame retardancy required. For example, it is preferable to use a curable epoxy resin. The solid content (non-volatile content) in the resin composition is blended in a range of 0.05 parts by mass to 20 parts by mass in 100 parts by mass. In addition, when a silicone-based flame retardant is used, a molybdenum compound, alumina, etc. can be used in combination.

Examples of inorganic flame retardants include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass, but they are not limited to these. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide, and zirconium hydroxide, but are not limited to these compounds. Metal oxides include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, oxide 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 to these compounds. Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc., but are not limited to these metals. Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax, but are not limited to these compounds. Examples of low-melting glass include hydrated glass, SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ series, ZnO-P ₂ O ₅ -MgO series, P ₂ O ₅ -B ₂ O ₃ -PbO- Glassy compounds such as MgO series, P-Sn-OF series, PbO-V ₂ O ₅ -TeO ₂ series, Al ₂ O ₃ -H ₂ O series, lead borosilicate series, etc. are not limited to these glasses. The blending amount of the inorganic flame retardant is appropriately selected according to the type of inorganic flame retardant, the other components of the epoxy resin composition, and the degree of flame retardancy required. For example, it is preferable to combine the epoxy resin (A ), curing agent (B), flame retardant, other fillers or additives, etc., in 100 parts by mass of the solid content (non-volatile content) in the epoxy resin composition, 0.05 to 20 parts by mass It is blended in the range of 0.5 to 15 parts by mass, and it is particularly preferable to blend it in the range of 0.5 parts by mass to 15 parts by mass.

Examples of organic metal salt flame retardants include ferrocene, acetone metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, metal atoms and aromatic compounds or heterocyclic compounds. Compounds formed by ionic bonds or coordinate bonds, etc., are not limited to these compounds. The blending amount of the organic metal salt flame retardant is appropriately selected according to the type of the organic metal salt flame retardant, the other components of the epoxy resin composition, and the degree of flame retardancy required. In 100 parts by mass of the solid content (non-volatile content) in the epoxy resin composition all blended with oxygen resin (A), hardener (B), flame retardant and other fillers or additives, 0.005 parts by mass It is blended in the range of -10 parts by mass.

Examples of halogen-based flame retardants include bromine compounds and chlorine compounds, and chlorine compounds are poor in terms of toxicity. Examples of bromine compounds include: p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetrabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, Hexabromocyclododecane, hexabromobenzene, 2,2'-ethylene bis(4,5,6,7-tetrabromoisoindoline-1,3-dione) [e.g. Setter ( SAYTEXBT-93 (manufactured by Albemarle), etc.], ethane-1,2-bis(pentabromophenyl) [e.g. SAYTEX 8010 (manufactured by Albemarle), etc.] , Or brominated epoxy oligomers [such as SR-T1000, SR-T2000 (the above are manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc.], but not limited to these compounds. The blending amount of the halogen-based flame retardant is appropriately selected according to the type of halogen-based flame retardant, other components of the epoxy resin composition, and the degree of flame retardancy required, for example, relative to epoxy resin (A), The solid content (non-volatile content) in the epoxy resin composition prepared by all blending of the curing agent (B), flame retardant, other fillers, additives, etc., preferably has a halogen content of 5 to 15% by mass. In addition, when halogen-based flame retardants are used as flame retardants, the following compounds can be used in combination as flame retardant additives: for example, antimony compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, tin oxide, and tin hydroxide Tin compounds, molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, boron compounds such as zinc borate and barium metaborate, silicone oil, silane coupling agent, high molecular weight silicone Such as silicon compounds, chlorinated polyethylene, etc.

In the oxazine resin composition, a filler may be used as necessary. Specific examples include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, Calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aromatic poly Amide fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer, pigment, etc. The reason why fillers are generally used is the 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 agent as described above, and has the effect of improving flame retardancy. Regarding the blending amount of these fillers, it is preferably 1 part by mass to 150 parts by mass relative to 100 parts by mass of the solid content excluding the filler in the oxazine resin composition (excluding the solvent, including resin, curing agent, and curing accelerator) Parts, more preferably 10 parts by mass to 70 parts by mass. If the blending amount is too large, the adhesiveness required for laminated board applications may decrease, and the hardened product may be brittle, and sufficient mechanical properties may not be obtained. In addition, if the blending amount is small, there may be no blending effect of fillers such as improvement of the impact resistance of the cured product.

