JP7026591B2 - Oxazine resin composition and its cured product - Google Patents

Description

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

In recent years, copper-clad laminates for printed wiring boards, adhesives for multi-layer wiring boards, sealing materials for semiconductors, adhesives for semiconductor mounting, modules for mounting semiconductors, parts used for automobiles, aircraft, building materials, etc. In the curable material used for the above, there is a demand for a heat-resistant material having excellent stability and reliability under high temperature and high humidity. Furthermore, in the energy field, research and development of fuel cells, various secondary batteries, and the like have progressed, and heat-resistant materials have become necessary. In particular, in hybrids, electric vehicles, and distributed power sources, power devices are often used mainly for inverters, and their power densities are dramatically increased. Therefore, the emergence of silicon carbide (SiC) devices that operate at high temperatures of 200 ° C. or higher is also expected. Further, since an electronics control unit (ECU) using an ordinary semiconductor chip is also mounted from the vehicle interior to the engine room where the environment is harsh, heat resistance that can withstand harsh conditions is also required. In response to such a requirement, a heat-resistant resin obtained by reacting a benzoxazine ring structure-containing compound with an epoxy resin has been studied (Patent Documents 1 and 2, Non-Patent Document 1). However, the curing rate of the benzoxazine resin is very slow, and it is necessary to heat it at a high temperature of 250 ° C. or higher for a long time in order to obtain sufficient curing. It was necessary to improve the curability in order to use it in.

As a method for improving the curability and reactivity of the resin, a benzoxazine resin having a constant molecular weight distribution has been proposed (Patent Document 3). However, although the reactivity is improved, the heat resistance is insufficient. Further, a method of using a dihydrobenzoxazine compound and a novolak type phenol resin in combination has also been proposed (Patent Document 4). However, the crosslink density of the cured product is lowered, and therefore the glass transition point is lowered, which is insufficient as a curable material that requires heat resistance of 175 ° C. or higher. Further, a method is known in which a compound having 3 or more reactive hydroxyphenylene groups in one molecule is used as a synthetic raw material, and a phenolic hydroxyl group is left in the molecule at a certain ratio when dihydrobenzoxazine is formed. (Patent Document 5). It has also been reported that by using a polyfunctional oxazine resin having a specific molecular weight distribution, the heat resistance is improved, but the low resin viscosity makes it difficult for uncured portions to remain even under low-temperature short-time curing conditions. (Patent Document 6). However, these polyfunctional oxazine compounds have poor fluidity due to their large molecular weight, and in order to be used industrially, it is necessary to adjust the viscosity and the non-volatile content with other resins, and the resulting deterioration of the characteristics is also caused. There was also, and the use was limited. Further, if the ring-opening reaction proceeds even a little during the synthesis, the fluidity is remarkably lowered, and it is difficult to carry out the synthesis with a stable molecular weight, leaving room for improvement. It was very difficult to combine such contradictory curability, high heat resistance, and fluidity.

Japanese Patent Application Laid-Open No. 2003-147165 Japanese Unexamined Patent Publication No. 2008-94941 Japanese Unexamined Patent Publication No. 2001-146545 Japanese Unexamined Patent Publication No. 9-272786 Japanese Unexamined Patent Publication No. 7-188364 Japanese Unexamined Patent Publication No. 2017-141389

Molding, Vol. 19, No. 10, 634-640 (2007)

The present invention provides an oxazine resin composition and a cured product thereof that can satisfy the fluidity required for industrial molding even under the curing conditions of low temperature and short time, which are industrially advantageous. With the goal.

As a result of diligent research to achieve the above object, the present inventors have improved heat resistance by using a polyfunctional oxazine resin having a specific molecular weight distribution and a specific hydroxyl group amount. However, they have found that curing is easy to proceed even under low temperature and short time conditions, and that the viscosity of the resin is low, so that the fluidity is improved, and the present invention has been completed.

That is, the present invention is an oxazine resin composition containing an oxazine resin (A) and a phenol compound (B), wherein the oxazine resin (A) is represented by the following formula (1) and gel permeation chromatography (GPC). ) In the measurement, n = 0 bodies are 15 to 60 area%, the total of n = 1 body and n = 2 bodies is 25 to 40 area%, and the content of n = 3 or more bodies is 15 to 45 areas. %, The weight average molecular weight (Mw) is 700 to 1300 in terms of standard polystyrene, and the molar ratio (OH / Z) of the hydroxyl group (OH) to the oxazine ring (Z) in the formula (1) is 10/90. It is an oxazine resin composition characterized by being about 30/70.

In the formula (1), A ¹ independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms and a carbon number of carbon atoms. An aromatic ring contains an alkoxy group of 1 to 6, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. It may have as a substituent.
X independently represents a divalent aliphatic cyclic hydrocarbon group or a crosslinked group represented by the following formula (1a) or formula (1b). R ¹ independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ² independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. m1 and m2 are independently 0, 1 or 2, respectively, and the sum of m1 and m2 bound to the same A1 is ¹ or 2. n is an average value and is a number of 0.7 to 2.1.
Further, in the formula ( ¹ ) A1, two adjacent carbon atoms in the aromatic ring and a ring-constituting atom composed of —C—N—C—O— are integrated to form an oxazine ring. For example, when A ¹ is a benzene ring, R ¹ is a phenyl group, and R ² is hydrogen, the structure has an N-phenyl-benzoxazine ring structure. In the present specification, the biphenyl ring as the aromatic ring group means -Ph-Ph- (where Ph is a phenylene group), and the oxazine ring is -C-N-C-OC-C. -Means a ring-shaped 6-membered ring (hydrooxazine ring).

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, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 6 carbon atoms. Even if it has any one of an aryl group having 10 to 10, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent of the aromatic ring. good.

The compounding ratio (A / B) of the oxazine resin (A) and the phenol compound (B) is preferably 99.5 / 0.5 to 50/50 (mass ratio).

Further, the oxazine resin composition can contain an epoxy resin (C), and contains 0.01 to 900 parts by mass with respect to 100 parts by mass of the total amount of the oxazine resin (A) and the phenol compound (B). That's good.

Further, the oxazine resin composition may contain 0.1 to 500 parts by mass of the epoxy resin curing agent (D) with respect to 100 parts by mass of the epoxy resin (C). As the curing agent (D) for an epoxy resin, one or more selected from the group consisting of an acid anhydride curing agent, an amine-based curing agent, and dicyandiamide is preferable.

Further, the oxazine resin composition may contain 0.01 to 10 parts by mass of the curing accelerator (E) with respect to 100 parts by mass of the total amount of the oxazine resin (A) and the phenol compound (B).

Further, the present invention is an oxazine resin composition containing an oxazine resin (A) and a phenol compound (B), wherein the oxazine resin (A) is represented by the novolak phenol compound (e) and the following formula (21). The novolak phenol compound (e) obtained from a monoamino compound and aldehydes represented by the following formula (22) is represented by the following formula (2), and k = 0 is 30 to 90 area% in GPC measurement. The total of k = 1 and k = 2 is 10 to 65 area%, k = 3 or more is 1 to 20 area%, and the weight average molecular weight is 330 to 550 in terms of standard polystyrene. It is an oxazine resin composition characterized by being present.

R ¹ -NH ₂ (21)
R2 ^- CHO (22)

In the formula (21), R ¹ represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. In formula (22), R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.

In equation (2), X is synonymous with X in equation (1). A ³ independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkylyloxy group having 7 to 12 carbon atoms as a substituent on the aromatic ring. May be good. k is the number of repeating units and indicates an integer of 0 or more, and the average value thereof is 0.1 to 1.3.

Further, the present invention is a prepreg or a laminated board, characterized in that the above-mentioned oxazine resin composition is used. Further, the present invention is a cured product obtained by curing the above oxazine resin composition.

Further, the present invention is a method for producing an oxazine resin by reacting a novolak phenol compound (e) with a monoamino compound and aldehydes, and the novolak phenol compound (e) is represented by the above formula (2). It is a method for producing an oxazine resin, which is characterized by using a phenol compound.

Aniline is preferable as the monoamino compound, and formaldehyde is preferable as the aldehydes.

The oxazine resin composition of the present invention is excellent in curability and fluidity, and is excellent in heat resistance even if it is a cured product obtained by curing under the curing conditions of low temperature and short time.

It is a GPC chart of an oxazine resin. It is an FT-IR chart of an oxazine resin. It is a GPC chart of a raw material novolak phenol compound. It is a GPC chart of an oxazine resin for comparison.

The oxazine resin composition of the present invention contains an oxazine resin (A) and a phenol compound (B).
The oxazine resin (A) used in the present invention is represented by the above formula (1), and n = 0 body, the total of n = 1 body and n = 2 bodies (n = 1 + 2 bodies), and n = 3 in GPC measurement. The body area% is 15 to 60%, 25 to 40%, and 15 to 45%, respectively. Here, n = 1 body means a component in which n is 1 in the formula (1), n = 0 body means a component in which n is 0, and n = 1 + 2 bodies means a component in which n is 1 and a component in 2. Both components are referred to, and n = 3 or more is a component in which n is 3 or more. The GPC measurement conditions follow the conditions described in the examples. Since the area% correlates with the content rate, it is also referred to as the content rate.
The Mw of this oxazine resin is 700 to 1300 in terms of standard polystyrene, and the molar ratio (OH / Z) of the hydroxyl group (OH) to the oxazine ring (Z) in the formula (1) is 10/90 to 30 /. It is 70.

In the formula (1), A ¹ is an aromatic ring group selected from any of a group consisting of a benzene ring, a naphthalene ring, or a biphenyl ring which may have a substituent. The aromatic ring of these aromatic ring groups can have a substituent, and the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl having 6 to 10 carbon atoms. It is either a group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different. However, the two carbons that form part of the hydrooxazine ring do not have substituents, and one carbon adjacent to these two carbons may also have no substituents. In the equations (1) to (7), (11), (21), and (22), the common symbols have the same meaning unless otherwise specified.

