CN110194843B

CN110194843B - Phosphorus-containing phenoxy resin, resin composition, material for circuit board, and cured product

Info

Publication number: CN110194843B
Application number: CN201910142063.3A
Authority: CN
Inventors: 佐藤洋; 军司雅男
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2018-02-26
Filing date: 2019-02-26
Publication date: 2023-01-03
Anticipated expiration: 2039-02-26
Also published as: KR20190103039A; TWI786271B; JP7055664B2; CN110194843A; KR102662809B1; JP2019147863A; TW201938639A

Abstract

The present invention relates to a phosphorus-containing phenoxy resin, a resin composition, a material for a circuit board, and a cured product. The invention provides a phosphorus-containing phenoxy resin and a resin composition using the same, wherein the phosphorus-containing phenoxy resin has excellent safety, flame retardance, adhesiveness, processability and heat resistance. The solution is a phosphorus-containing phenoxy resin represented by the following formula (1), the weight average molecular weight of which is 10,000 to 200,000. Wherein X is a 2-valent group containing a group (X1) represented by the formula (2), Y is each independently a hydrogen atom or a glycidyl group, and n is 25 to 500.A is a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and Z is a phosphorus-containing group represented by formula (3).

Description

Phosphorus-containing phenoxy resin, resin composition, material for circuit board, and cured product

Technical Field

The present invention relates to a phosphorus-containing phenoxy resin having excellent flame retardancy and adhesion and high heat resistance, and also relates to a resin composition containing the phosphorus-containing phenoxy resin and a curable resin component, and a cured product thereof.

Background

Epoxy resins are widely used mainly as electrical insulating materials because of their excellent electrical insulating properties, electrical characteristics, adhesiveness, mechanical characteristics of cured products, and the like. In view of safety, these electrical insulating materials are required to have high flame retardancy, and are made flame retardant by using a halogen flame retardant, an antimony compound, a phosphorus flame retardant, or the like in combination. However, in recent years, regulations on materials used for such flame retardants have been increasing from the viewpoint of environmental pollution and toxicity. Among them, organic halogen substances such as dioxin have been problematic in toxicity and carcinogenicity, and reduction and elimination of halogen-containing substances have been strongly demanded. Further, in view of the problem of carcinogenicity of antimony, there is an increasing demand for reduction and elimination of antimony compounds. Under such circumstances, phosphorus flame retardants have been proposed and studied as substitutes for these.

In some applications, an epoxy resin is used as a phenoxy resin, which is converted to a high molecular weight by various methods to impart film formability. In particular, the properties required for phenoxy resins for electrical insulating material applications include flame retardancy, high heat resistance, and the like. In order to develop flame retardancy without using halogen for environmental problems, some documents disclose phenoxy resins containing phosphorus atoms, but they have poor water absorption properties, poor solvent solubility due to limitations on the solvent in which the phenoxy resins are dissolved, and the like (patent documents 1 and 2). Further, although a method of improving water absorption and solvent solubility is disclosed, since an aliphatic skeleton is used in a large amount, flame retardancy cannot be secured unless the content of phosphorus atoms is increased (patent documents 3 and 4).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2001-310939

[ patent document 2] Japanese patent application laid-open No. 2002-3711

[ patent document 3] Japanese patent laid-open publication No. 2015-196719

[ patent document 4] Japanese patent laid-open No. 2015-196720.

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention has an object to provide a phosphorus-containing phenoxy resin which solves the above-mentioned problems and is excellent in flame retardancy, high in heat resistance and excellent in low water absorption, which is applicable to the electric/electronic field, a resin composition using the phosphorus-containing phenoxy resin, a material for a circuit board, and a cured product thereof. It is another object of the present invention to provide a phosphorus-containing phenoxy resin having flame retardancy, high heat resistance, low water absorption, and a good balance of low linear expansion, ductility, high thermal conductivity, solvent solubility, low dielectric constant, low dielectric loss tangent, and the like.

[ means for solving the problems ]

That is, the present invention provides a phosphorus-containing phenoxy resin represented by the following formula (1), which has a weight average molecular weight of 10,000 to 200,000.

In the formula (1), X is a 2-valent group, and at least a part of X is a group (X1) represented by the following formula (2). And Y is each independently a hydrogen atom or a glycidyl group. n is the number of repetitions and has an average value of 25 to 500.

In formula (2), a is an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups may have any one of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms as a substituent. Z is a phosphorus-containing group represented by the following formula (3).

In the formula (3), R ¹ And R ² The hydrocarbon group may have hetero atoms and may have 1 to 20 carbon atoms, and may be different or the same, and may be linear, branched or cyclic. In addition, R ¹ And R ² Or may be bonded and form a cyclic structure. k1 and k2 are independently 0 or 1.

The phosphorus-containing group is preferably a phosphorus-containing group represented by the following formula (3 a) or (3 b).

In the formulae (3 a) and (3 b), R ³ And R ⁴ Each independently a hydrocarbon group having 1 to 11 carbon atoms. m1 is independently an integer of 0 to 4, and m2 is independently an integer of 0 to 5.

The X preferably contains the group (X1) and a phosphorus-free group (X2) containing no phosphorus in a range of 25 to 75 mol% relative to the number of moles of the whole X.

The phosphorus-free group (X2) preferably contains at least one group selected from 1 group having a valence of 2 represented by the following formulae (4 a) to (4 c).

In the formula (4 a), R ⁵ Is a direct bond or is selected from hydrocarbon radicals of 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -and-C (CF) ₃ ) ₂ -2-valent radical of (a).

In the formulae (4 a) to (4 c), R ⁶ 、R ⁷ And R ⁸ Each independently a hydrocarbon group having 1 to 11 carbon atoms. m3 and m4 are each independently an integer of 0 to 4, and m5 is an integer of 0 to 6.

The phosphorus content is preferably 1 to 10 mass%.

The present invention is a resin composition obtained by blending a curable resin component with the phosphorus-containing phenoxy resin. The curable resin component is preferably at least one selected from the group consisting of epoxy resins, acrylate resins, melamine resins, isocyanate resins, and phenol resins.

The present invention is a material for circuit boards obtained from the resin composition, and is a cured product of the resin composition.

[ Effect of the invention ]

The phosphorus-containing phenoxy resin of the present invention is free of halogen, exhibits excellent flame retardancy and high heat resistance, and has properties such as solvent solubility, low linear expansion, ductility, high thermal conductivity, low water absorption, low dielectric constant, and low dielectric loss tangent in a well-balanced manner according to the application. Therefore, the phosphorus-containing phenoxy resin of the present invention or the resin composition containing the phosphorus-containing phenoxy resin can be applied to various fields such as adhesives, paints, building materials for civil engineering, insulating materials for electric/electronic parts, and the like, and is particularly useful as an insulating injection molding material, a laminating material, a sealing material, and the like in the electric/electronic fields.

Detailed Description

The embodiments of the present invention will be described in detail below. The phosphorus-containing phenoxy resin of the present invention has a weight average molecular weight (Mw) as shown in the formula (1) and measured by Gel Permeation Chromatography (GPC) of 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 25,000 to 100,000, still more preferably 30,000 to 80,000. When Mw is low, film formability and stretchability of the film are poor, and when Mw is too high, handling of the resin is significantly deteriorated. The GPC measurement method was performed under the conditions described in the examples.

In the formula (1), X is a 2-valent group, and the group (X1) represented by the formula (2) is contained as an essential component. Here, the group (X1) contains an aromatic ring, an oxygen atom and Z, and since Z is a phosphorus-containing group, the group (X1) is a phosphorus-containing group.

X is not particularly limited if it contains the above-mentioned oxygen-containing group (X1), but preferably has both the oxygen-containing group (X1) and a phosphorus-free group (X2) containing no phosphorus, and examples of the phosphorus-free group (X2) include groups represented by the above-mentioned formulas (4 a) to (4 c). Further, a P-containing group (X3) other than the group (X1) may be contained as the phosphorus-containing group.