In the oxazine resin composition, various additives such as a silane coupling agent, an antioxidant, a release agent, a defoamer, an emulsifier, a thixotropy imparting agent, a smoothing agent, a flame retardant, and a pigment, can be further adjusted as necessary. The compounding amount of these additives is preferably 0.01% by mass to 20% by mass relative to the oxazine resin composition.

When the oxazine resin composition is used as a plate-shaped substrate or the like, in terms of its dimensional stability, bending strength, etc., a fibrous filler can be cited as a preferable filler. More preferably, a glass fiber substrate obtained by knitting glass fibers into a mesh is used.

The oxazine resin composition can be impregnated into a fibrous base material to produce a prepreg used in a printed wiring board or the like. The fibrous substrate can be woven or non-woven fabrics of inorganic fibers such as glass or polyester resins, polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyamide resins. Limited to this. The method for producing a 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 heated and dried to make the resin component half. Hardening (B-staged) to obtain a prepreg, for example, can be heated and dried at 100°C to 200°C for 1 minute to 40 minutes. Here, the amount of resin in the prepreg is preferably 30% by mass to 80% by mass of the resin component.

In addition, when hardening the prepreg, the hardening method of the laminated board generally used when manufacturing a printed wiring board can be used, but it is not limited to this. For example, when a prepreg is used to form a laminate, one or more pieces of the prepreg are laminated, metal foils are arranged on one side or both sides to form a laminate, and the laminate is heated and pressurized to be integrated.化. Here, as the metal foil, individual, alloy, or composite metal foils such as copper, aluminum, brass, nickel, etc. can be used. Furthermore, the prepreg can be hardened by heating the produced laminate under pressure to obtain a laminate. At this time, 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. Obtain the target hardened object. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the heating temperature is high, the oxazine resin composition may start to decompose. In addition, if the pressing pressure is low, air bubbles may remain in the resulting laminated plate and the electrical characteristics may decrease. If the pressing pressure is high, the resin may flow before curing, and a cured product of the desired thickness may not be obtained. Furthermore, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if the heating and pressing time is long, the oxazine resin composition in the prepreg may be thermally decomposed, which is undesirable.

The oxazine resin composition can be cured by the same method as the well-known oxazine resin composition to obtain a cured epoxy resin. The method used to obtain the hardened product can be the same as the well-known oxazine resin composition, and can be suitably used: injection molding, injection, potting, dipping, drip coating, transfer molding, compression Molding or the like, or methods such as forming a resin sheet, copper foil with resin, prepreg, etc., by laminating and heating and pressing hardening to form a laminated plate. 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 oxazine resin of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film, and the like.

The oxazine resin composition of the present invention can be formed into a sheet shape or a film shape and used. In this case, a previously well-known method can be used to form a sheet or film. An example of a suitable forming method is the following method: the oxazine resin composition is dissolved in a solvent, and the resultant is obtained by a previously well-known method. The resin solution is coated on a metal foil, polyester film, polyimide film and other substrates with a peeling treatment on the surface, and then dried and peeled from the substrate to form an insulating sheet, insulating film, adhesive sheet or Adhesive film.

The method of manufacturing the adhesive sheet is not particularly limited. For example, the polyester film, polyimide film, and other carrier films that do not dissolve in the epoxy resin composition are coated with a thickness of 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 be molded into a sheet shape. The resin sheet is formed by a method generally called a casting method. At this time, if the sheet to be coated with the epoxy resin composition is surface-treated with a release agent in advance, the molded 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 way is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles with an epoxy resin composition.