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

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

X is a divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the above formula (1a) or the above formula (1b). The number of carbon atoms of the divalent aliphatic cyclic hydrocarbon group is preferably 5 to 15, more preferably 5 to 10. Here, the divalent aliphatic cyclic hydrocarbon group is an unsaturated cyclic fat such as dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorbona-2-ene, α-pinene, β-pinene, and limonene. Examples thereof include divalent aliphatic cyclic hydrocarbon groups derived from group hydrocarbon compounds. Among these aliphatic cyclic hydrocarbon groups, a divalent hydrocarbon group derived from dicyclopentadiene is particularly preferable from the viewpoint of heat resistance.
Further, in the formulas (1a) and (1b), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² has the same meaning as A ¹ in the above formula (1) except that the valence is divalent.

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

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

m1 and m2 are independently 0, 1 or 2, respectively, and the sum of m1 and m2 bound to the same A1 is ¹ or 2, which corresponds to the number of hydroxyl groups of the raw material novolak phenol compound. m1 indicates the number of oxazine rings, and m2 indicates the number of unreacted hydroxyl groups.

n is a repeating unit and indicates an integer of 0 or more, and its average value (number average) is 0.7 to 2.1, preferably 0.8 to 1.8, and more preferably 0.85. It is about 1.5, and more preferably 0.9 to 1.3. Within this range, curability, heat resistance, and fluidity can be combined, which is preferable. In addition, n in the above formula (1) can be obtained as follows.

According to the above GPC measurement, the styrene-equivalent number average molecular weights Mn (α0, α1, α2, α3) corresponding to each of n = 0, n = 1, n = 2, and n = 3 and n = Ratios (β0 / α0, β1 / α1, β2 / α2, β3 / α3) to the theoretical molecular weights (β0, β1, β2, β3) of 0, n = 1, n = 2, and n = 3 respectively. ), And the average value of these (β0 / α0 to β3 / α3) is obtained. The value obtained by multiplying the above Mn by this average value is defined as the average molecular weight Mn'. Next, the value of n is calculated by using the theoretical molecular weight of the above formula (1) as the average molecular weight Mn'.

For example, in the case of the oxazine resin of Example 1 described later, the structural formula is the formula (11) described later. Theoretically, the molar ratio (OH / Z) of the hydroxyl group (OH) to the oxazine ring (Z) is such that all L is the compound (11y) of the formula (13) and all L is the compound (11z) of the formula (12). The molar ratio of is the same. Since the molar ratio (OH / Z) is 21/79, the theoretical molecular weight of the compound (11y) is 200 + 106n, and the theoretical molecular weight of the compound (11z) is 434 + 223n, the theoretical molecular weight of the oxazine resin of Example 1 is 384. .86 + 198.43n = Mn'. Further, from the GPC measured value, Mn is 509, and the average value of (β0 / α0 to β3 / α3) is 1.21. Therefore, from 384.86 + 198.43n = 509 × 1.21, it can be calculated as n = 1.2.

The oxazine resin (A) used in the present invention must have a predetermined amount of hydroxyl groups, and the molar ratio (OH / Z) of the hydroxyl groups (OH) to the oxazine ring (Z) is 10/90 to It is 30/70, preferably 12/88 to 25/75, and even more preferably 15/85 to 20/80. The hydroxyl group is derived from the raw material phenol, and the molar ratio of the hydroxyl group to the oxazine ring is synonymous with the amount of residual hydroxyl group (mol%). For example, the molar ratio of hydroxyl group to oxazine ring (OH / Z) = 30/70 and the amount of residual hydroxyl group = 30 mol% have the same meaning.

Further, it is essential that the oxazine resin (A) has a specific molecular weight distribution, and the content of n = 0 and the content of n = 1 + 2 are in the range of specific quantities, respectively, and n = It is important that the content of 3 or more bodies is not more than a specific amount. If the content of n = 0 is more than 60% (area%), the heat resistance is lowered, and if it is less than 15%, the viscosity is increased and the fluidity may be deteriorated. The content of n = 0 is preferably 20 to 55%, more preferably 25 to 50%, and even more preferably 30 to 50%. Further, if the content of n = 3 or more is more than 45%, the fluidity is remarkably deteriorated and there is a possibility that industrial molding cannot be performed. The content of n = 3 or more is preferably 40% or less, more preferably 35% or less. Within the above range, when the content of n = 0 bodies is low, it is preferable that the content of n = 3 or more bodies is also low. When the content of n = 0 is high, the content of n = 3 or more may be high. Therefore, the difference between the content of n = 0 and the content of n = 3 or more is preferably 0 to 30%. When there is a specific amount of n = 1 or n = 2, the cured product has a high Tg, but the reactivity is also improved. Since this tendency occurs regardless of whether n = 1 or n = 2, it is preferable to control the content at n = 1 + 2, which is the total content of n = 1 and n = 2. .. The total content of n = 1 body and n = 2 body is preferably 25 to 35%.

The weight average molecular weight Mw is 700 to 1300, preferably 720 to 1200, more preferably 750 to 1100, and even more preferably 800 to 1000.

In addition to the oxazine resin (A) represented by the above formula (1), the novolak phenol compound (e) is a compound self-polymerized with a monoamino compound and aldehydes at the peak of n = 2 or more in the GPC measurement. However, since these compounds cannot be separated, each content was determined by the contained area%. Therefore, the area% is calculated by taking the total of the n = 0 or more components in the formula (1) and the small amount components such as the novolak phenol compound (e) and the compound self-polymerized with aldehydes as 100%.

The oxazine resin (A) is an oxazine represented by the following formula (11) derived from a phenol novolac 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 m1 + m2 = 1. It is preferably a resin.

HL- ( _CH2 -L) n- _CH2 -L-H (11)

In the formula (11), L independently represents a divalent group represented by the following formula (12) or the formula (13), and the abundance ratio of the groups represented by the formula (12) and the formula (13) ( The molar ratio) is 70:30 to 90:10. n is synonymous with n in equation (1).
Since there is only one OH of phenol in the phenol novolac resin, some phenols form an oxazine ring of the formula (12), and the other part remains unreacted as the phenol of the formula (13). In this case, the ^number of moles of the oxazine ring and A1 do not match.
When the phenol content of the phenol novolac resin is divalent phenol, one OH group in the divalent phenol may be involved in the formation of the oxazine ring, and the other OH group may remain unreacted. Yes, in this case the oxazine ring and the _number of moles of A1 may match.

The oxazine resin (A) is obtained from a novolak phenol compound (e) having a specific molecular weight distribution, a monoamino compound and aldehydes. R ¹ of the above formula (1) is a substituent derived from a monoamino compound, and R ² is a substituent derived from aldehydes.

The novolak phenol compound (e) is represented by the above formula (2). k is a repeating unit and indicates an integer of 0 or more, and its average value (number average) is 0.1 to 1.3, preferably 0.15 to 1.2, and more preferably 0.2. It is ~ 1.1, and more preferably 0.3 to 1.0. In GPC measurement, k = 0 body is 30 to 90% (area%), the total content of k = 1 body and k = 2 body is 10 to 65%, and the content rate of k = 3 or more bodies. Has a specific molecular weight distribution of 1 to 20% and Mw of 330 to 550 in terms of standard polystyrene. By having such a molecular weight distribution, the oxazine resin used in the present invention can be obtained in good yield.

The content (area%) of k = 0 is preferably 30 to 80%, more preferably 35 to 75%, still more preferably 40 to 70%. Further, the content of the high molecular weight body of k = 3 or more is preferably 2 to 15%, and it is more preferable that the high molecular weight body of k = 5 or more is not contained at all. The total content of k = 1 and k = 2 is preferably 10 to 60%, more preferably 12 to 50%, and even more preferably 15 to 45%. In particular, the content of k = 1 body is preferably 10 to 30%, and the content of k = 2 bodies is preferably 5 to 15%. Further, Mw is preferably 350 to 500, more preferably 375 to 475. The dispersity (Mw / Mn) is preferably 1.03 to 1.10. The GPC measurement conditions for the novolak phenol compound (e) are the same as the GPC measurement conditions for the oxazine resin (A).

Examples of the phenols used to obtain the novolak phenol compound (e) include phenol, cresol, ethylphenol, butylphenol, styrated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol and the like. Without limitation, these phenols may be used alone or in combination of two or more. Among these phenols, monophenols such as phenol and alkylphenol are preferable. As the alkyl group in the case of an alkylphenol, an alkyl group having 1 to 6 carbon atoms is suitable.

Examples of the cross-linking agent for obtaining the novolak phenol compound (e) include aldehydes such as formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, amylaldehyde and benzaldehyde represented by the following formula (4), and the following formula (5). Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone represented by them, p-xylylene glycol represented by the following formula (6), p-xylylene glycol dimethyl ether, p-xylylene chloride chloride, 4,4'. -Crossing agents such as dimethoxymethylbiphenyl, 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, dichloromethylnaphthalene, divinylbenzene represented by the following formula (7), divinylbiphenyl, divinylnaphthalene, etc. Examples thereof include cycloalkyldienes such as cyclopentadiene and dicyclopentadiene, but the present invention is not limited to these, and these cross-linking agents may be used alone or in combination of two or more. You may. X of the formula (1) and the formula (2) becomes a divalent aliphatic cyclic hydrocarbon group when cycloalkyldiene is used, and when the cross-linking agent of the formula (4) or the formula (5) is used, it becomes. It becomes a cross-linking group represented by the formula (1a), and when the cross-linking agent of the formula (6) or the formula (7) is used, it becomes a cross-linking group represented by the formula (1b). Among these cross-linking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-xylylenechloride, and 4,4'-dichloromethylbiphenyl are preferable, and formaldehyde is particularly preferable. Preferred forms when formaldehyde is used in the reaction include formalin aqueous solution, paraformaldehyde, trioxane and the like.