And Y is each independently a hydrogen atom or a glycidyl group.

n is the number of repetitions and has an average value of 25 to 500, preferably 40 to 400, more preferably 50 to 350, still more preferably 70 to 300.n is associated with the Mw.

In the formula (2), A represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring. Also, these aromatic cyclic groups may have any one of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms as a substituent. For example, as the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a hexyl group and the like are exemplified, as the cycloalkyl group having 5 to 8 carbon atoms, a cyclohexyl group and the like are exemplified, as the aryl group or aryloxy group having 6 to 10 carbon atoms, a phenyl group, a naphthyl group, a phenoxy group, a naphthoxy group and the like are exemplified, and as the aralkyl group or aralkyloxy group having 7 to 11 carbon atoms, a benzyl group, a phenethyl group, a 1-phenylethyl group, a benzyloxy group, a naphthylmethyloxy group and the like are exemplified. Preferred a is: a benzene ring, a methyl-substituted compound of a benzene ring, a 1-phenylethyl-substituted compound of a benzene ring, a naphthalene ring, a methyl-substituted compound of a naphthalene ring, or a 1-phenylethyl-substituted compound of a naphthalene ring. For applications where solvent solubility is more required, a benzene ring, a methyl-substituted compound of a benzene ring, or a 1-phenylethyl-substituted compound of a benzene ring is preferable, and for applications where flame retardancy and heat resistance are more required, a naphthalene ring, a methyl-substituted compound of a naphthalene ring, or a 1-phenylethyl-substituted compound of a naphthalene ring is preferable.

In the formula (2), Z is a phosphorus-containing group represented by the formula (3).

In the formula (3), R ¹ And R ² Represents a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, may be different or the same, and may be linearBranched, cyclic. In addition, R ¹ And R ² Or may be bonded and form a cyclic structure. Aromatic ring groups are particularly preferred. R ¹ And R ² When the aromatic ring group is used, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or an aralkyloxy group having 7 to 11 carbon atoms may be used as a substituent. As the hetero atom, an oxygen atom and the like are exemplified, which may be contained between carbons constituting a hydrocarbon chain or a hydrocarbon ring.

n1 and n2 are 0 or 1, and may be the same or different.

The phosphorus-containing group represented by the formula (3) includes groups represented by the above-mentioned formula (3 a) or (3 b).

In the formulae (3 a) and (3 b), R ³ And R ⁴ Each independently a hydrocarbon group having 1 to 11 carbon atoms, specifically methyl, ethyl, tert-butyl, cyclohexyl, phenyl, tolyl, and benzyl, and examples thereof include methyl, cyclohexyl, phenyl, tolyl, and benzyl, with methyl, phenyl, and benzyl being preferred.

m1 is each independently an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1. m2 is each independently an integer of 0 to 5, preferably 0 to 2, more preferably 0 or 1.

As another preferred example of the phosphorus-containing group represented by the above formula (3), phosphorus-containing groups represented by the following formulae (a 1) to (a 10) are exemplified.

The group (X1) imparts a phosphorus-containing phenoxy resin having excellent flame retardancy and heat resistance. The chemical structure of the group (X1) has higher rigidity than the structure of the phosphorus atom-containing skeleton (for example, a structure represented by formula (5) described later) in the conventional phosphorus-containing phenoxy resin, and can restrict molecular motion more strongly, so that the heat resistance is further improved, the volume is larger, and the hydrophobicity and rigidity are considered to be higher, and the water absorption property can be reduced. On the other hand, although it is preferable to introduce a structure other than a phosphorus-containing group for improving other characteristics, since the desired effect can be exhibited even with a small amount of the group (X1), more other structures can be introduced and other characteristics can be easily imparted.

In the formula (1), at least a part of X is a group (X1). The group (X1) is 1 to 100 mol%, preferably 2 to 75 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 40 mol%, and particularly preferably 15 to 35 mol%, relative to the entire X. And 1 has 1 or more groups (X1) in the molecule on average.

Preferred structures of the group (X1) include, but are not limited to, structures represented by the following formulae (2 a) to (2 f). Particularly preferred are structures represented by the following formulae (2 a ') to (2 f').

X may contain a P-containing group (X3) containing a phosphorus atom other than the group (X1). The P-containing group (X3) preferably includes a 2-valent group represented by the following formula (5) having one Z.

In the formula (5), A and Z are synonymous with A and Z of the formula (2), respectively.

Further, X in the formula (1) may contain a phosphorus-free group (X2) containing no phosphorus atom, and the phosphorus-free group (X2) is preferably a 2-valent group represented by the above-mentioned formulae (4 a) to (4 c).

In the formula (4 a), R ⁵ Is a direct bond or is selected from C1-20 hydrocarbon group, -CO-, -O-, -S-, -SO ₂ -、-C(CF ₃ ) ₂ -2-valent radical of (a). As the hydrocarbon group, there can be exemplified: -CH ₂ -、-CH(CH ₃ )-、-C ₂ H ₄ -、-C(CH ₃ ) ₂ -, cyclohexylene, cyclododecylene, cyclopentylene, methylcyclopentylene, trimethylcyclopentylene, cyclohexylene, methylcyclohexylene, trimethylcyclohexylene, tetramethylcyclohexylene, cyclooctylene, cyclododecylene, bicyclo [4.4.0 ] ene]Decyl radical, imino radicalCyclohexyl, phenylene, xylylene, phenylmethylene, diphenylmethylene, 9H-fluoren-9-ylidene, or norbornylene, adamantylene, tetrahydrodicyclopentadienyl, tetrahydrotricyclopentadienyl, 2-valent group having norbornane structure, tetrahydrodicyclopentadiene structure, tetrahydrotricyclopentadienyl structure. Of these, the direct bond, -CH is preferred ₂ -、-CH(CH ₃ )-、-C(CH ₃ ) ₂ -、-CO-、-O-、-S-、-SO ₂ -, cyclohexylene, trimethylcyclohexylene, cyclooctylene, cyclododecylene, dicyclohexylene, 9H-fluoren-9-ylidene or 2-valent radical having a tetrahydrodicyclopentadiene structure, more preferably a direct bond, -CH ₂ -、-C(CH ₃ ) ₂ -、-CO-、-SO ₂ -, trimethylcyclohexylene, 9H-fluoren-9-ylidene or a 2-valent radical having a tetrahydrodicyclopentadiene structure.

R ⁵ In the case of direct bonding, the biphenyl skeleton may be any of a 2,2' -biphenyl skeleton, a 2,3' -biphenyl skeleton, a 2,4' -biphenyl skeleton, a 3,3' -biphenyl skeleton, a 3,4' -biphenyl skeleton, and a 4,4' -biphenyl skeleton, but a 4,4' -biphenyl skeleton is preferred. In addition, R ⁵ In the case other than direct bonding, the bonding position to the aromatic ring may be any of 2,2' position, 2,3' position, 2,4' position, 3' position, 3,4' position and 4,4' position, but is preferably 4,4' position.

R ⁶ Each independently a hydrocarbon group having 1 to 11 carbon atoms, preferably R of formula (3 a) ³ The same group. m3 are each independently an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

In the formulas (4 b) and (4 c), R ⁷ 、R ⁸ And said R ⁶ The same description applies. m4 is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1. m5 is an integer of 0 to 6, preferably 0 to 2, more preferably 0 or 1.

The introduction of the phosphorus-free group (X2) into X in the formula (1) contributes to improvement of properties other than flame retardancy, for example, solvent solubility, low linear expansion, elongation, high thermal conductivity, low dielectric constant, low dielectric loss tangent and the like, and further improvement of heat resistance and low water absorption, and therefore the amount of introduction is preferably determined in accordance with the purpose. The content of the phosphorus-free group (X2) is preferably 25 to 75 mol% relative to the number of moles of the whole X.