Next, a method of manufacturing a laminated board using the prepreg or insulating adhesive sheet of the present invention will be described. When a prepreg is used to form a laminate, one or more prepregs are laminated, metal foils are arranged on one or both sides to form a laminate, and the laminate is heated and pressurized to integrate the laminate . Here, as the metal foil, individual, alloy, or composite metal foils such as copper, aluminum, brass, nickel, and the like can be used. Regarding the conditions for heating and pressing the laminate, as long as the epoxy resin composition is hardened, the conditions are adjusted appropriately and the heat and pressure are applied. If the pressure is too low, the inside of the resulting laminate may remain Air bubbles reduce electrical properties, so it is desirable to pressurize under conditions that satisfy moldability. For example, the temperature can be set to 160℃～220℃, the pressure can be set to 49.0 N/cm ² ～490.3 N/cm ² (5 kgf/cm ² ～50 kgf/cm ² ), and the heating time can be set to 40 minutes～ 240 minutes. Furthermore, the single-layer laminated board obtained in this way can be used as an inner layer material, and a multilayer board can be manufactured. In this case, first, circuit formation is performed on the laminated board by an additive method or a subtractive method, etc., and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed on one or both sides of the circuit formation surface of the inner layer material by using a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

In the case of forming an insulating layer using an insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is arranged between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, thereby forming a hardened product of the insulating adhesive sheet as an insulating layer, and forming a multilayered inner layer material. Or, the hardened product of the insulating adhesive sheet formed between the inner layer material and the metal foil as the conductor layer is used as the insulating layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated plate used as the inner layer material can be used. In addition, the heating and press molding can be performed under the same conditions as the molding of the inner layer material. When an epoxy resin composition is applied to a laminate to form an insulating layer, the resin on the circuit formation surface of the outermost layer of the inner layer material is coated with the epoxy resin composition in a thickness of preferably 5 μm to 100 μm, and then It is formed into a sheet by heating and drying at 100°C to 200°C for 1 minute to 90 minutes. It is formed by a method generally called a casting method. The thickness after drying is desirably 5 μm to 80 μm. Furthermore, it is possible to form a printed wiring board by performing via hole formation or circuit formation on the surface of the multilayer laminated board formed like this by an additive method or a subtractive method. In addition, it is possible to further use the printed wiring board as an inner layer material and repeat the construction method, thereby further forming a multilayer laminate board.

In addition, in the case of using a prepreg to form an insulating layer, one piece of prepreg or a laminate of multiple pieces of prepreg is placed on the circuit forming surface of the inner layer material, and a metal foil is placed on the outside to form a laminate . Then, the laminate is heated and pressurized to be integrally molded, thereby forming a hardened prepreg as an insulating layer, and forming a metal foil on the outer side as a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated plate used as the inner layer plate can also be used. In addition, the heating and press molding can be performed under the same conditions as the molding of the inner layer material. Furthermore, the surface of the multilayer laminated board formed in this way can be formed by via-hole formation or circuit formation by an additive method or a subtractive method, and a printed wiring board can be molded. In addition, it is possible to further use the printed wiring board as an inner layer material and repeat the construction method to form a multilayer multilayer board.

Sealing materials obtained by using the oxazine resin composition include tape-shaped sealing materials for semiconductor wafers, potting type liquid sealants, underfill resins, and semiconductor interlayer insulating films, and can be suitably used for these applications.

In order to prepare the oxazine resin composition as a semiconductor sealing material, the following method can be mentioned: after premixing the oxazine resin composition with other coupling agents, mold release agents and other additives or inorganic fillers, etc., as required, Use an extruder, kneader, roller, etc. to mix thoroughly until it becomes uniform. When used as a tape-shaped sealant, the following method may be mentioned: the resin composition obtained by the method described above is heated to produce a semi-cured sheet, and after the sealant tape is made, the sealant The tape is placed on a semiconductor wafer, heated to 100°C to 150°C to soften and shape, and completely hardened at 170°C to 250°C. Furthermore, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then coated on a semiconductor wafer or electronic part, and directly cured That's it.