In equations (4) and (5), R ³ and R ⁴ are synonymous with R ³ and R ⁴ in equation (1a), respectively. In formulas (6) and (7), R ⁵ , R ⁶ and A ² are synonymous with R ⁵ , R ⁶ and A ² in formula (1b), respectively, where Y is independently a hydroxyl group, an alkoxy group or a halogen. Indicates an atom.

Acidic catalysts used to obtain the novolak phenol compound (e) include protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitrate and toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, zinc chloride and chloride. Examples thereof include Lewis acid such as iron, oxalic acid, and monochloroacetic acid, but the present invention is not limited thereto, and these acidic catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid and oxalic acid are preferable.

The above-mentioned novolak phenol compound (e) can be obtained by adjusting the molar ratio of phenols and aldehydes, removing a low molecular weight component from the obtained novolak phenol compound (e), or post-adding a low molecular weight component. Obtainable. It can also be obtained by using a production method as shown in JP-A-2002-19441 and JP-A-2007-126683.

The molar ratio of phenols to the cross-linking agent is indicated by the molar ratio of phenols to 1 mol of the cross-linking agent (phenols / cross-linking agent), and the molar ratio is 1 or more, but the molar ratio is large. In, a large number of k = 0 and k = 1 are produced, and conversely, when the molar ratio is small, a large number of high molecular weight bodies of k = 3 or more are produced, and a small number of k = 0 and k = 1. Further, in order for the oxazine resin to have a specific molecular weight distribution, it is necessary to make the novolak phenol compound (e) have a specific molecular weight distribution. In order to keep the above range, the molar ratio of phenols to the cross-linking agent (phenols / cross-linking agent) is preferably 3 or more and 6 or less, and more preferably 4 or more and 5 or less. The novolak phenol compound (e) having a specific molecular weight distribution is obtained by adding another phenol to the novolak phenol compound (e) obtained by adjusting the molar ratio of the phenols and the cross-linking agent in this way. be able to.
Examples of the other phenols include those having k = 0 of the novolak phenol compound (e) and its concentration increased, and the phenols and alkylphenols mentioned as the phenols used to obtain the novolak phenol compound (e). Can be used.

The monoamino compound used to obtain the oxazine resin is represented by the above formula (21), and the aldehydes are represented by the above formula (22).

In equation (21), R ¹ is synonymous with R ¹ in equation (1). Specifically, R ¹ is a methyl amine of a methyl group, an ethyl amine of an ethyl group, a propyl amine of a propyl group, a butyl amine of a butyl group, an aniline of a phenyl group, a methyl aniline of a tolyl group, a dimethyl aniline of a xsilyl group, and a benzyl group. Examples thereof include, but are not limited to, benzylamine. Among these monoamino compounds, aromatic monoamine compounds are preferable, and aniline and methylaniline are more preferable.

In equation (22), R ² is synonymous with R ² in equation (1). As the aldehydes, the same aldehydes used to obtain the novolak phenol compound (e) are used. Among these aldehydes, formaldehyde, acetaldehyde and benzaldehyde are preferable, and formaldehyde is particularly preferable. Preferred forms when formaldehyde is used include formalin aqueous solution, paraformaldehyde, trioxane and the like.

The amount of each raw material used is preferably 0.7 to 0.9 mol, more preferably 0.8 to 0.9 mol, with respect to 1 mol (equivalent) of the hydroxyl group of the novolak phenol compound (e). The aldehydes are preferably 1.5 to 1.9 mol, more preferably 1.7 to 1.9 mol. In particular, aldehydes may be added in a slightly excessive amount. The theoretical amount is 1 mol of monoamino compound and 2 mol of aldehydes with respect to 1 mol of dihydrobenzoxazine ring, but as a side reaction, polymerization of novolak phenol compound or reaction product of monoamino compound and aldehydes alone occurs. Further, since the separable unreacted substance is removed in the post-treatment step, monoamino compounds and aldehydes may remain. The total of these impurities is preferably 5% by mass or less.

It is calculated that 1 mol of the novolak phenol compound (e) has a hydroxyl group of m × (k + 2) mol, and 1 mol of the hydroxyl group is calculated as 1 equivalent.

There is no special manufacturing method as the manufacturing method, and a generally used manufacturing method can be used. Examples of a general production method include a method in which the novolak phenol compound (e) and the monoamino compound are heated and stirred under a solvent, aldehydes are added, and the mixture is kept at 70 to 120 ° C. for 20 minutes to 24 hours. After the reaction, the product is put into a poor solvent having low dissolving power for the product such as methanol, isolated and purified by a method of reprecipitation or a synthetic chemical method such as solvent extraction, and 120 volatile components such as condensed water are added. The oxazine resin (A) used in the present invention can be obtained by reducing the pressure and removing by drying at a temperature of ° C. or lower.

If the reaction temperature is less than 70 ° C., the reaction for forming the oxazine ring becomes very slow, and the reaction does not proceed substantially. When the reaction temperature exceeds 120 ° C., the generated oxazine ring is opened, a binding reaction occurs with the vicinity of another phenolic hydroxyl group, a side reaction for increasing the molecular weight is promoted, and an insoluble gel is easily produced. .. In the reaction at high temperature, this ring-opening cross-linking reaction of the oxazine ring tends to occur in parallel with the oxazine ring formation reaction. The reaction temperature is preferably 70 to 110 ° C, more preferably 80 to 100 ° C, in order to improve the oxazine ring formation reaction and reduce gel generation.

Regarding the reaction time, the formation of the oxazine ring is not sufficient in 20 minutes or less, and the ring-opening cross-linking reaction of the oxazine ring gradually formed in parallel in the solvent occurs in 24 hours or more. Therefore, in order to improve the oxazine ring formation reaction and reduce gel generation, the reaction time is preferably 1 to 10 hours, more preferably 1.5 to 6 hours.

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

By adding a poor solvent such as methanol into the reaction mixture thus obtained, the resin component is precipitated to obtain an oxazine resin. Alternatively, after the reaction is completed, an oxazine resin can be obtained by performing a water wash or an alkali wash operation as necessary to remove the solvent, water, monoamino compounds, and aldehydes.

Next, the phenol compound (B) blended in the oxazine resin composition of the present invention will be described. The phenol compound (B) is not particularly limited, and any compound having one or more phenolic hydroxyl groups can be applied, and a polyfunctional phenol compound having two or more phenolic hydroxyl groups is preferable. The phenol compound may be used alone or in combination of two or more. Among the curing agents for epoxy resins described later, the compound having a phenolic hydroxyl group is treated as corresponding to the phenol compound (B).

In the oxazine resin composition, the compounding ratio (A / B) of the oxazine resin (A) and the phenol compound (B) is preferably 99.5 / 0.5 to 50/50, preferably 99/1 to 60, on a mass basis. / 40 is more preferable, 97/3 to 70/30 is more preferable, and 95/5 to 80/20 is particularly preferable. The phenol compound (B) acts as a curing catalyst for the oxazine resin (A) and promotes curing at a low temperature. If the blending amount is large, the crosslink density of the cured product may decrease, and satisfactory heat resistance may not be obtained. Further, when the epoxy resin (C) is blended with the oxazine resin composition, the phenol compound (B) also acts as a curing agent for the epoxy resin (C).

Specific examples of the phenol compound (B) include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, and tetramethyl bisphenol Z. , Dihydroxydiphenylsulfide, bisphenols such as 4,4'-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert- Examples thereof include, but are not limited to, dihydroxybenzenes such as butylhydroquinone and di-tert-butylhydroquinone, and hydroxynaphthalene such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene and trihydroxynaphthalene.

In addition, phenol novolak resin (for example, Shonor (registered trademark) BRG-555 (manufactured by Aika Kogyo Co., Ltd.), etc.), cresol novolak resin (for example, DC-5 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), Bisphenol A novolak resin, trishydroxyphenylmethane type novolak resin (for example, Regitop (registered trademark) TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), etc.), naphthol novolak resin and other phenols, naphthols and / or bisphenols Condensates of and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthols and / or condensates of bisphenols and xylylene glycol, phenols , Naftols and / or condensates of bisphenols and isopropenyl acetophenone, phenols, naphthols and / or reactants of bisphenols with dicyclopentadiene, phenols, naphthols and / or biphenyl-based cross-linking with bisphenols. Examples thereof include, but are not limited to, phenol compounds so-called novolak phenol compounds such as condensates with agents.

In the case of novolak phenol compounds, examples of phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol and the like, and examples of naphthols include 1-naphthol and 2-naphthol. And the like, and the above-mentioned bisphenols are also mentioned. Aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyl aldehyde, barrel aldehyde, capron aldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glioxal, malon aldehyde, succin aldehyde, glutal aldehyde, adipin aldehyde, pimelin aldehyde, and sebacin aldehyde. , Acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like are exemplified. Examples of the biphenyl-based cross-linking agent include, but are not limited to, bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.

Further, the epoxy resin (C) may be used in the oxazine resin composition of the present invention, if necessary. The epoxy resin (C) that can be used is not particularly limited, and various known epoxy resins can be applied. Examples thereof include, but are not limited to, polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins, and these epoxy resins are used alone. It may be used together, or two or more kinds may be used together.

The amount of the epoxy resin (C) used is 0 to 900 parts by mass, preferably 0.01 to 900 parts by mass, based on 100 parts by mass of the total amount of the oxazine resin (A) and the phenol compound (B). 10 to 500 is more preferable, 100 to 400 is further preferable, and 120 to 400 is particularly preferable. If the amount of the epoxy resin (C) used is large, the crosslinks may become too dense and an uncured portion may remain.