Hereinafter, the "phosphorus-free group (X2)" may be simply referred to as the group (X2) and the "phosphorus-containing group" may be simply referred to as the group (X3).

X may have a group (X1), a group (X2) and a group (X3), but it is essential that X1 is present and 1 molecule contains 1 or more groups (X1). Otherwise, it may be contained in an amount of 1 mol% or more.

The group (X3) improves flame retardancy as in the group (X1), but the group (X1) exhibits a sufficient effect when the amount is small because the effect is larger than that of the group (X3). However, the introduction of the group (X3) has an advantage that it is easily available because it is commercially available.

The group (X2) enhances characteristics different from those of the groups (X1) and (X3). The phenoxy resin may have the above-mentioned properties depending on the application, and desired properties can be imparted by the kind and amount of the group (X2). When the group (X1) and the group (X3) are small in amount, they can exhibit the effect, and thus can contain a sufficient amount of the group (X2) and impart sufficient desired properties.

For example, in the case of the use of the thermoplastic resin as a flame retardant, it is preferable that the group (X1) and the group (X3) are contained only without containing the phosphorus-containing group (X2), and it is preferable that only the group (X1) is contained from the viewpoint of flame retardancy, but it is preferable that the group (X1) and the group (X3) are mixed from the viewpoint of productivity.

In addition, in the conventional phosphorus-containing phenoxy resin containing no phosphorus group (X2) and no phosphorus group (X3), it is necessary to add the group (X2) for imparting new characteristics and improving certain characteristics, but when there is no margin in flame retardancy, there is no other way than to give up the characteristic imparting of the phenoxy resin itself and to cope with it by separately blending. In such a case, the base (X2) can be introduced to provide the phenoxy resin itself with necessary characteristics because the base (X1) provides a margin for flame retardancy by using a part or all of the base (X3).

The structure not containing the phosphorus-containing group (X2) may be selected depending on the properties to be imparted. For example, in order to further improve heat resistance, a 2-valent group having a norbornylene group, an adamantylene group, or the like, or a 9H-fluoren-9-ylidene group, or the like is exemplified. Examples of the solvent solubility include biphenylene group, methylenebismethylphenyl group and methylenebisxylyl group having a methyl substituent. Examples of the use for improving the dielectric characteristics include a 2-valent group having a tetrahydrodicyclopentadiene structure, a tetrahydrotricyclopentadiene structure or the like, or a 2-valent group having a trifluoromethyl group, a benzyl group substituent, a 1-phenylethyl group substituent or the like. Examples of the moisture absorption property can include a 2-valent group having a trifluoromethyl group and a 9H-fluoren-9-ylidene group.

From such a viewpoint, the content of the group (X1) in X is preferably in the range.

The content of the phosphorus-free group (X2) varies depending on the use, but is 0 to 99 mol%, preferably within the above range, more preferably 45 to 55 mol%.

The content of the group (X3) is preferably 0 to 50 mol%, more preferably 20 to 40 mol%.

The content of phosphorus derived from X constituting the phenoxy resin may be 1 to 10 mass%, preferably 1 to 8 mass% of the phenoxy resin in terms of phosphorus atoms.

The phenoxy resin of the present invention may be used in the form of an epoxy group terminal, a phenolic hydroxyl group terminal, or a mixture thereof. In general, the phenoxy resin does not consider the reaction at the epoxy group, and there is no need to specifically define the epoxy equivalent (g/eq.), but may be 5,000 or more. If the amount is less than 5,000, the film formability and stretchability of the film are not preferable. In addition, when the phenolic hydroxyl group ends, the epoxy group concentration becomes 0, so the epoxy equivalent becomes infinite. Therefore, the upper limit of the epoxy equivalent is defined substantially without critical meaning. However, from the viewpoint of improving the workability, it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, and particularly preferably 20,000 or less.

The method for producing the phosphorus-containing phenoxy resin of the present invention includes, but is not limited to, the following one-stage method (direct method) and two-stage method (indirect method).

The one-stage method is a method of reacting an epihalohydrin such as epichlorohydrin or epibromohydrin with a phenol compound containing a phosphorus-containing 2-functional phenol compound represented by the following formula (6 a) in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The phenol compound of the raw material may contain, in addition to the phosphorus-containing 2-functional phenol compound, a phosphorus-free 2-functional phenol compound represented by the following formula (6 b) and another phosphorus-containing 2-functional phenol compound represented by the following formula (6 c).

H-X ¹ -H(6a)

H-X ² -H(6b)

H-X ³ -H(6c)

Here, X ¹ 、X ² 、X ³ Are synonymous with the radicals (X1), (X2) and (X3), respectively.

The two-stage process is a process in which a 2-functional phenol compound is reacted with a 2-functional epoxy resin, usually in the presence of a catalyst.

As the 2-functional phenol compound and the 2-functional epoxy resin, 1 or 2 or more kinds of phenol compounds or epoxy resins having the group (X1), the group (X2) or the group (X3) can be used. At this time, at least 1 of the 2-functional phenol compound or the 2-functional epoxy resin contains the group (X1).

Examples of the 2-functional phenol compound include phenol compounds represented by the above-mentioned formulas (6 a) to (6 c). As the 2-functional epoxy resin, epoxy resins obtained by epoxidizing the phenol compounds represented by the above-mentioned formulas (6 a) to (6 c) can be cited. The 2-functional epoxy resin and phenol compound may contain 2 or more of the group (X1), the group (X2) and the group (X3) in the molecule.

The ratio of the group (X1), the group (X2) or the group (X3) in the phenoxy resin can be controlled by changing the ratio of the raw materials.

The Mw and epoxy equivalent of the phosphorus-containing phenoxy resin can be adjusted to the target ranges by adjusting the feed molar ratio of the epihalohydrin to the 2-functional phenol compound in the one-stage process, and can be adjusted to the target ranges by adjusting the feed molar ratio of the 2-functional epoxy resin to the 2-functional phenol compound in the two-stage process. The phosphorus-containing phenoxy resin of the present invention can be obtained by any production method, but in general, a two-stage method is preferably used because a phenoxy resin can be obtained more easily than a one-stage method.

The method for producing the phosphorus-containing 2-functional phenol compound represented by the above formula (6 a) is not particularly limited, but is preferably a method in which a quinone compound is used in a range of 0.5 mol or more and less than 1.0 mol based on 1 mol of an organic phosphorus compound represented by the following formula (7), and a reaction is carried out in an organic solvent in which water is present in an amount of 0.05 to 0.5 mol based on 1 mol of the organic phosphorus compound at a reaction temperature of 100 to 200 ℃, preferably in a reflux state.

In the formula (7), R ¹ 、R ² K1 and k2 are each independently R of formula (3) ¹ 、R ² K1 and k2 are synonymous.

In the reaction, a phosphorus compound having a structure represented by the formula (5) is by-produced. In order to isolate the target phosphorus-containing 2-functional phenol compound, after the reaction is completed, the reaction product is mixed with a good solvent, and the target phosphorus-containing 2-functional phenol compound is dissolved and the by-produced phosphorus compound is removed as an insoluble component. The solution after the solid content separation is preferably further purified for high purity, because most of the phosphorus-containing 2-functional phenol compound which is the target product is present, but a slight amount of the by-produced phosphorus compound may remain. In the purification method, the solution is mixed with a poor solvent to precipitate crystals of the phosphorus-containing 2-functional phenol compound which is a target product. Also, by-products and the like are dissolved in the poor solvent solution. In addition, other purification methods may be used, such as extraction, washing, and distillation. Further, since the phosphorus compound having the structure represented by the formula (5) can give the group (X3), it is also possible to use the compound as it is without separating a part or all of it as a useful component for exhibiting flame retardancy.