An oxazine resin composition was prepared and cured by heating to evaluate the cured product. As a result, an oxazine resin with a specific molecular weight distribution was obtained from a novolac compound (e) having a specific molecular weight distribution, a monoamine-based compound, and aldehydes ( A) Compared with oxazine resins other than oxazine resin (A), the viscosity of the resin is lower, so it is easy to harden even under low temperature and short time conditions, and the hardened product has excellent heat resistance and dimensional stability. The modulus of elasticity is also relatively low, and the workability is good. Not only that, but it also has high heat resistance and good dimensional stability, and is especially useful for film laminates. [Example]

Examples and comparative examples are given to specifically describe the present invention, but the present invention is not limited to these examples as long as it does not exceed the gist. Unless otherwise specified, "parts" means parts by mass, and "%" means% by mass.

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

Epoxy equivalent: Measured in accordance with the Japanese Industrial Standard (JIS) K7236 standard.

Softening point: Measured in accordance with JISK7234 standard and 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 by the following formula from the value of the total amine value (Y). In addition, the method for measuring the total amine value is based on the JISK7237 standard, but chloroform is used instead of the o-nitrotoluene used in the mixed solvent. Z=56110/Y

n=0 body content rate, n=1 body content rate, n=2 body content rate, n=3 body content or more, 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 with serially connected columns (manufactured by Tosoh Co., Ltd., TSKgelG4000H _XL , TSKgelG3000H _XL , TSKgelG2000H _XL ). The column temperature was set to 40°C. In addition, Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 1 mL/min, and the differential refractive index detector was used as the detector. As the measurement sample, 50 μL of a sample obtained by dissolving 0.05 g of the sample in 10 mL of THF and filtering it with a microfilter was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Co., Ltd. was used. n=0 body content rate, n=1 body content rate, n=2 body content rate, n=3 body content rate and above are converted based on the area% of the peak, Mn, Mw, Mw/Mn are based on the single standard 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) to calculate the calibration curve. The same applies to the measurement of k=0 to 4 body, Mn, etc. of the phenol novolak resin.

Tg and ΔTg: According to IPC-TM-6502.4.25.c, measured with a differential scanning calorimetry device (made by Hitachi High-Tech Science Co., Ltd., DSC7000X), and the Tgm (relative to the glass state The glass transition temperature (Tg) is the temperature of the tangent to the variation curve of the rubber state). Regarding the measurement conditions, after raising the temperature to 275°C at a rate of 10°C/min and keeping it for 10 minutes, cooling to 20°C at 100°C/min and holding it for 20 minutes, and then raising the temperature to 275°C at 20°C/min. Let Tgm in the first temperature increase as Tg(1st) and Tgm in the second temperature increase as Tg(2nd), and ΔTg is calculated from Tg(2nd)-Tg(1st).

Modulus of elasticity: At 50°C when measured with a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., Extar 6000DMA6100) at a temperature increase of 5°C/min The value of E'of is regarded as the modulus of elasticity (50°C), and the value of E'at 220°C is regarded as the modulus of elasticity (220°C).

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

Flammability: Evaluate by vertical method according to UL94 standard.

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

Copper foil peeling strength and interlayer adhesion: Measured in accordance with JISC6481 standard, and interlayer adhesion is measured after peeling between the 7th and 8th layers.

Synthesis Example 1 (Synthesis of phenol novolac resin) In a glass separable flask equipped with a stirring device, a thermometer, a nitrogen introduction device, a condenser, and a dripping device, 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate were added to one side While injecting nitrogen gas, it is stirred and heated to increase the temperature. Then, while stirring at 80°C, 474.1 parts of 37.4% formalin was added dropwise over 30 minutes and reacted. Furthermore, the reaction temperature was maintained at 92°C and the reaction was carried out for 3 hours. The temperature was increased to 110°C while removing the water produced by the reaction out of the system. The remaining phenol was recovered at 160° C. under reduced pressure, and the temperature was further increased to 250° C. to recover a part of k=0 body to obtain a phenol novolak resin (e-1). Regarding 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 volume content: 11%, k=4 volume or more content: 10%, Mn: 529, Mw: 587. The GPC measurement spectrum is shown in FIG. 3. In the figure, _{the crest shown in (a 0} ) represents k=0 body, the _{group of crests shown in (b 0} ) represents k=1 body and k=2 body, and _{the crest shown in (c 0} ) represents k=3 Body, _{the peak group shown by (d 0} ) means k=4 body or more.