Specific examples of the polyglycidyl ether compound include bisphenol A type epoxy resin (for example, Epototo (registered trademark) YD-127, YD-128, YD-8125, YD-825GS (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.)). Etc.), Bisphenol F type epoxy resin (for example, Epototo YDF-170, YDF-1500, YDF-8170, YDF-870GS (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc.), Tetramethylbisphenol F type epoxy resin (for example, YSLV-80XY, YSLV-70XY (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), biphenol type epoxy resin (for example, YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.), ZX-1251 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), etc. ), Hydroquinone type epoxy resin (for example, Epototo YDC-1312, ZX-1027 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), Bisphenol fluorene type epoxy resin (for example, ZX-1201 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), etc. ), Naphthalenediol type epoxy resin (for example, ZX-1355 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Epicron (registered trademark) HP-4032D (manufactured by DIC Co., Ltd.), etc.), Bisphenol S type epoxy resin (for example, TX-0710). (Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron EXA-1515 (manufactured by Dainippon Chemical Industry Co., Ltd.), etc.), Diphenyl sulfide type epoxy resin (for example, YSLV-50TE, YSLV-120TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)) Etc.), Diphenyl ether type epoxy resin (for example, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), Resolsinol type epoxy resin (for example, Epototo ZX-1684 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)), Denacol EX-201 (Nagase) Chemtex Co., Ltd.), etc.), Phenol novolak type epoxy resin (for example, Epototo YDPN-638 (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), jER152, jER154 (above, Mitsubishi Chemical Co., Ltd.), Epicron N-740, N- 770, N-775 (manufactured by DIC Co., Ltd.), etc.), Cresol Novolak type epoxy resin (for example, Epototo YDCN-700 series (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Epicron N-660, N-665, N-670 , N-673, N-695 (all manufactured by DIC Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-10 4S (above, manufactured by Nippon Kayaku Co., Ltd.), alkyl novolac type epoxy resin (for example, Epototo ZX-1071T, ZX-1270, ZX-1342 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc.), styrenated phenol Novolak type epoxy resin (for example, Epototo ZX-1247, GK-5855, TX-1210, YDAN-1000 (all manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.), bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin (for example, Epototo ZX-1142L (manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.), β-naphthol aralkyl type epoxy resin (for example, ESN-155, ESN-185V, ESN-175 (manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.), Naphthalene Diol aralkyl type epoxy resin (for example, ESN-300 series ESN-355, ESN-375 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), α-naphthol aralkyl type epoxy resin (for example, ESN-400 series ESN- 475V, ESN-485 (above, manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.), Biphenyl aralkylphenol type epoxy resin (eg, NC-3000, NC-3000H (above, manufactured by Nippon Kayaku Co., Ltd.), etc.), Trihydroxyphenyl Methane-type epoxy resin (for example, EPPN-501, EPPN-502 (manufactured by Nippon Kayaku Co., Ltd.), etc.), Tetrahydroxyphenylethane-type epoxy resin (for example, YDG-414 (manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.) , Dicyclopentadiene type epoxy resin (for example, Epicron HP7200, HP-7200H (above, manufactured by DIC Co., Ltd.), etc.), alkylene glycol type epoxy resin (Epototo PG-207, PG-207GS (above, manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.) ), SR-16H, SR-16HL, SR-PG, SR-4PG, SRSBA, SR-EGM, SR-8EGS (all manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), etc.), aliphatic cyclic epoxy resin (for example, Santoto (for example) Registered trademarks) ST-3000, Epototo ZX-1658, ZX-1658GS, FX-318 (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), HBPA-DGE (manufactured by Maruzen Petrochemical Co., Ltd.), etc. It is not limited to.

Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resins (for example, Epototo YH-434, YH-434GS (all manufactured by Nippon Steel & Sumitomo Metal Corporation), ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), and Araldite (for example). Registered trademarks) MY720, MY721, MY9512, MY9663 (above, manufactured by Huntsman Advanced Chemicals), etc.), Metaxylenediamine type epoxy resin (eg, TETRAD-X (manufactured by Mitsubishi Gas Chemicals, Inc.), etc.), 1,3 -Bisaminomethylcyclohexane type epoxy resin (for example, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.), isocyanurate type epoxy resin (for example, TEPIC-P (manufactured by Nissan Chemical Industry Co., Ltd.), etc.), aniline type epoxy Resins (eg, GAN, GOT (above, manufactured by Nippon Kayaku Co., Ltd.), etc.], hidden-in type epoxy resins (eg, Y238 (manufactured by Huntsman Advanced Materials), etc.), aminophenol type epoxy resins (eg, ELM120). , ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), jER630 (manufactured by Mitsubishi Chemical Co., Ltd.), Araldite MY0510, MY0600, MY0610 (manufactured by Huntsman Advanced Materials Co., Ltd.), etc., but are limited thereto. It's not a thing.

Specific examples of the polyglycidyl ester compound include dimer acid type epoxy resin (for example, Epototo YD-171 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), jER871 (manufactured by Mitsubishi Chemical Co., Ltd.), etc.) and hexahydrophthalic acid type epoxy. Examples thereof include, but are not limited to, resins (for example, SR-HHPA (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)).

Specific examples of the alicyclic epoxy compound include aliphatic cyclic epoxy resins (for example, seroxide (registered trademark) 2021, 2021A, 2021P, 3000 (all manufactured by Daicel Chemical Industries, Ltd.), DCPD-EP, MCPD-. EP, TCPD-EP (above, manufactured by Maruzen Petrochemical Co., Ltd.), etc.), etc., but are not limited thereto.

Specific examples of the other modified epoxy resin include urethane modified epoxy resin (for example, AER4152 (manufactured by Asahi Kasei Co., Ltd.)), oxazolidone ring-containing epoxy resin, and epoxy modified polybutadiene rubber derivative (for example, PB-3600 (Dycel Chemical Industry Co., Ltd.)). (Manufactured by Nippon Steel & Sumitomo Metal Corporation), etc.), CTBN-modified epoxy resin (eg, YR-102, YR-450 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc.), phosphorus-containing epoxy resin (eg, Epototo FX-305, FX-289B, etc.) Examples include, but are not limited to, FX-1225, TX-1320A, TX-1328 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

When the epoxy resin (C) is used in the oxazine resin composition of the present invention, an epoxy resin curing agent (D) may be used in combination, if necessary. Examples of the epoxy resin curing agent (D) that can be used in combination include commonly used curing agents such as acid anhydride-based curing agents, amine-based curing agents, and other curing agents. These epoxy resin curing agents are 1 You may use only one type or two or more types together.

As described above, since the phenol compound (B) acts as a curing agent for the epoxy resin, the amount of the curing agent (D) for the epoxy resin may be an amount that compensates for the shortage, and the oxazine resin (A) and the phenol compound. It is 0 to 900 parts by mass with respect to 100 parts by mass of the total amount of (B). If the amount used is large, the curing speed may be too high and the molding may be completed before the molding is completed.

Specific examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, and trimellitic anhydride. , Phthalic anhydride, phthalic anhydride and the like, but are not limited thereto.

Specific examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, metaxylenedamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulphon, diaminodiphenylether, benzyldimethylamine, and 2,4,6-tris (dimethylaminomethyl). ) Examples thereof include, but are not limited to, amine compounds such as polyamideamine which is a condensate of acids such as phenol, dicyandiamide and dimer acid and polyamines.

Specific examples of other curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, and Bronsted acid salts such as aliphatic sulfonium salts, aromatic sulfonium salts, and iodonium salts. , Organic acid hydrazides such as adipic acid dihydrazide and phthalic acid dihydrazide, polycarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, trimellitic acid and carboxyl group-containing polyester, 2-methylimidazole, 2-phenylimidazole. , 2-Ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole and other imidazoles, and imidazole salts which are salts of imidazole and trimellitic acid, isocyanuric acid, boric acid and the like. , Tertiary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, salts of diazabicyclo compounds with phenols, phenol novolac resins, etc., complex compounds of boron trifluoride with amines, ether compounds, etc. However, it is not limited to these.

Further, a curing accelerator (E) can be used in the oxazine resin composition, if necessary. Examples of the curing accelerator (E) include, but are not limited to, imidazole derivatives, tertiary amines, phosphorus compounds such as phosphins, metal compounds, Lewis acids, amine complex salts and the like. .. These curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator (E) used is 0 to 10 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total amount of the oxazine resin (A) and the phenol compound (B). , 0.05 to 5.0 parts by mass is more preferable. By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened. The curing conditions of the oxazine resin composition of the present invention are 200 to 240 ° C. for 2 to 5 hours when the curing accelerator is not used, and 170 to 200 ° C. and 0.5 to 5 hours when the curing accelerator is used. Is.

The imidazole derivative may be any compound having an imidazole skeleton and is not particularly limited. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4- Alkyl-substituted imidazole compounds such as dimethylimidazole and 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1- Aryl groups such as benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, etc. Examples thereof include, but are not limited to, imidazole compounds substituted with a hydrocarbon group containing a ring structure such as an aralkyl group. Among these imidazole derivatives, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole is preferable because of its curability at low temperature.

Examples of tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene ( DBU) and the like, but are not limited to these.

Examples of phosphines include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenylborane.

Examples of the metal compound include, but are not limited to, tin octylate.

As the amine complex, the boron trifluoride monoethylamine complex, the boron trifluoride diethylamine complex, the boron trifluoride isopropylamine complex, the boron trifluoride chlorophenylamine complex, the boron trifluoride benzylamine complex, and the boron trifluoride aniline complex. , Or boron trifluoride complexes such as a mixture thereof, but the present invention is not limited thereto.

Among these curing accelerators, 2-dimethylaminopyridine, 4-dimethylaminopyridine and the like are excellent in heat resistance, dielectric properties, solder resistance, etc. when used for build-up materials and circuit boards. Imidazoles are preferred. Further, when used as a semiconductor encapsulating material, triphenylphosphine and DBU are preferable because they are excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability and the like. Further, it is preferable to use boron trifluoride complexes because ring opening of the oxazine resin occurs preferentially, the generated phenol group reacts with the epoxy group to increase the crosslink density, and higher heat resistance can be obtained.