Examples of the organic solvent usable for the reaction include: alcohols such as 1-methoxy-2-propanol, acetates such as diethylene glycol monoethyl ether acetate, benzoates such as methyl benzoate, ciclesonide (cellosolve) such as methyl ciclesonide, carbitols such as butyl carbitol, ethers such as diethylene glycol diethyl ether, aromatic hydrocarbons such as toluene, amides such as N, N-Dimethylformamide (DMF), dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, and the like. These organic solvents can be used alone or mixed with 2 or more.

The quinone compound usable in the above reaction can be used without any problem if the purity is 90% or more in the case of industrial products.

When A in the formula (2) is a benzene ring, examples of the quinone compound used include: benzoquinone, methylbenzoquinone, ethylbenzoquinone, butylbenzoquinone, dimethylbenzoquinone, diethylbenzoquinone, dibutylbenzoquinone, methylisopropylbenzoquinone, diethoxybenzoquinone, methylmethoxybenzoquinone, phenylbenzoquinone, tolylbenzoquinone, ethoxyphenylbenzoquinone, diphenylbenzoquinone, and the like.

When A in the formula (2) is a naphthalene ring, examples of the quinone compound used include: naphthoquinone, menadione, cyclohexyl naphthoquinone, methoxy naphthoquinone, ethoxy naphthoquinone, dimethyl isopropyl naphthoquinone, methyl methoxy naphthoquinone, etc.

When A in the formula (2) is an anthracycline, examples of the quinone compound used are: anthraquinone, methylanthraquinone, ethylanthraquinone, methoxyanthraquinone, dimethoxyanthraquinone, diphenoxyanthraquinone, etc.

When A in the formula (2) is a phenanthrene ring, examples of the quinone compound to be used include: phenanthrenequinone, methylphenanthaquinone, isopropylphenanthrenequinone, methoxyphenanthrene quinone, butoxyphenanthrene quinone, dimethoxyphenanthrenequinone, and the like.

These quinone compounds may be used alone or in combination of 2 or more.

As the organophosphorus compound represented by the formula (7), for example: dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, dibenzyl phosphine oxide, cyclooctylene phosphine oxide, tolyl phosphine oxide, bis (methoxyphenyl) phosphine oxide, and the like; phenyl phenylphosphonite, ethyl phenylphosphonite, tolyl phenylphosphonite, benzyl benzylphosphinate, and the like; 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 8-methyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6, 8-tri-tert-butyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6, 8-dicyclohexyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like; diphenyl phosphite, ditolyl phosphite, diphenylmethyl phosphite, 5-dimethyl-1, 3, 2-dioxaphosphorinane, and the like. These organic phosphorus compounds can be used alone or in combination of 2 or more.

Examples of the good solvent include ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetate, benzoate, and the like. These solvents can be used alone or in a mixture of 2 or more. Among these solvents, acetic acid esters are preferable, and benzyl acetate is more preferable.

Examples of the poor solvent include methanol, ethanol, butanol, and acetone. These solvents can be used alone or in a mixture of 2 or more. Among these solvents, methanol, ethanol and acetone are preferable, and methanol and ethanol are more preferable. These solvents may be aqueous solvents, and in this case, water may be contained up to 100 parts by mass relative to 100 parts by mass of the solvent.

The 2-functional phenol compound used in the production of the one-stage method and the two-stage method is not particularly limited, and the phosphorus-containing 2-functional phenol compound represented by the formula (6 a) may be used in combination with another 2-functional phenol compound.

For example, a 2-functional phenol compound containing no phosphorus represented by the above formula (6 b), such as a phenol compound having a 2-valent group represented by the formulae (4 a) to (4 c), or a 2-functional phenol compound containing phosphorus represented by the formula (6 c), such as a phenol compound having 1 phosphorus-containing group represented by the formula (3), may be used in combination.

The phosphorus-containing 2-functional phenol compound having 1 phosphorus-containing group represented by the formula (3) can be obtained by reacting an organophosphorus compound represented by the formula (7) with a quinone compound by a known synthesis method. The synthesis method includes, for example, the methods shown in Japanese patent application laid-open Nos. 60-126293 and 61-236787, zh. Obshch. Khim,42 (11), and pages 2415-2418 (1972), but is not limited thereto.

As the above-mentioned phosphorus-free 2-functional phenol compound which may be used in combination, there may be mentioned, for example: bisphenols such as bisphenol a, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, bisphenol acetophenone, and bisphenol fluorenone; a dihydroxy compound having a norbornane structure, a tetrahydrodicyclopentadiene structure, a tetrahydrotricyclopentadiene structure or an adamantane structure; biphenols; monocyclic 2-functional phenols such as catechol, resorcinol, hydroquinone, and the like; dihydroxynaphthalenes, and the like.

As the phosphorus-containing 2-functional phenol compound which can be used in combination, there may be mentioned, for example: 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, abbreviated as DOPO-HQ), 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, abbreviated as DOPO-NQ), diphenylphosphonyl hydroquinone, diphenylphenylphosphino-1, 4-dioxynaphthalene, 1, 4-cyclooctylphosphonyl-1, 4-phenylenediol, 1, 5-cyclooctylphosphonyl-1, 4-phenylenediol, and the like.

In addition, these may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. These 2-functional phenol compounds may be used in combination in various forms.

First, a one-stage method is explained.

In the case of the one-stage method, 0.985 to 1.015 mol (preferably 0.99 to 1.012 mol, more preferably 0.995 to 1.01 mol) of epihalohydrin is reacted in a non-reactive solvent in the presence of an alkali metal hydroxide with respect to 1 mol of a 2-functional phenol compound, the epihalohydrin is consumed, and a condensation reaction is performed so that Mw becomes 10,000 or more, whereby a phosphorus-containing phenoxy resin can be obtained. After the reaction is completed, the by-produced salt must be removed by filtration or washing with water.

The 2-functional phenol compound represented by the formula (6 a) used as the raw material is preferably 1 to 100 mol%, more preferably 2 to 75 mol%, still more preferably 5 to 50 mol%, particularly preferably 10 to 40 mol%, most preferably 15 to 35 mol% in the raw material 2-functional phenol compound.

The 2-functional phenol compound represented by the formula (6 b) is used for imparting characteristics other than flame retardancy, but is preferably 0 to 75 mol%, more preferably 25 to 75 mol%, and still more preferably 45 to 55 mol%.

The 2-functional phenol compound represented by the formula (6 c) is used in combination for imparting flame retardancy, but it is preferably 0 to 50 mol%, more preferably 10 to 40 mol%. When the 2-functional phenol compound represented by the formula (6 c) is used in combination, it is usually advantageous to use the 2-functional phenol compound represented by the formula (6 a) as a mixture without isolating it.

The reaction can be carried out under normal pressure or under reduced pressure. In general, the reaction temperature is preferably from 20 to 200 ℃, more preferably from 30 to 170 ℃, still more preferably from 40 to 150 ℃, particularly preferably from 50 to 100 ℃ when the reaction is carried out under normal pressure. When the reaction is carried out under reduced pressure, it is preferably from 20 to 100 ℃, more preferably from 30 to 90 ℃, still more preferably from 35 to 80 ℃. When the reaction temperature is within this range, side reactions are less likely to occur and the reaction is likely to proceed. The reaction pressure is usually normal pressure. When it is necessary to remove the reaction heat, it is usually carried out by an evaporation/condensation/reflux method using a solvent due to the reaction heat, an indirect cooling method, or a combination of these methods.

As the non-reactive solvent, for example: aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dibutyl ether, dioxane, tetrahydrofuran, etc.; alcohols such as ethanol, isopropanol, and butanol; stachy materials such as Stachy methyl Stachy and Stachy ethyl Stachy; glycol ethers such as ethylene glycol dimethyl ether, but not particularly limited thereto, and these solvents may be used alone or in a mixture of 2 or more.

In addition, a catalyst may be used. As the catalyst which can be used, for example: quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4, 6-tris (dimethylaminomethyl) phenol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine, etc. These catalysts may be used alone or in combination of 2 or more.

Next, the two-stage method is described.