Synthesis Example 2 (Synthesis of Phenol Novolak) A phenol novolak resin (e-2) was obtained in the same manner as in Synthesis Example 1, except that the recovery temperature of 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= Three-body content: 10%, k=4 or more content: 9%, Mn: 510, Mw: 567.

The description of the abbreviations used in the examples and comparative examples is as follows.

[Novolac compound] (e-1): Phenolic novolak resin of Synthesis Example 1 (e-2): Phenolic novolak resin of Synthesis Example 2 BRG-555: Phenolic novolak 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 rate: 10 area%, k=4 body content or more: 33 area%, Mn: 353, Mw: 547)

[Epoxy resin] YDPN-638: Phenolic novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotohto YDPN-638, epoxy equivalent: 176) YD-128: Bisphenol A Type liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Albert (Epotohto) YD-128, epoxy equivalent: 186) FX-1225: Phosphorus epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. Manufactured by the company, Epotohto FX-1225, epoxy equivalent: 320, phosphorus content: 2.5%)

[Hardening agent] BRG-557: phenol novolac resin (manufactured by Showa Denko Co., Ltd., Shonol BRG-557, softening point: 80°C, hydroxyl equivalent: 105) GK-5855P: aromatic modified novolac resin Resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., GK-5855P, hydroxyl equivalent: 230) GDP9140: Dicyclopentadiene/phenol co-condensed resin (manufactured by Kunei Chemical Industry Co., Ltd., GDP9140, 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 (manufactured by Daha Chemical Industry Co., Ltd., PX-200, phosphorus content: 9%)

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

Example 1 In the same device as in Synthesis Example 1, 200 parts of the phenol novolak resin (e-1) obtained in Synthesis Example 1 as the novolac compound (e), 189 parts of aniline, and 256 parts of toluene were added. While injecting nitrogen gas, it is stirred and heated to increase the temperature. Then, while stirring at 50°C, 134 parts of 92% paraformaldehyde was added over 1 hour, and then 13 parts of water was added dropwise. Furthermore, the temperature was kept at 85°C and the reaction was carried out for 2 hours. The temperature was increased, and the temperature was increased to 120°C while removing the water produced by the reaction to the outside of the system. The remaining aniline and toluene were recovered under reduced pressure while maintaining 120° C. to obtain an oxazine resin (resin 1). The GPC measurement spectrum chart of the obtained resin 1 is shown in FIG. 1. In the figure, the crest shown in (a) represents n=0 body, the crest group shown in (b) represents n=1 body and n=2 body, and the crest group shown in (c) represents n=3 body the above. The FT-IR measurement spectrum is shown in FIG. 2.

Example 2 Except having used 200 parts of phenol novolak resin (e-2) as the novolak compound (e), it carried out similarly to Example 1, and obtained resin 2.

Example 3 Except having used 180 parts of aniline and 128 parts of 92% paraformaldehyde, it carried out similarly to Example 1, and obtained resin 3.

Reference example 1 Except having used 200 parts of BRG-555 as the novolac compound (e), it carried out similarly to Example 1, and obtained the comparative resin 1. The GPC measurement spectrum chart of the obtained comparative resin 1 is shown in FIG. 4. In the figure, the crest shown in (a) represents n=0 body, the crest group shown in (b) represents n=1 body and n=2 body, and the crest group shown in (c) represents n=3 body the above.

The n=0 body content, n=1 body content, n=2 body content of Resin 1 to Resin 3 and Comparative Resin 1 and Comparative Resin 2 to Comparative Resin 3 obtained from Example 1 to Example 3 and Reference Example 1 Table 1 shows the measurement results of the content rate, the content rate of n=3 or more, Mn, Mw, oxazine ring equivalent, and softening point.