For the oxazine resin composition, an organic solvent or a reactive diluent can be used for adjusting the viscosity.

The organic solvent is not particularly specified, but for example, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, ethers such as ethylene glycol monomethyl ether, acetone, methyl ethyl ketone and methyl isobutyl. Ketones such as ketones and cyclohexanones, alcohols such as methanol, ethanol, 1-methoxy-2-propanol, benzyl alcohol, butyl diglycol and pine oil, butyl acetate, cellosolve acetate, ethyl diglycol acetate and propylene glycol monomethyl. Acetate esters such as ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as benzene, toluene and xylene, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone and the like. However, it is not limited to these.

Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, resorcinol glycidyl ether, neopentyl glycol glycidyl ether, and 1,6-hexanediol diglycidyl ether. Examples thereof include, but are not limited to, bifunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and polyfunctional glycidyl ethers such as pentaerythritol polyglycidyl ether.

It is preferable to use these organic solvents or reactive diluents alone or in admixture of a plurality of types at a concentration of 90% by mass or less of the organic compound in the oxazine resin composition, and the appropriate type and amount thereof are used. Is appropriately selected depending on the application. For example, for printed wiring board applications, a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferable, and the amount used is preferably 40 to 80% by mass in terms of non-volatile content. For adhesive film applications, for example, ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the amount used is the non-volatile content concentration. Is preferably an amount of 30 to 60% by mass.

The oxazine resin composition may contain other thermosetting resins and thermoplastic resins as long as the characteristics are not impaired. For example, phenol resin, acrylic resin, petroleum resin, inden resin, kumaron inden resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether. Examples thereof include, but are not limited to, a resin, a polyether sulfone resin, a polysulfone resin, a polyether ether ketone resin, a polyphenylene sulfide resin, and a polyvinyl formal resin.

Various known flame retardants can be used in the oxazine resin composition for the purpose of improving the flame retardancy of the obtained cured product. Examples of the flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like. From the viewpoint of the environment, halogen-free flame retardants are preferable, and phosphorus-based flame retardants are particularly preferable. These flame retardants may be used alone or in combination of two or more.

Phosphorus-based flame retardants are divided into two types: additive-based phosphorus-based flame retardants (phosphorus-containing additives) and reactive phosphorus compounds, and reactive phosphorus compounds are further divided into phosphorus-containing epoxy resins and phosphorus-containing curing agents. Divided. When comparing the additive-based phosphorus-based flame retardant and the reactive phosphorus compound, the reactive phosphorus compound has a large flame-retardant effect and is reactive in terms of not bleeding out during curing and having good compatibility. It is preferable to use the phosphorus compound of.

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

Further, the red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide and hydroxylation. Method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) Inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and phenol. Method of coating with a mixture of thermosetting resin such as resin, (3) Thermocurable resin such as phenol resin on the film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Examples thereof include, but are not limited to, a method of double-coating treatment.

Examples of the organophosphorus compound include phosphoric acid ester compounds (for example, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-). Ethylhexyl) Phosphates, Monoisodecyl Acid Phosphates, Lauryl Acid Phosphates, Tridecyl Acid Phosphates, Oleyl Acid Phosphates, Tetracosyl Acid Phosphates, Stearyl Acid Phosphates, Isostearyl Acid Phosphates, Butyl Pyrophosphates, Ethylene Glycol Acid Phosphates, (2- (Hydroxyethyl) methacrylate acid phosphate, etc.), condensed phosphate esters (eg, PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), etc.), phosphonic acid compounds, phosphinic acid compounds, phosphin oxide compounds (eg, diphenylphosphine oxide, etc.) General-purpose organophosphorus compounds such as triphenylphosphine oxides, phosphorane compounds (eg, triphenyl (9H-fluoren-9-iriden) phosphorane, etc.) and nitrogen-containing organophosphorus compounds (eg, SPS-100, SPB-). 100, SPE-100 (above, manufactured by Otsuka Chemical Co., Ltd.), phosphinic acid metal salts (eg, EXOLIT® OP1230, OP1240, OP930, OP935 (above, manufactured by Clariant), etc.), as well as phosphorus Phosphorus compounds having an active hydrogen group directly linked to an atom (for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO), diphenylphosphine oxide, etc.) and phosphorus-containing phenols. Compounds (eg, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated 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 abbreviated as DOPO-NQ), diphenylphosphinylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4 -Organic phosphorus compounds such as phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, etc., and derivatives obtained by reacting these organic phosphorus compounds with compounds such as epoxy resin and phenol resin. Examples thereof include, but are not limited to, a phosphorus-containing epoxy resin and a phosphorus-containing curing agent.

Further, as the reactive phosphorus compound used for the phosphorus-containing epoxy resin and the phosphorus-containing curing agent, the phosphorus compound having an active hydrogen group directly linked to the phosphorus atom and the phosphorus-containing phenols are preferable, and they are easily available. DOPO, DOPO-HQ, DOPO-NQ and the like are more preferable.

Examples of the phosphorus-containing epoxy resin include, but are not limited to, the above-mentioned Epototo FX-305, FX-289B, FX-1225, TX-1320A, TX-1328 and the like.

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

As the phosphorus-containing curing agent, in addition to the above-mentioned phosphorus-containing phenols, for example, DOPO, aldehydes and phenol compounds are reacted by a production method as shown in Japanese Patent Publication No. 2008-501063 and Japanese Patent No. 4548547. By doing so, a phosphorus-containing phenol compound can be obtained. In this case, the phosphorus compound is condensed and added to the aromatic ring of the phenol compound via aldehydes and incorporated into the molecule. Further, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by further reacting with aromatic carboxylic acids by a production method as shown in JP2013-185002A. In addition, a phosphorus-containing benzoxazine compound can be obtained by a production method as shown in WO2008 / 010429, which was published in Japan.

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

The blending amount of the phosphorus compound is appropriately selected depending on the type of the phosphorus compound, the components of the oxazine resin composition, and the desired degree of flame retardancy. When the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, an oxazine resin (A), a phenol compound (B), a flame retardant, and an epoxy resin (C) blended as needed. , Phosphorus content relative to the solid content (nonvolatile content) in the oxazine resin composition containing all of the curing agent (D) for epoxy resin, curing accelerator (E), other fillers and additives, etc. , 0.2 to 6% by mass, more preferably 0.4 to 4% by mass, still more preferably 0.5 to 3.5% by mass, and even more preferably 0.6 to 3% by mass. If the phosphorus content is low, it may be difficult to secure flame retardancy, and if it is too high, the heat resistance may be adversely affected.

Here, the phosphorus-containing epoxy resin is treated as corresponding to both the phosphorus compound and the epoxy resin (C). Similarly, the phosphorus-containing curing agent is treated as corresponding to both the phosphorus compound and the phenol compound (B) in the case of the phosphorus-containing phenol compound, and is otherwise treated as both the phosphorus compound and the epoxy resin curing agent (D). Treat as applicable. Therefore, when a phosphorus-containing curing agent is used, it may not be necessary to use other phenol compounds, epoxy resin curing agents, or phosphorus compounds. Similarly, when a phosphorus-containing epoxy resin is used, it may not be necessary to use another epoxy resin or phosphorus compound.

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

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

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine and the like, and triazine compounds, cyanuric acid compounds and isocyanuric acid compounds are preferable. Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon [2,4,6-tris (cyanoamino) -1,3,5-triazine], and melam [4,4'-iminobis (1,3,5). -Triazine-2,6-diamine)], ethylenedimelamine, melamine polyphosphate, triguanamine, etc., for example, aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, aminotriazine-modified phenolic resin (for example). , LA-7052 (manufactured by DIC Co., Ltd.), etc.), and aminotriazine-modified phenolic resins modified with tung oil, isomerized flaxseed oil, etc., but are not limited thereto. Examples of the cyanuric acid compound include, but are not limited to, cyanuric acid and melamine cyanuric acid. The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the oxazine resin composition, and the desired degree of flame retardancy. For example, in the oxazine resin composition. It is preferable to mix in the range of 0.05 to 10 parts by mass, and particularly preferably in the range of 0.1 to 5 parts by mass in 100 parts by mass of the solid content (nonvolatile content). When using a nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like 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, and examples thereof include, but are not limited to, silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, other components of the oxazine resin composition, and the desired degree of flame retardancy. For example, in the oxazine resin composition. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the solid content (nonvolatile content). Further, when using a silicone flame retardant, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glasses. Examples of the metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like. .. Examples of the metal oxide include zinc molybdenum oxide, molybdenum trioxide, zinc tintate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, and bismuth oxide. Examples thereof include, but are not limited to, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like. Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate and the like, but are not limited thereto. do not have. Examples of the metal powder include, but are not limited to, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin and the like. Examples of the boron compound include, but are not limited to, zinc borate, zinc metaborate, barium metaborate, boric acid, and borax. Examples of the low melting point glass include hydrated glass, SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O ₅ -MgO system, P ₂ O ₅ -B ₂ O ₃ -PbO. Examples thereof include glassy compounds such as -MgO-based, PSn-OF-based, PbO-V _{2O 5} -TeO ₂ -based, Al2O _{- 3} - _H2O -based, and lead borosilicate-based, but are limited thereto. It's not something. The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the oxazine resin composition, and the desired degree of flame retardancy. For example, the solid in the oxazine composition. It is preferable to mix in the range of 0.05 to 20 parts by mass, and particularly preferably in the range of 0.5 to 15 parts by mass in 100 parts by mass of the component (nonvolatile content).

Examples of the organometallic salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound, or a heterocyclic compound. Examples thereof include, but are not limited to, position-bonded compounds. The blending amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, other components of the oxazine resin composition, and the desired degree of flame retardancy, and is, for example, an oxazine resin. It is preferable to blend in the range of 0.005 to 10 parts by mass in 100 parts by mass of the solid content (nonvolatile content) in the composition.