As the 2-functional epoxy resin to be the raw material epoxy resin in the two-stage process, a 2-functional epoxy resin represented by the following formula (8) obtained by reacting the phosphorus-free 2-functional phenol compound represented by the above formula (6 b) with epihalohydrin is preferable. Furthermore, in the case of phosphorus-containing 2-functional epoxy resins, these areIs represented by X of the formula (8) ² Substitution by X ¹ Or X ³ The structure of (1).

In formula (8), X ² And X of formula (6 b) ² Synonymously, and preferably 2-valent radicals of the formulae (4 a) to (4 c). G is epoxypropyl. J is the number of repetitions and has an average value of 0 to 6, preferably 0 to 3, more preferably 0 to 1.

In the reaction of the 2-functional phenol compound and the epihalohydrin to obtain the raw material epoxy resin in the two-stage process, 0.8 to 1.2 times by mole (preferably 0.85 to 1.05 times by mole) of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used with respect to the functional group in the 2-functional phenol compound. When the content is less than this range, the amount of the residual hydrolyzable chlorine increases, which is not preferable. The metal hydroxide is used in the form of an aqueous solution, an alcohol solution or a solid.

In the epoxidation reaction, epihalohydrin is used in an excess amount to the 2-functional phenol compound. The epihalohydrin is generally used in an amount of 1.5 to 15 times by mole, but preferably 2 to 10 times by mole, and more preferably 5 to 8 times by mole, relative to 1 mole of the functional group in the 2-functional phenol compound. If the amount is more than this range, the production efficiency is lowered, and if the amount is less than this range, the amount of the high molecular weight material of the epoxy resin is increased, and the epoxy resin becomes unsuitable as a raw material for the phenoxy resin containing phosphorus.

The epoxidation reaction is usually carried out at a temperature below 120 ℃. When the reaction temperature is high, the amount of the so-called hardly hydrolyzable chlorine increases, and it becomes difficult to increase the purity. Preferably 100 ℃ or lower, and even more preferably 85 ℃ or lower.

As the 2-functional epoxy resin to be a raw material in the two-stage process, a 2-functional epoxy resin represented by the formula (8) is preferable, and an epoxy resin having a 2-valent group of the formulae (4 a) to (4 c) is more preferable. In addition, these epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. Further, a 2-functional epoxy resin such as an alkylene glycol type epoxy resin or an aliphatic cyclic epoxy resin may be used within a range not to impair the object of the present invention.

The use ratio (molar ratio) of the raw materials is preferably 0.95 to 1.10, more preferably 1.00 to 1.05 in terms of 2-functional epoxy resin/2-functional phenol compound.

In the two-stage method, a catalyst may be used, and any compound having a catalytic ability to promote the reaction of an epoxy group with a phenolic hydroxyl group may be used. Examples thereof include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles, and the like. These catalysts may be used alone or in combination of 2 or more.

As the alkali metal compound, for example: alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium hydrogen carbonate, sodium chloride, lithium chloride and potassium chloride, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal phenoxide, sodium hydride and lithium hydride, and alkali metal salts of organic acids such as sodium acetate and sodium stearate.

As the organic phosphorus compound, for example: tri-n-propylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, triphenylphosphine, trimethylphenylphosphine, trimethoxyphenylphosphine, tricyclohexylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc.

As the tertiary amine, for example: triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, etc. As the quaternary ammonium salt, for example: tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, and the like.

As imidazoles, there may be mentioned, for example: 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole and the like.

As cyclic amines, there may be mentioned, for example: 1, 4-diazabicyclo [2,2,2] octane (DABCO), 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU), 1, 5-diazabicyclo [4,3,0] -5-nonene (DBN), tetrahydro-1, 4-oxazine (morpholine), N-methylmorpholine, N-Dimethylaminopyridine (DMAP), and the like.

The amount of the catalyst used is usually 0.001 to 1% by mass relative to the reaction solid content. When an alkali metal compound is used as a catalyst, the phosphorus-containing phenoxy resin contains alkali metal components remaining therein, and the insulating properties of electronic/electric parts and printed wiring boards using the catalyst are deteriorated, and therefore the total content of alkali metals such as lithium, sodium, and potassium in the phosphorus-containing phenoxy resin is preferably 100ppm or less, more preferably 60ppm or less, and still more preferably 50ppm or less.

Further, when an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, a cyclic amine, an imidazole or the like is used as a catalyst, the phosphorus-containing phenoxy resin preferably contains 300ppm or less, more preferably 200ppm or less, and still more preferably 100ppm or less of phosphorus or nitrogen because the phosphorus-containing phenoxy resin remains as a catalyst residue and deteriorates the insulating properties of electronic/electric parts and printed wiring boards, similarly to the case where an alkali metal component remains.

In the case of the two-stage method, a solvent may be used, and any solvent may be used as long as it dissolves the phosphorus-containing phenoxy resin and does not adversely affect the reaction. Examples thereof include aromatic hydrocarbons, ketones, ester solvents, ether solvents, amide solvents, glycol ether solvents, and the like. These solvents can be used alone or in a mixture of 2 or more.

Examples of the aromatic hydrocarbons include benzene, toluene, and xylene.

As ketones, there may be mentioned, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, acetylacetone, and the like.

As the ester-based solvent, for example: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone, and the like.

As the ether solvent, for example: diethyl ether, dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, etc.

As the amide solvent, for example: formamide, N-methylformamide, DMF, acetamide, N-methylacetamide, N-dimethylacetamide, 2-pyrrolidinone, N-methylpyrrolidinone, and the like.

As the glycol ether solvent, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, and the like.

The amount of the solvent to be used may be appropriately selected depending on the reaction conditions, but in the case of two-stage production, for example, the solid content concentration is preferably 35 to 95% by mass. When a highly viscous product is produced during the reaction, the reaction may be continued by adding a solvent in the middle of the reaction. After the reaction is completed, the solvent may be removed by distillation or the like, if necessary, and a further solvent may be added.

The reaction in the two-stage process is carried out in a temperature range in which the catalyst used is not decomposed. When the reaction temperature is too high, the resulting phosphorus-containing phenoxy resin may deteriorate, and when it is too low, the reaction may not proceed and the target molecular weight may not be achieved. Therefore, the reaction temperature is preferably 50 to 230 ℃, more preferably 120 to 200 ℃. In addition, the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low boiling point solvent such as acetone, methyl ethyl ketone, etc. is used, the reaction temperature can be secured by conducting the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, the reaction is usually carried out by an evaporation/condensation/reflux method using a solvent due to the heat of reaction, an indirect cooling method, or a combination of these methods.

The phosphorus-containing phenoxy resin of the present invention is flame-retardant per se and is a flexible thermoplastic resin and can be used alone. The compound of formula (1) is useful as a flame retardant for thermoplastic resins such as polycarbonate resins because the phosphorus content is high when most of X is the group (X1).

In addition, a thermosetting resin composition may be prepared by blending a curable resin component. In this case, a part of X is introduced with a phosphorus-free group (X2) to prepare a flame-retardant phenoxy resin having the desired properties of the resin composition.

Next, the resin composition of the present invention will be described.

The resin composition of the present invention is obtained by blending a curable resin component with the phosphorus-containing phenoxy resin.

As the curable resin component, for example: epoxy resins, acrylate resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, isocyanate resins, alkyd resins, thermosetting polyimide resins, and the like. Among these, epoxy resins, phenol resins, melamine resins, and isocyanate resins are preferable, and epoxy resins are more preferable. These curable resin components can be used alone or in combination of 2 or more.

Examples of the curable resin component include: a resin composition in which an epoxy resin is hardened by a hardener, a resin composition in which an acrylate resin is hardened by a radical polymerization initiator, a resin component in which a phenol resin, a melamine resin, an isocyanate resin, or the like is self-polymerized by heat, and the like. It is understood that when a curing agent, a catalyst, an accelerator, or the like is required for curing the curable resin, the curable resin component contains these components.