[Table 1]

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

Examples 5 to 7 and Comparative Examples 1 to 4 were blended in the blending amounts (parts) of the formulations in Table 2, and the cured products were obtained in the same manner as in Example 4. The same test as in Example 4 was performed, and the results are shown in Table 2. In addition, (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 (molar ratio) of the sum of the oxazine ring (Z) to the epoxy group (E).

[Table 2]

According to Table 2, if the resin of the example is used, a cured product with a small ΔTg can be obtained. A small ΔTg means that there are few unreacted parts, and the cured product or laminate using the resin of the example can be said to have good dimensional stability. Although the Tg of the cured product of the conventional polyfunctional oxazine resin is increased, the uncured part remains and the dimensional stability is deteriorated, that is, the 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 the trade-off of the conventional technology can be eliminated.

Example 8 28 parts (solid content: 21 parts) of resin 1 MEK varnish (non-volatile content (NV.) 75%), 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 mixed with the formula in Table 3. A mixed solvent of MEK and propylene glycol monomethyl ether (mass ratio = 1/1) was dissolved to obtain a resin varnish of NV.50%.

The obtained resin varnish was impregnated into glass cloth WEA628XS13 (manufactured by Nitto Textile Co., Ltd., 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulation furnace at 150° C. for 9 minutes to obtain a prepreg. The obtained prepreg was stacked on 8 sheets, and copper foil (manufactured by Mitsui Metal Mining Co., Ltd., 3EC) was stacked on top and bottom, and heated at 130°C, 15 minutes and 190°C, 20 kg/cm ² , 80 minutes. Press to obtain a laminated board. The elastic modulus (50°C) and elastic modulus (220°C) of the laminated plate were measured. The results are shown in Table 3.

Examples 9 to 10 and Comparative Examples 5 to 7 were blended in the blending amounts (parts) of the formulations in Table 3, and the laminates were obtained in the same manner as in Example 8. The same test as in Example 8 was performed, and the results are shown in Table 3.

[table 3]

According to Table 3, if the resin of the example is used, the modulus of elasticity is small even at a temperature exceeding the glass transition temperature, and the elasticity is low. Recently, along with the thinning of the laminated board, there has been a problem of warpage of the laminated board. The resin used in order to improve the problem is expected to have a low elastic modulus, but the conventional technology cannot obtain an oxazine resin composition that satisfies the characteristics. However, compared with the conventional oxazine resin, the resin of the example has lower elasticity at a temperature exceeding the glass temperature, and therefore can further improve the warpage of the laminated board.

Examples 11 to 13 and Comparative Examples 8 to 9 were blended in the blending amounts (parts) of the formulations in Table 4, and the laminated plates were obtained in the same manner as in Example 8. The flame retardancy, relative permittivity, dielectric loss tangent, copper foil peel strength, and interlayer adhesion were tested, 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. Figure 2 is a Fourier Transform-Infrared Spectroscopy (FT-IR) spectrum of the oxazine resin of the present invention. Figure 3 is the GPC spectrum of the raw novolac compound. FIG. 4 is a GPC chart of the oxazine resin of Comparative Example 1. FIG.

Claims (12)

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 in the gel permeation chromatography measurement, the content of n=0 body is 15 area% or less, the total content of n=1 body and n=2 body is 35 area% to 70 area%, and n=3 body or more The content rate is less than 50 area%, and the number average molecular weight is 400～2500 based on standard polystyrene conversion value;

(In the formula, 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 with 6 to 10 carbons, an aryloxy group with 6 to 10 carbons, an aralkyl group with 7 to 12 carbons, or an aralkyloxy group with 7 to 12 carbons as an aromatic ring 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); R ₁ each independently represents an alkyl group having 1 to 6 carbon atoms , An aryl group having 6 to 12 carbons or an aralkyl group having 7 to 12 carbons; R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or 7 ～12 aralkyl group; m is 1 or 2; n is a number from 1 to 5 based on the average value);