Examples of the halogen-based flame retardant include bromine compounds and chlorine compounds, but chlorine compounds are not preferable due to toxicity problems. Examples of the bromine compound include p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, 2, 2'-ethylenebis (4,5,6,7-tetrabromoisoindolin-1,3-dione (eg, SAYTEX® BT-93 (manufactured by Albemar), etc.), ethane-1,2 -Bis (pentabromophenyl) (for example, SAYTEX 8010 (manufactured by Albemar), etc.), brominated epoxy oligomer (for example, SR-T1000, SR-T2000 (above, manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc.), etc. However, the amount of the halogen-based flame retardant is appropriately selected depending on the type of the halogen-based flame retardant, other components of the oxadin resin composition, and the desired degree of flame retardancy. However, for example, the halogen content is preferably 5 to 15% by mass with respect to the solid content (nonvolatile content) in the oxadin resin composition. Examples of the agent include antimony compounds such as antimony trioxide, antimone tetroxide, and antimone pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum compounds such as molybdenum oxide and ammonium molybdenate, zirconium oxide, and water. A zirconium compound such as zirconium oxide, a boron compound such as zinc borate and barium metaborate, a silicone oil, a silane coupling agent, a silicon compound such as high molecular weight silicone, and chlorinated polyethylene may be used in combination.

If necessary, a filler can be used in the oxazine resin composition. Specifically, 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, Examples thereof include boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer, pigment and the like. Generally, the reason for using a filler is the effect of improving impact resistance. Further, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant aid as described above and has an effect of improving flame retardancy. The blending amount of these fillers is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the solid content (excluding the solvent, including the resin, the curing agent and the curing accelerator) excluding the filler in the oxazine resin composition. Up to 70 parts by mass is more preferable. If the blending amount is large, the adhesiveness required for laminated board applications may decrease, and the cured product may be brittle, making it impossible to obtain sufficient mechanical properties. Further, if the blending amount is small, there is a possibility that the blending effect of the filler may not be obtained, such as improvement of the impact resistance of the cured product.

The oxazine resin composition may further contain various additives such as a silane coupling agent, an antioxidant, a mold release agent, a defoaming agent, an emulsifier, a rocking denaturing agent, a smoothing agent, and a pigment, if necessary. can. The blending amount of these additives is preferably 0.01 to 20% by mass with respect to the oxazine resin composition.

When the oxazine resin composition is a plate-shaped substrate or the like, a fibrous filler is preferable in terms of dimensional stability, bending strength and the like. More preferably, a glass fiber substrate in which glass fibers are knitted in a mesh shape can be mentioned.

By impregnating the fibrous base material with the oxazine resin composition, a prepreg used in a printed wiring board or the like can be prepared. As the fibrous base material, inorganic fibers such as glass, woven fabrics or non-woven fabrics of organic fibers such as polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin such as polyester resin can be used, but are limited thereto. It's not something. The method for producing the prepreg from the oxazine resin composition is not particularly limited. For example, the oxazine resin composition is dipped in a resin varnish prepared by adjusting the viscosity with a solvent, impregnated, and then heat-dried to form a resin. It is obtained by semi-curing (B-stage) the components, and can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes, for example. Here, the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin content.

Further, in order to cure the prepreg, a method for curing a laminated board generally used when manufacturing a printed wiring board can be used, but the method is not limited thereto. For example, when forming a laminated board using a prepreg, one or a plurality of prepregs are laminated, metal foils are arranged on one side or both sides to form a laminate, and the laminate is heated and pressed to be integrated. To become. Here, as the metal foil, a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used. Then, the prepared laminate is pressurized and heated to cure the prepreg, and a laminate can be obtained. At that time, it is preferable that the heating temperature is 160 to 220 ° C., the pressurizing pressure is 50 to 500 N / cm ² , and the heating and pressurizing time is 40 to 240 minutes, and the desired cured product can be obtained. If the heating temperature is low, the curing reaction does not proceed sufficiently, and if it is high, decomposition of the oxazine resin composition may start. In addition, if the pressurizing pressure is low, air bubbles may remain inside the obtained laminated board and the electrical characteristics may deteriorate, and if it is high, the resin will flow before curing, and a cured product of the desired thickness can be obtained. There is a risk that it will not be possible. Further, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if it is long, the oxazine resin composition in the prepreg may be thermally decomposed, which is not preferable.

The oxazine resin composition can be cured in the same manner as the known oxazine resin composition to obtain a cured product. For example, casting, injection, potting, dipping, drip coating, transfer molding, compression molding, etc., resin sheets, copper foil with resin, prepreg, etc. are laminated and cured by heating and pressure to form a laminated board. Method is preferably used. The curing temperature at that time is usually in the range of 100 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 or the like.

The oxazine resin composition of the present invention can be used by molding it into a sheet or a film. In this case, it is possible to form a sheet or a film by using a conventionally known method, but as an example of a suitable molding method, the above oxadin resin composition is dissolved in a solvent, and the obtained resin solution is used. A base material such as a metal foil, polyester film, or polyimide film whose surface has been peeled off is coated by a conventionally known method, dried, and peeled off from the base material to form an insulating sheet, an insulating film, an adhesive sheet, or an adhesive. There is a way to make it into a film.

The method for producing the adhesive sheet is not particularly limited, but for example, the oxazine resin composition of the present invention is preferably 5 to 5 on a carrier film that does not dissolve in the oxazine resin composition such as a polyester film and a polyimide film. After applying to a thickness of 100 μm, it is heated and dried at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A resin sheet is formed by a method generally called a casting method. At this time, if the sheet to which the oxazine resin composition is applied is surface-treated with a mold release agent in advance, the molded adhesive sheet can be easily peeled off. Here, it is desirable that the thickness of the adhesive sheet is 5 to 80 μm. The adhesive sheet thus obtained is usually an insulating adhesive sheet having insulation, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles with an oxadin resin composition. be able to.

Next, a method of manufacturing a laminated board using the prepreg and the insulating adhesive sheet of the present invention will be described. When forming a laminated board using a prepreg, one or a plurality of prepregs are laminated, metal foils are arranged on one side or both sides to form a laminate, and the laminate is heated and pressed to integrate the laminate. do. Here, as the metal foil, a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used. As a condition for heating and pressurizing the laminate, it is sufficient to appropriately adjust and heat and pressurize under the condition that the oxazine resin composition is cured. However, if the pressure of the pressurization is too low, bubbles are generated inside the obtained laminate. Since it may remain and the electrical characteristics may deteriorate, it is desirable to pressurize under conditions that satisfy the moldability. For example, the temperature can be set to 160 to 220 ° C., the pressure can be set to 49.0 to 490.3 N / cm ² (5 to 50 kgf / cm ² ), and the heating time can be set to 40 to 240 minutes. Further, the multilayer board can be produced by using the single-layer laminated board thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminated board by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution and blackened to obtain an inner layer material. An insulating layer is formed on one side or both side of the circuit forming surface of the inner layer material with a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.

When the insulating layer is formed by the insulating adhesive sheet, the insulating adhesive sheet is arranged on the reference number circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is placed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the insulating adhesive sheet is formed as an insulating layer, and a multi-layered inner layer material is formed. Alternatively, the inner layer material and the metal foil which is the conductor layer are formed as the insulating layer by forming the cured product of the insulating adhesive sheet. Here, as the metal foil, the same metal leaf as that used for the laminated board used as the inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. When the oxazine resin composition is applied to the laminated board to form an insulating layer, the circuit forming surface resin of the outermost layer of the inner layer material is applied to the above-mentioned oxazine resin composition to a thickness of preferably 5 to 100 μm, and then 100. Heat and dry at ~ 200 ° C. for 1 to 90 minutes to form a sheet. It is formed by a method generally called the casting method. It is desirable to form the thickness after drying to 5 to 80 μm. A printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, it is possible to further form a multi-layer laminated board.

When the insulating layer is formed by the prepreg, one or a plurality of prepregs are arranged on the circuit forming surface of the inner layer material, and a metal foil is further arranged on the outside to form the laminate. do. Then, by heating and pressurizing this laminate and integrally molding it, a cured product of the prepreg is formed as an insulating layer, and a metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal leaf as that used for the laminated board used as the inner layer board can also be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Further, by repeating the above-mentioned construction method using this printed wiring board as an inner layer material, it is possible to further form a multi-layer board.

Examples of the encapsulant obtained by using the oxazine resin composition include a tape-shaped encapsulant for a semiconductor chip, a potting type liquid encapsulant, an underfill resin, and an interlayer insulating film for a semiconductor, which are preferably used. be able to.

In order to prepare the oxazine resin composition for the semiconductor encapsulation material, other coupling agents, mold release agents and other additives and inorganic fillers to be added to the oxazine resin composition as necessary are reserved. After mixing, a method of sufficiently mixing until uniform using an extruder, a kneader, a roll or the like can be mentioned. When used as a tape-shaped sealant, the resin composition obtained by the above-mentioned method is heated to prepare a semi-curing sheet, which is used as a sealant tape, and then the sealant tape is placed on a semiconductor chip. Can be mentioned as a method of placing in a plastic, heating to 100 to 150 ° C., softening and molding, and completely curing at 170 to 250 ° C. Further, when used as a potting type liquid encapsulant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, then applied onto a semiconductor chip or an electronic component and cured directly. Just do it.

As a result of preparing an oxazine resin composition and evaluating the cured product by heat curing, a novolak phenol compound (e) having a specific molecular weight distribution, a monoamino compound, and a specific molecular weight distribution obtained from aldehydes were specified. The oxazine resin (A) having an amount of hydroxyl groups is more likely to be cured even under low temperature and short time conditions than the oxazine resins other than the oxazine resin (A), and the cured product is not only excellent in heat resistance. It also has industrially effective fluidity, and is particularly useful for thin-film laminated plates.