The amount of the curable resin component to be blended is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, still more preferably 25/75 to 75/25 in terms of the phosphorus-containing phenoxy resin/curable resin component (mass ratio). By blending a curable resin component, a material having more excellent heat resistance can be obtained.

When the curable resin component is an epoxy resin, a conventionally known epoxy resin can be used. The epoxy resin is an epoxy resin having at least 1 epoxy group, but is preferably an epoxy resin having 2 or more epoxy groups, and more preferably an epoxy resin having 3 or more epoxy groups. Specific examples thereof include: a polypropylene oxide ether compound, a polypropylene oxide amine compound, a polypropylene oxide compound, an alicyclic epoxy compound, other modified epoxy resins, and the like. These epoxy resins may be used alone, or 2 or more kinds of the same epoxy resin may be used in combination, or different epoxy resins may be used in combination.

As the polypropylene oxide ether compound, there can be specifically mentioned: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, tetramethylbisphenol F-type epoxy resin, biphenol-type epoxy resin, hydroquinone-type epoxy resin, bisphenol fluorene-type epoxy resin, naphthalenediphenol-type epoxy resin, bisphenol S-type epoxy resin, diphenyl thioether-type epoxy resin, diphenyl ether-type epoxy resin, resorcinol-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, alkyl novolac-type epoxy resin, styrenated phenol novolac-type epoxy resin, bisphenol novolac-type epoxy resin, naphthol novolac-type epoxy resin, β -naphthol aralkyl-type epoxy resin, naphthalenediol aralkyl-type epoxy resin, α -naphthol aralkyl-type epoxy resin, biphenylaralkyl phenol-type epoxy resin, trihydroxyphenyl methane-type epoxy resin, tetrahydroxyphenyl ethane-type epoxy resin, dicyclopentadiene-type epoxy resin, alkylene glycol-type epoxy resin, aliphatic cyclic epoxy resin, and the like.

As the polyoxypropylamine compound, there may be specifically mentioned: diaminodiphenylmethane epoxy resins, m-xylylenediamine epoxy resins, 1, 3-diaminomethylcyclohexane epoxy resins, isocyanurate epoxy resins, aniline epoxy resins, hydantoin epoxy resins, aminophenol epoxy resins, and the like.

As the poly (propylene oxide) compound, specifically, there can be mentioned: dimer acid type epoxy resins, hexahydrophthalic acid type epoxy resins, trimellitic acid type epoxy resins, and the like.

The alicyclic epoxy compound includes aliphatic cyclic epoxy resins such as CELLOXIDE 2021 (manufactured by Daicel chemical industries, ltd.).

Specific examples of the other modified epoxy resins include: urethane-modified epoxy resins, epoxy resins containing an oxazolidone ring, epoxy-modified polybutadiene rubber derivatives, carboxyl-terminated butadiene nitrile rubber (CTBN) -modified epoxy resins, polyvinylarene polyoxides (e.g., divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resins, and the like.

In the case of epoxy resin formulation, a curing agent is contained. The hardener refers to a substance that contributes to a crosslinking reaction and/or a chain length extension reaction between epoxy groups of the epoxy resin.

The compounding amount of the curing agent is used as needed in an amount of 0.1 to 100 parts by mass, preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, and still more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the epoxy resin.

The curing agent is not particularly limited, and any of the conventional curing agents can be used as the curing agent for epoxy resins. From the viewpoint of improving heat resistance, preferred examples thereof include phenol-based curing agents, amide-based curing agents, and imidazoles. In addition, from the viewpoint of reducing water absorption, an active ester-based curing agent is preferably used. Further, there can be enumerated: amine-based curing agents, acid anhydride-based curing agents, organophosphines, phosphonium salts, benzoxazine compounds, tetraphenylborate salts, organic acid dihydrazides, halogenated boron amine complexes, polythiol-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, and the like. These curing agents may be used alone, or 2 or more of the same kind of curing agents may be used in combination, or other kinds may be used in combination.

As the phenolic curing agent, for example: dihydric phenol compounds such as bisphenol a, bisphenol F, dihydroxydiphenylmethane, dihydroxydiphenyl ether, bis (hydroxyphenoxy) benzene, dihydroxydiphenyl sulfide, dihydroxydiphenyl ketone, dihydroxydiphenyl sulfone, fluorene bisphenol, hydroquinone, resorcinol, catechol, tert-butyl hydroquinone, dihydroxynaphthalene, and dihydroxymethylnaphthalene; phenol compounds having 3 or more members such as phenol novolak, bisphenol a novolak, cresol novolak, xylenol novolak, tris-hydroxyphenyl methane novolak, dicyclopentadiene phenol, naphthol novolak, styrenated phenol novolak, terpene phenol, heavy oil-modified phenol, phenol aralkyl, naphthol aralkyl, polyhydroxystyrene, phloroglucinol, pyrogallol, t-butyl pyrogallol, benzenetriol, trihydroxynaphthalene, trihydroxydiphenyl ketone, trihydroxyacetophenone and the like; phosphorus-containing phenol compounds such as 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide. A compound obtained by addition reaction of such a phenol compound with an aromatic compound such as indene or styrene may be used as the curing agent. The phenolic hardener is preferably used in a range of 0.8 to 1.5 in terms of a molar ratio of active hydroxyl groups in the hardener to epoxy groups in the epoxy resin.

Examples of the amide-based curing agent include dicyanodiamide (dicyanodiamide) and derivatives thereof, and polyamide resins. The amide-based curing agent is preferably used in a range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the entire epoxy resin component.

As imidazoles, there may be mentioned, for example: 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-sym triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-sym triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-sym triazine trimerization adduct, 2-phenylimidazole trimerization adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the imidazoles, and the like. The imidazole is preferably used in a range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the entire epoxy resin component. Furthermore, imidazoles are generally classified as a curing accelerator described later because of their catalytic ability, but are classified as a curing agent in the present invention.

The active ester-based curing agent is preferably a compound having 1 molecule of 2 or more ester groups having high reactivity, such as a phenol ester, a thiophenol ester, an N-hydroxylamine ester, or an ester of a heterocyclic hydroxyl compound, and more preferably a phenol ester obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid as described in japanese patent No. 5152445. As the carboxylic acid compound, for example: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the aromatic compound having a phenolic hydroxyl group include: catechol, dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and the like. Commercially available products include EPICLON HPC-8000-65T (DIC Co., ltd.), but are not limited thereto. The active ester-based hardener is preferably used in such a manner that the molar ratio of active ester groups in the hardener to epoxy groups in the resin composition is in the range of 0.2 to 2.0.

As the amine-based curing agent, for example: amine compounds such as polyamidoamines which are condensates of polyamines with acids such as diethylenetriamine, triethylenetetramine, m-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, dicyanodiamine, and dimer acid. The amine-based hardener is preferably used in a range in which the molar ratio of active hydrogen groups in the hardener to epoxy groups in the resin composition is 0.5 to 1.5.

Examples of the acid anhydride-based curing agent include: methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methylnadic anhydride, maleic anhydride, and the like. The acid anhydride-based hardener is preferably used in a range of 0.5 to 1.5 in terms of the molar ratio of acid anhydride groups in the hardener to epoxy groups in the resin composition.

The active hydrogen group means a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen which generates an active hydrogen by hydrolysis or the like and exhibiting a similar curing action), and specifically includes an acid anhydride group, a carboxyl group, an amine group, a phenolic hydroxyl group, and the like. Further, the active hydrogen group, carboxyl (-COOH) and phenolic hydroxyl (-OH) are present in an amount of 1 mol, and the amino (-NH) ₂ ) Calculated as 2 moles. When the active hydrogen group is not clearly defined, the active hydrogen equivalent can be determined by measurement. For example, the active hydrogen equivalent of the hardener used can be determined by reacting a monoepoxy resin having a known epoxy equivalent such as phenylglycidyl ether with a hardener having an unknown active hydrogen equivalent, and measuring the amount of the monoepoxy resin consumed.