(In the formula, R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms; 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 with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, an aryl group with 6 to 10 carbons, an aryloxy group with 6 to 10 carbons, and 7 -12 aralkyl group or C7-12 aralkyloxy group as the substituent of the aromatic ring). The oxazine resin composition as described in item 1 of the scope of the patent application, wherein: the epoxy resin hardener (C) is further formulated. The oxazine resin composition described in item 2 of the scope of patent application, wherein: the active hydrogen (H) of the epoxy resin hardener (C) and the oxazine ring (Z) of the oxazine resin (A) are combined The epoxy resin hardener (C) is blended so that the molar ratio (H/Z) becomes 0/10 to 9/1. The oxazine resin composition as described in item 2 or item 3 of the scope of the patent application, wherein: 1 mol relative to the epoxy group of the epoxy resin (B) and the oxazine ring of the oxazine resin (A) The epoxy resin hardener (C) is prepared so that the sum of the number of moles of active hydrogen of the epoxy resin hardener (C) becomes 0.2 mol to 1.5 mol. The oxazine resin composition described in item 2 or item 3 of the scope of patent application, wherein the hardener (C) for epoxy resin is a phenolic hardener. The oxazine resin composition according to one of items 1 to 3 in the scope of the patent application, wherein: relative to 100 parts by mass of the epoxy resin (B), 0.01 parts by mass to 10 parts by mass are further formulated to promote hardening Agent (D). A prepreg characterized by using the oxazine resin composition as described in one of items 1 to 6 of the scope of the patent application. A laminated board is characterized by using the oxazine resin composition according to one of items 1 to 6 in the scope of the patent application. A hardened product obtained by hardening the oxazine resin composition described in one of items 1 to 6 in the scope of the patent application. 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 composed of a novolac compound (e), The monoamine compound represented by the following formula (21) and the aldehydes represented by the following formula (22) are obtained. The novolak phenol compound (e) is represented by the following formula (2) and is In the gel permeation chromatography measurement, the content of k=0 body is 20 area% or less, the total content of k=1 body and k=2 body is 50 area% to 95 area%, and the content rate of k=3 body 15 area% or less, the content rate of the high molecular weight body with k=4 or more is 15 area% or less, and the number average molecular weight is 350-1500 in terms of standard polystyrene conversion value;

(In the formula, 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 with 6 to 10 carbons, an aryloxy group with 6 to 10 carbons, an aralkyl group with 7 to 12 carbons, or an aralkyloxy group with 7 to 12 carbons as an aromatic ring Substituents; 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 The number of 3);

(In the formula, R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms; 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 with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, an aryl group with 6 to 10 carbons, an aryloxy group with 6 to 10 carbons, and 7 ～12 aralkyl group or C7-12 aralkyloxy group as the substituent of the aromatic ring); R ₁ -NH ₂ (21) R ₂ -CHO (22) (R ₁ and R ₂ are each independent Ground represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 12 carbons). A method for producing an oxazine resin by reacting a novolac compound (e), a monoamine compound represented by the following formula (21), and an aldehyde represented by the following formula (22) to produce an oxazine resin, and The method for producing the oxazine resin is characterized in that the novolak urushiol compound (e) is represented by the following formula (2), and has the following molecular weight distribution in the gel permeation chromatography measurement: the content of k=0 body The rate is 20 area% or less, the total content of k=1 body and k=2 body is 50 area% to 95 area%, the content rate of k=3 body is 15 area% or less, k=4 body or more high molecular weight The content of the body is less than 15% by area, and the number average molecular weight is 350-1500 in terms of standard polystyrene conversion value;

(In the formula, 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 carbons, an aryloxy group having 6 to 10 carbons, an aralkyl group having 7 to 12 carbons, or an aralkyloxy group having 7 to 12 carbons is used as an aromatic Substituents of the 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 calculated as an average value Is a number from 0.8 to 3);

(In the formula, R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms; 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 with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, an aryl group with 6 to 10 carbons, an aryloxy group with 6 to 10 carbons, and 7 Any one of the aralkyl group having ～12 or the aralkyloxy group having 7-12 carbon atoms as the substituent of the 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 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 12 carbons). The method for producing oxazine resin as described in item 11 of the scope of patent application, wherein: the monoamine compound is aniline, and the aldehyde is formaldehyde.

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