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto as long as the gist thereof is not exceeded. Unless otherwise specified, "parts" represents parts by mass and "%" represents% by mass.

The analysis method and measurement method are shown below. The unit of equivalent is "g / eq.".

Viscosity: Measured according to JIS Z8803 standard. Specifically, the viscosity at 120 ° C. was measured using an ICI viscosity measuring device (MODEL CV-1D manufactured by Toa Kogyo Co., Ltd.).

Amount of residual hydroxyl group: The amount of residual hydroxyl group (Y) of the oxazine resin was calculated from the theoretical oxazine ring equivalent (Z _t ) and the measured oxazine ring equivalent (Z) by the following formula. As the oxazine ring equivalent ( _Z ), the value of the tertiary amine value (AV) was used. The method for measuring the tertiary amine value was in accordance with JIS K7237 standard, but chloroform was used instead of orthonitrotoluene used as a mixed solvent.
Y = (1 / Z) / (1 / Z _t ) × 100
Z = ₅₆₁₁₀ / AV

Gel time: The time from when a 0.1 g sample is placed in the sample recess of a gelling tester (GT-D manufactured by Eucalyptus Giken Co., Ltd.) heated to 210 ° C. until the melt does not draw threads (gel time). ) Was measured. The stirring was performed while drawing a circle using a stirring rod made of Teflon (registered trademark).

n = 0 body, n = 1 body, n = 2 body, n = 3 or more body, number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (Mw / Mn): determined by GPC measurement. Specifically, a column (manufactured by Tosoh Co., Ltd., HLC-8220GPC) equipped with a column (manufactured by Tosoh Co., Ltd., TSKgel (registered trademark) G4000H _XL , TSKgelG3000H _XL , TSKgelG2000H _XL ) in series is used, and the column temperature is used. Was set to 40 ° C. In addition, THF was used as the eluent at a flow rate of 1 mL / min, and a differential refractive index detector was used as the detector. As the measurement sample, 0.05 g of the sample was dissolved in 10 mL of THF, and 50 μL of the sample filtered through a microfilter was used. For data processing, GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation was used. From n = 0 body, n = 1 body, n = 2 body, n = 3 or more body to the peak area%, Mn, Mw, Mw / Mn are standard monodisperse polystyrene (manufactured by Tosoh Corporation, A-500, From the calibration curve obtained from A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, F-80, F-128) Converted. The same applies to the measurement of k = 0 to 3 or more bodies, Mn, Mw, etc. of the novolak phenol resin.

Tg: IPC-TM-650 2.4.25. In accordance with c, measure with a differential scanning calorimetry device (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.), and set the temperature of Tgm (intermediate temperature of the variation curve with respect to the tangent line between the glass state and the rubber state) to the glass transition temperature (glass transition temperature). Tg). The measurement conditions were a temperature rise to 275 ° C. at a rate of 10 ° C./min, holding for 10 minutes, cooling to 20 ° C. at 100 ° C./min, holding for 20 minutes, and then raising the temperature to 275 ° C. at 20 ° C./min.

IR: Absorbance with a wave number of 650 to 4000 cm ^-1 was measured by a total internal reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (manufactured by PerkinElmer Precision, Spectrum One FT-IR Spectrometer 1760X).

Impregnation property: The following judgment was made based on the time required when the composition varnish was impregnated into a glass cloth having a size of 320 mm × 155 mm.
○: Less than 5 minutes ×: 5 minutes or more

Resin content: The resin content ( _RC ) was calculated from the weight of the prepreg per unit area (P) and the weight of the glass cloth per unit area (G) by the following formula.
_RC = (PG) / P × 100

Resin flow: IPC-TM-650 2.3.17. Measured according to.

Laminated plate pass / fail judgment: Visual evaluation and plate thickness measurement were evaluated, and the following judgments were made.
◯: No abnormality × 1: Since the resin viscosity is low, the resin flow during laminating plate molding increases, and the thickness can be made thinner than the specified thickness. It is difficult to reduce the resin flowability, and the productivity is deteriorated.
× 2: When the compounded varnish is impregnated into the glass cloth, the resin gets on only the surface of the glass cloth due to the high viscosity of the resin, and the resin does not enter the inside of the glass cloth. As a result, the amount of powder dropped from the prepreg increases, the appearance becomes poor, and the product is rejected.
× 3: The gelation time of the compounded varnish is short, and the resin cures without flowing. In the laminated board obtained by molding it, there are some places where there is no resin, and a uniform laminated board cannot be obtained.

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

Relative permittivity and dielectric loss tangent: Obtain the relative permittivity and dielectric loss tangent at a frequency of 1 GHz using a material analyzer (manufactured by Agilent Technologies) in accordance with the IPC-TM-650 2.5.5.9 standard. Evaluated by.

Copper foil peeling strength and interlayer adhesive strength: Measured according to JIS C6481 standard, and interlayer adhesive strength was measured by peeling between the 7th layer and the 8th layer.

Synthesis Example 1 In a glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introduction device, a cooling tube and a dropping device, 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate are charged and nitrogen gas is charged. Stirring was performed while injecting, and heating was performed to raise the temperature. Next, 474 parts of 37.4% formalin was added dropwise over 30 minutes while stirring at 80 ° C. for reaction. Further, the reaction temperature was kept at 92 ° C. and the reaction was carried out for 3 hours. The temperature was raised to 110 ° C. while removing the reaction-generated water from the system. The residual phenol was recovered at 160 ° C. under reduced pressure, and then a separately synthesized k = 0 body (BPF) was added in a small amount to obtain a phenol novolac resin (e-1). The obtained phenol novolac resin (e-1) has a hydroxyl group equivalent of 105, k = 0 body: 67 area%, k = 1 body: 22 area%, k = 2 body: 7 area%, k = 3 or more body. : 4 area%, Mn: 384, Mw: 415. The GPC measurement chart is shown in FIG. In the figure, the peak indicated by (a0) indicates k = 0, the peak group indicated by (b0) indicates k = 1 and k = 2, and the peak group indicated by (c0) indicates k = 3 or more. Is shown.

Synthesis example 2
A phenol novolac resin (e-2) was obtained in the same manner as in Synthesis Example 1 except for the amount of k = 0 added. The obtained phenol novolac resin (e-2) has a hydroxyl group equivalent of 105, k = 0 body: 41 area%, k = 1 body: 38 area%, k = 2 body: 14 area%, k = 3 or more body. : 7 area%, Mn: 441, Mw: 467.

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

[Raw material phenol compound]
(E-1): Phenol novolak resin of Synthesis Example 1 (e-2): Phenol novolak resin of Synthesis Example 2 BPF: Bisphenol F (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., SP-2000, hydroxyl group equivalent: 102, k = 0) Body: 97 area%, k = 1 body: 3 area%, Mn: 319, Mw: 323)
PN1: Phenol novolak resin (manufactured by Nippon Steel & Sumitomo Metal Corporation, SP-2060, hydroxyl group equivalent: 105, k = 0 body: 10 area%, k = 1 body: 45 area%, k = 2 body: 23 area%, k = 3 or more body: 22 area%, Mn: 528, Mw: 586)

[Phenol compound (B)]
PN2: Phenol novolac resin (manufactured by Aica Kogyo Co., Ltd., Shonor BRG-557, softening point: 80 ° C., hydroxyl group equivalent: 105)
DCPD: Dicyclopentadiene type novolak resin (manufactured by Gun Ei Chemical Industry Co., Ltd., GDP-6140, softening point: 130 ° C., hydroxyl group equivalent: 196)

[Epoxy resin (C)]
YDCN-700-7: Orthocresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo YDCN-700-7, epoxy equivalent: 202)
TX-1328A: Phosphorus-containing epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., TX-1328A, epoxy equivalent: 234, phosphorus content: 3%)

[Curing accelerator (D)]
TBZ: 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (manufactured by Shikoku Chemicals Corporation, Curesol® TBZ)

[others]
FR: Cyclophosphazene oligomer (manufactured by Otsuka Chemical Co., Ltd., SPB-100, phosphorus content: 13%)

Example 1
In the same apparatus as in Synthesis Example 1, 210 parts of the phenol novolac resin (e-1) obtained in Synthesis Example 1 as a raw material phenol compound, 151 parts of aniline and 205 parts of toluene were charged, and the mixture was stirred while injecting nitrogen gas. The temperature was raised by heating. Next, 107 parts of 92% paraformaldehyde was charged over 1 hour while stirring at 50 ° C., and then 10 parts of water was added dropwise. Further, the temperature was maintained at 85 ° C. and the reaction was carried out for 2 hours. The temperature was raised to 120 ° C. while removing the reaction-generated water from the system. The residual aniline and toluene were recovered under reduced pressure while being maintained at 120 ° C. to obtain an oxazine resin (resin 1). The GPC measurement chart of the obtained resin 1 is shown in FIG. In the figure, the peak shown in (a) shows n = 0 bodies, the peak group shown in (b) shows n = 1 body and n = 2 bodies, and the peak group shown in (c) shows n = 3 or more bodies. Is shown. The FT-IR measurement chart is shown in FIG.

Example 2
Resin 2 was obtained in the same manner as in Example 1 except that 210 parts of the phenol novolac resin (e-2) was used instead of the phenol novolac resin (e-1).

Example 3
Resin 3 was obtained in the same manner as in Example 1 except that 162 parts of aniline and 114 parts of 92% paraformaldehyde were used.

Reference example 1
Resin H1 was obtained in the same manner as in Example 1 except that 204 parts of BPF was used instead of the novolak phenol compound (e-1), 193 parts of aniline and 137 parts of 92% paraformaldehyde were used.

Reference example 2
Resin H2 was obtained in the same manner as in Example 1 except that 204 parts of BPF was used instead of the novolak phenol compound (e-1).