When the epoxy resin is blended, a curing accelerator may be used as needed. As the hardening accelerator, for example: imidazole derivatives, tertiary amines, phosphorus compounds such as phosphines, metal compounds, lewis acids, amine complex salts, and the like. These hardening accelerators may be used alone or in combination of 2 or more.

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. Examples of such may be: alkyl-substituted imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2, 4-dimethylimidazole and 2-heptadecylimidazole; and imidazole compounds substituted with a hydrocarbon group having a ring structure such as an aryl group or an aralkyl group, such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2' -cyanoethyl) imidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, and the like.

As the tertiary amines, for example: 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1, 8-diaza-bicyclo [5.4.0] -7-undecene (DBU), and the like.

As phosphines, there may be mentioned, for example: triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and the like.

As the metal compound, tin octylate and the like are exemplified.

As the amine complex salt, for example: and boron trifluoride complexes such as boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzyl amine complex, boron trifluoride aniline complex, and mixtures thereof.

Among these curing accelerators, 2-dimethylaminopyridine, 4-dimethylaminopyridine and imidazoles are preferable from the viewpoint of excellent heat resistance, dielectric properties, solder resistance and the like when used for build-up (build up) material applications and circuit board applications. When used for semiconductor sealing materials, triphenylphosphine and DBU are preferred because they are excellent in curing properties, heat resistance, electrical characteristics, moisture resistance reliability, and the like.

The amount of the hardening accelerator to be blended may be appropriately selected depending on the purpose of use, but is used as needed in an amount of 0.01 to 15 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the epoxy resin component in the resin composition. By using the hardening accelerator, the hardening temperature can be lowered or the hardening time can be shortened.

Examples of the resin composition in which an acrylate resin as a curable resin component is cured by a radical polymerization initiator include a thermosetting resin composition of a (meth) acrylate compound and a photocurable resin composition. An acrylate having at least 1 or more (meth) acryloyl groups in a molecule, which is used as a viscosity adjusting and curing component of the (meth) acrylate compound. A part of the (meth) acrylate compound preferably has 2 or more (meth) acryloyl groups. The resin composition in this case contains a (meth) acrylate compound and a thermal polymerization initiator, a photopolymerization initiator, or both as essential components.

Examples of the (meth) acrylate compounds include: isoborneol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexane-1, 4-dimethanol mono (meth) acrylate, tetrahydrofuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, orthophenylphenol monoethoxy (meth) acrylate, orthophenylphenol polyethoxy (meth) acrylate, p-isopropylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and like monofunctional (meth) acrylates, 1, 4-butanediol di (meth) acrylate, 1-6-hexane (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and dimethyloldecane di (meth) acrylate, polyol (meth) acrylates obtained by reacting a tricycloalkane diol compound with a polyisocyanate compound, and a polyol (meth) acrylate, epoxy acrylates obtained by reacting an epoxy compound with a (meth) acrylate, and the like. These (meth) acrylate compounds may be used alone or in combination of 2 or more.

The compound that can be used as a polymerization initiator for the (meth) acrylate compound is not particularly limited as long as it can generate a radical by a method such as heating or irradiation with active energy ray light. The polymerization initiator may be any initiator that can be used in ordinary radical thermal polymerization, such as azo-based initiators including azobisisobutyronitrile and benzoyl peroxide, and peroxide-based initiators, for example, when it is cured by heating. In addition, when radical polymerization is carried out by radical photopolymerization, any initiator that can be used in general radical photopolymerization such as benzoins, acetophenones, anthraquinones, thioxanthones, ketals, diphenylketones, and phosphine oxides can be used. These polymerization photoinitiators may be used alone or in the form of a mixture of 2 or more. The photo radical polymerization initiator may be used in combination with a tertiary amine compound, an accelerator such as ethyl N, N-dimethylaminobenzoate, or the like.

In addition, the resin composition of the present invention may use an organic solvent or a reactive diluent for viscosity adjustment. These organic solvents or reactive diluents may be used alone or in admixture of 2 or more.

As the organic solvent, for example: amides such as DMF and N, N-dimethylacetamide; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl glycol and pine oil; acetates such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cetone acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and benzyl alcohol acetate; benzoic acid esters such as methyl benzoate and ethyl benzoate; stachy materials such as Stachy methyl Stachy, stachy butyl Stachy, and the like; carbitols such as methyl carbitol, butyl carbitol and the like; aromatic hydrocarbons such as benzene, toluene, and xylene; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane and cyclohexane; acetonitrile, N-methylpyrrolidinone, and the like, but is not limited thereto.

As the reactive diluent, for example: monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether; difunctional glycidyl ethers such as resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, and propylene glycol diglycidyl ether; polyfunctional glycidyl ethers such as glycerol polyoxypropylene ether, trimethylolpropane polyoxypropylene ether, trimethylolethane polyoxypropylene ether and pentaerythritol polyoxypropylene ether; glycidyl esters such as glycidyl neodecanoate; glycidyl amines such as phenyldiglycidyl amine and tolyldiglycidyl amine, but are not limited thereto.

The organic solvent is preferably used alone or in combination of two or more such solvents in an amount of 20 to 90 mass% in terms of nonvolatile content, and the kind and amount of the organic solvent are suitably selected depending on the application. For example, in the case of printed wiring board applications, polar solvents having a boiling point of 160 ℃ or lower, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferred, and the amount used is preferably 40 to 80% by mass in terms of non-volatile matter. In addition, for the adhesive film application, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are preferably used, and the amount thereof is preferably 30 to 60% by mass in terms of non-volatile matter.

The reactive diluent is mainly used when the viscosity is reduced and the gel time is adjusted in a solvent-free system. When the amount is large, the curing reaction may not proceed sufficiently, and unreacted components may bleed out from the cured product, or physical properties of the cured product such as mechanical strength may be deteriorated, and therefore, it is not preferable to use the amount in excess of the necessary amount. Therefore, the content of the epoxy resin is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

The resin composition of the present invention can be used with various non-halogen flame retardants substantially free of halogen atoms within a range that does not reduce reliability, for the purpose of improving the flame retardancy of the cured product obtained. Examples of the non-halogen flame retardant that can be used include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. These non-halogen flame retardants are not limited to any particular one, and may be used alone, or 2 or more kinds of the same flame retardants may be used in combination, or different flame retardants may be used in combination.

The phosphorus-containing phenoxy resin of the present invention has excellent flame retardancy, and therefore, blending of a flame retardant is not necessary or can be significantly reduced.

As the phosphorus-based flame retardant, any of inorganic phosphorus-based compounds and organic phosphorus-based compounds can be used. Examples of the inorganic phosphorus-containing compound include red phosphorus, monoammonium phosphate, diammonium phosphate, ammonium phosphates such as triammonium phosphate and ammonium polyphosphate, and nitrogen-containing inorganic phosphorus-containing compounds such as phosphoric acid amides.

The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis, and examples of the surface treatment method include: (1) A method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (2) A method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide and a thermosetting resin such as a phenol resin; (3) And a method of coating a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide with a thermosetting resin such as a phenol resin at two degrees.

As the organophosphorus compound, for example: examples of the phosphorus-containing compound include general-purpose organic phosphorus-based compounds such as phosphate ester compounds, condensed phosphate esters, phosphonic acid compounds, hypophosphorous acid compounds, phosphine oxide compounds, phosphine alkane compounds, nitrogen-containing organic phosphorus-based compounds, metal phosphinates, and the like, and also organic phosphorus-based compounds such as phosphorus compounds having an active hydrogen group directly bonded to a phosphorus atom (e.g., DOPO, diphenylphosphine oxide, etc.) or phosphorus-containing phenol compounds (e.g., DOPO-HQ, DOPONQ, diphenylphosphonohydroquinone, diphenylphenylphosphino-1, 4-dioxynaphthalene, 1, 4-cyclooctylphosphonyl-1, 4-phenyldiol, 1, 5-cyclooctylphosphonyl-1, 4-phenyldiol, etc.), and derivatives obtained by reacting these organic phosphorus-based compounds with compounds such as epoxy resins or phenol resins.