Reference example 3
Resin H3 was obtained in the same manner as in Example 1 except that 210 parts of PN1 was used instead of the novolak phenol compound (e-1). The GPC measurement chart of the obtained resin H3 is shown in FIG. In the figure, the peak shown in (a) shows n = 0 bodies, the peak group shown in (b) shows n = 1 body and n = 2 bodies, and the peak group shown in (c) shows n = 3 or more bodies. Is shown.

N = 0 body, n = 1 body, n = 2 body, n = 3 or more body, Mn of the resins 1 to 3 obtained in Examples 1 to 3 and the resins H1 to H3 obtained in Reference Examples 1 to 3. , Mw, and hydroxyl group equivalents are shown in Table 1.

Example 4
95 parts of resin 1 and 5 parts of PN2 were mixed on a hot plate at 120 ° C. and cooled sufficiently, and then the gel time of the pulverized compound resin at 210 ° C. and the viscosity at 120 ° C. were measured. The compounded solid pulverized product was cured at 130 ° C. for 15 minutes and at 200 ° C. for 2 hours with a vacuum press, and the Tg of the cured product was measured. The results are shown in Table 2.

Examples 5 to 6 and Comparative Examples 1 to 3
Except for the fact that the resins 1 and 2 obtained in Examples 2 to 3 and the resins H1 to H3 obtained in Reference Examples 1 to 3 were used as the resins, the resins were blended in the blending amounts shown in Table 2 in the same manner as in Example 4. To obtain a cured product. The same test as in Example 4 was performed, and the results are shown in Table 2.

From Table 1, when the resin of the example was used, a cured product having a short gel time, an industrially moldable viscosity, and a high Tg was obtained. It can be said that the short gel time means that the curing start temperature is low and the curing is easy to proceed. The conventional cured product using an oxazine resin has a drawback that the Tg is lowered or the fluidity is impaired even if the curability can be improved by leaving a hydroxyl group. However, the cured product of the example can be molded without damaging Tg while having the same gel time (curability) as the conventional oxazine resin, and the trade-off of the conventional technology can be eliminated.

Example 8
86.7 parts (solid content: 65 parts) of MEK varnish (nonvolatile content (NV.) 75%) of resin 1 and 33.3 parts (solid content: 25) of MEK varnish (NV. 75%) of YDCN-700-7. Parts), 15.4 parts (solid content: 10 parts) of MEK varnish (NV. 65%) of PN2 were mixed, and MEK varnish (0.05 g / mL) of TBZ was added to the resin composition at 171 ° C. for 5 minutes. The amount to be gelled (listed in Table 2) was blended and adjusted with a mixed solvent of MEK and propylene glycol monomethyl ether (mass ratio = 1/1) to obtain NV. A 50% composition varnish was obtained.

The obtained composition varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki 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. Eight obtained prepregs are stacked, copper foil (3EC manufactured by Mitsui Mining & Smelting Co., Ltd.) is stacked on top and bottom, heated and pressurized at 130 ° C for 15 minutes and 200 ° C x 20 kg / cm for ² x 120 minutes, and laminated. I got a board. Each test of the impregnation property, the resin content, and the resin flow of the laminated board was performed, and the pass / fail of the laminated board was judged.

Examples 9 to 10 and Comparative Examples 4 to 6
Except for using the resins 2 to 3 obtained in Examples 2 to 3 and the resins H1 to H3 obtained in Reference Examples 1 to 3 as the resins, the resins were blended in the blending amounts of the formulations shown in Table 3 and the same as in Example 8. A laminated board was obtained in the same manner. The same test as in Example 8 was performed, and the results are shown in Table 3. The non-volatile content of MEK varnish of each resin is 75%.

From Table 3, when the resin of the example is used, the amount of catalyst is small, and the resin content and flowability of the prepreg are appropriate and there is no problem. As shown in the comparative example, in the conventional technique, an oxazine resin composition which satisfies the curability but the molding characteristics has not been obtained. However, the resin of the example can produce a laminated board more efficiently than the conventional oxazine resin.

Example 11
80 parts of MEK varnish (NV 75%) of resin 1 (solid content: 60 parts), 100 parts of MEK varnish (NV 75%) of TX-1328A (solid content: 75 parts), 20 parts of MEK varnish (NV 60%) of DCPD Solid content: 12 parts) and 15 parts of FR were mixed and dissolved, and adjusted with a mixed solvent of MEK and propylene glycol monomethyl ether (mass ratio = 1/1) to obtain a composition varnish having an NV of 50%.

The obtained composition varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki 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. Eight obtained prepregs are stacked, copper foil (3EC manufactured by Mitsui Mining & Smelting Co., Ltd.) is stacked on top and bottom, heated and pressurized at 130 ° C for 15 minutes and 200 ° C x 20 kg / cm for ² x 120 minutes, and laminated. I got a board. Each test of Tg, flame retardancy, copper foil peeling strength, interlayer adhesive strength, relative permittivity, and dielectric loss tangent of the laminated board was performed, and the results are shown in Table 4.

Examples 12 to 13 and Comparative Example 7
The mixture was blended in the blending amount (part) of the formulation shown in Table 4, and a laminated board was obtained in the same manner as in Example 11. The same test as in Example 11 was performed, and the results are shown in Table 4.

Claims (12)

An oxazine resin composition containing an oxazine resin (A) and a phenol compound (B), the oxazine resin (A) is represented by the following formula (1), and n = 0 bodies are present in the gel permeation chromatography measurement. 15 to 60 area%, the total of n = 1 and n = 2 is 25 to 40 area%, the content of n = 3 or more is 15 to 45 area%, and the weight average molecular weight is standard. Oxazine is 700 to 1300 in terms of polystyrene, and the molar ratio (OH / Z) of the hydroxyl group (OH) to the oxazine ring (Z) in the formula (1) is 10/90 to 30/70. Resin composition.

(In the formula, A ¹ independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. An alkoxy group of 6, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkylyloxy group having 7 to 12 carbon atoms is used as a substituent for the aromatic ring. X independently represents a divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b). R ¹ is each independently. It represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R ² is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms. It indicates an aryl group of 6 to 12 and an aralkyl group having 7 to 12 carbon atoms. M1 and m2 are independently 0, 1 or 2, respectively, and the sum of m1 and m2 bonded to the same A1 is ¹ or 2. There is an average value of 0.7 to 2.1.)

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² is an aroma selected from a benzene ring, a naphthalene ring or a biphenyl ring. Group ring groups are shown, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms may be used as a substituent on the aromatic ring.) The oxazine resin composition according to claim 1, wherein the compounding ratio (A / B) of the oxazine resin (A) and the phenol compound (B) is 99.5 / 0.5 to 50/50 (mass ratio). The oxazine resin composition according to claim 1 or 2, further comprising 0.01 to 900 parts by mass of the epoxy resin (C) with respect to a total of 100 parts by mass of the oxazine resin (A) and the phenol compound (B). .. The oxazine resin composition according to claim 3, further comprising 0.1 to 500 parts by mass of the epoxy resin curing agent (D) with respect to 100 parts by mass of the epoxy resin (C). The oxazine resin composition according to claim 4, wherein the curing agent (D) for an epoxy resin is an acid anhydride curing agent, an amine-based curing agent, or dicyandiamide. Further, any one of claims 1 to 5 in which the curing accelerator (E) is blended in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the oxazine resin (A) and the phenol compound (B). The oxazine resin composition according to. An oxazine resin composition containing an oxazine resin (A) and a phenol compound (B), wherein the oxazine resin (A) is a novolak phenol compound (e), a monoamino compound represented by the following formula (21), and the following formula (A). The novolak phenol compound (e) obtained from the aldehydes represented by 22) is represented by the following formula (2), and in the gel permeation chromatography measurement, k = 0 is 30 to 90 area%. , K = 1 body and k = 2 bodies total 10 to 65 area%, k = 3 or more bodies 1 to 20 area%, and weight average molecular weight is 330 to 550 in standard polystyrene conversion value. An oxazine resin composition comprising.

R ¹ -NH ₂ (21)
R2 ^- CHO (22)

(R ¹ represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ² is a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. , An aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms.)

( ^In the formula, A3 independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. An alkoxy group of 6, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkylyloxy group having 7 to 12 carbon atoms is used as a substituent for the aromatic ring. X independently represents a divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b). M is 1 or 2. .K is a number from 0.1 to 1.3 on average.)

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² is an aroma selected from a benzene ring, a naphthalene ring or a biphenyl ring. Group ring groups are shown, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms may be used as a substituent on the aromatic ring.) A prepreg using the oxazine resin composition according to any one of claims 1 to 7. A laminated board characterized by using the oxazine resin composition according to any one of claims 1 to 7. A cured product obtained by curing the oxazine resin composition according to any one of claims 1 to 7. A method for producing an oxazine resin by reacting a novolak phenol compound (e) with a monoamino compound represented by the following formula (21) and an aldehyde represented by the following formula (22), wherein the novolak phenol compound (e) is used. However, in the gel permeation chromatography measurement, k = 0 is 30 to 90 area%, and the total of k = 1 and k = 2 is 10 to 65 area%. A method for producing an oxazine resin, which comprises 1 to 20 area% of k = 3 or more, and a weight average molecular weight of 330 to 550 in terms of standard polystyrene.

R ¹ -NH ₂ (21)
R2 ^- CHO (22)

(R ¹ represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ² is a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. , An aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms.)

( ^In the formula, A3 independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. An alkoxy group of 6, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkylyloxy group having 7 to 12 carbon atoms is used as a substituent for the aromatic ring. X independently represents a divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b). M is 1 or 2. .K is a number from 0.1 to 1.3 on average.)

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² is an aroma selected from a benzene ring, a naphthalene ring or a biphenyl ring. Group ring groups are shown, and these aromatic ring groups are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms may be used as a substituent on the aromatic ring.) The method for producing an oxazine resin according to claim 11, wherein the monoamino compound is aniline and the aldehydes are formaldehyde.

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