The reactive phosphorus compound used for the phosphorus-containing epoxy resin and the phosphorus-containing curing agent that can be used is preferably a phosphorus-containing 2-functional phenol compound having 1 or 2 phosphorus-containing groups represented by the formula (3) or an organophosphorus compound represented by the formula (7).

Phosphorus-containing epoxy resins are disclosed in, for example, japanese patent application laid-open Nos. H04-11662, H05-214070, 2000-309624, and 2002-265562. Specific examples of the phosphorus-containing epoxy resin include: epotohto FX-305, epotohto FX-289B, epotohto FX-1225, YDFR-1320, TX-1328 (manufactured by Nissin iron-on-Steel chemical Co., ltd., above), and the like, but are not limited thereto.

These phosphorus-containing epoxy resins preferably have an epoxy equivalent (g/eq.) of 200 to 800, more preferably 300 to 780, and still more preferably 400 to 760. The phosphorus content is preferably 0.5 to 7% by mass, more preferably 1 to 6% by mass, still more preferably 2 to 5.5% by mass, and particularly preferably 3 to 5% by mass.

The phosphorus-containing curing agent may be obtained by reacting a phosphorus compound having a structural moiety represented by the formula (3) with an aldehyde and a phenol compound by the production methods disclosed in JP-A-3008-501063 and JP-A-4548547, in addition to the above-mentioned phosphorus-containing 2-functional phenol compound. In this case, the phosphorus compound having the structural moiety represented by formula (3) is incorporated into the molecule by condensation addition via aldehydes to the aromatic ring of the phenol compound. In addition, in the production method disclosed in Japanese patent application laid-open No. 2013-185002, a phosphorus-containing active ester compound can be obtained from a phosphorus compound phenol compound having a structural unit represented by formula (3) by further reacting with an aromatic carboxylic acid. In addition, in the production method disclosed in japanese unexamined patent publication No. WO2008/010429, a phosphorus-containing benzoxazine compound having a structural portion represented by formula (3) can be obtained.

The blending amount of the phosphorus compound to be used in combination is appropriately selected depending on the kind and phosphorus content of the phosphorus compound, the components of the resin composition, and the desired degree of flame retardancy. When the phosphorus compound is a reactive phosphorus compound (i.e., a phosphorus-containing epoxy resin or a phosphorus-containing curing agent), the phosphorus content is preferably 0.2 to 6 mass%, more preferably 0.4 to 4 mass%, even more preferably 0.5 to 3.5 mass%, and particularly preferably 0.6 to 3.0 mass%, based on the total solids content of the resin composition (usually, the total solids content in the resin composition means the total of components other than the solvent in the resin composition) in which the phosphorus-containing phenoxy resin, the curable resin component, the flame retardant, and other fillers or additives have all been formulated. When the phosphorus content is low, it may be difficult to ensure flame retardancy, and when the phosphorus content is too high, it may adversely affect heat resistance and solvent solubility. Therefore, when red phosphorus is used, the actual blending amount is preferably in the range of 0.1 to 2% by mass, and when an organophosphorus compound is used, the actual blending amount is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 6% by mass, based on the total solid content in the resin composition.

In addition, hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, calcium carbonate, zinc molybdate, and the like can be used as a flame retardant aid in combination with the resin composition of the present invention.

In the present invention, when a flame retardant is used in combination, a phosphorus flame retardant is preferably used, but the flame retardants described below may be used in combination.

As the nitrogen-based flame retardant, for example, triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazine and the like can be exemplified, and triazine compounds, cyanuric acid compounds, isocyanic acid compounds are preferable. The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the kind of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but for example, it is preferably blended in the range of 0.05 to 10% by mass, particularly preferably 0.1 to 5% by mass, based on the total solid content in the resin composition. When a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone flame retardant to be blended is appropriately selected depending on the type of the silicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but is preferably blended in the range of 0.05 to 20 mass% relative to the total solid content in the resin composition, for example. When a silicone flame retardant is used, a molybdenum compound, alumina, or the like may be used in combination.

As the inorganic flame retardant, for example: metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glasses, and the like. The amount of the inorganic flame retardant to be blended is appropriately selected depending on the kind of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but is preferably in the range of 0.05 to 20 mass%, particularly preferably in the range of 0.5 to 15 mass%, based on the total solid content of the resin composition in which all of the phenoxy resin, the curable resin component, the flame retardant, and other fillers or additives are blended.

As the organic metal salt-based flame retardant, for example: ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, compounds in which a metal atom is ionically or coordinately bonded to an aromatic compound or a heterocyclic compound, and the like. The amount of the organic metal salt flame retardant to be blended is appropriately selected depending on the type of the organic metal salt flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but for example, it is preferably blended in the range of 0.005 to 10 mass% with respect to the total solid content of the resin composition in which the phenoxy resin, the curable resin component, the flame retardant, and other fillers or additives have been blended.

The resin composition may contain, as necessary, other additives such as fillers, thermoplastic resins, thermosetting resins other than epoxy resins, coupling agents, antioxidants, release agents, antifoaming agents, emulsifiers, thixotropic agents, smoothing agents, and pigments, within a range not to impair the properties.

Examples of the filler include: inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, diaspore, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, and carbon; fibrous fillers such as carbon fibers, glass fibers, alumina fibers, silica alumina fibers, silicon carbide fibers, polyester fibers, cellulose fibers, aramid fibers, and ceramic fibers; fine particle rubber, and the like.

Among these, a filler which is not decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate used for the surface roughening treatment of the cured product is preferable, and fused silica and crystalline silica are particularly preferable because fine particles can be easily obtained. In addition, in particular, when the amount of the filler to be blended is large, fused silica is preferably used. Although the molten silica may be used in a crushed form or a spherical form, it is more preferable to use mainly spherical molten silica in order to increase the amount of the molten silica to be blended and to suppress an increase in the melt viscosity of the molding material. In order to further increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. Generally, the filler is used for the reasons of improving the impact resistance of the cured product and reducing the linear expansion of the cured product. In addition, when a metal hydroxide such as aluminum hydroxide, diaspore, or magnesium hydroxide is used, it acts as a flame retardant aid and has an effect of improving flame retardancy. In order to improve the thermal conductivity, alumina, silicon nitride, boron nitride, aluminum nitride, fused silica, and crystalline silica are preferable, and alumina, boron nitride, fused silica, and crystalline silica are more preferable. When used for an electrically conductive paste or the like, an electrically conductive filler such as silver powder or copper powder can be used.

In view of the low linear expansion and flame retardancy of the cured product, it is preferable that the amount of the filler to be blended is high. The content is preferably 1 to 98% by mass, more preferably 3 to 90% by mass, still more preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass, relative to the total solid content in the resin composition. When the amount is large, the adhesiveness required for the purpose of laminating the sheets may be reduced, and the cured product may be brittle and sufficient mechanical properties may not be obtained. In addition, when the amount of the filler is small, the effect of blending the filler such as improvement of impact resistance of the cured product may not be exhibited.

When the particle size of the inorganic filler is too large, voids tend to remain in the cured product, and when it is too small, the inorganic filler tends to aggregate and the dispersibility is deteriorated. The average particle diameter is preferably 0.01 to 5 μm, more preferably 0.05 to 1.5. Mu.m, still more preferably 0.1 to 1 μm. When the average particle diameter of the inorganic filler is within the above range, the fluidity of the resin composition is maintained. The average particle diameter can be measured by a particle size distribution measuring apparatus.

The resin composition of the present invention may contain a thermoplastic resin other than the phosphorus-containing phenoxy resin of the present invention. As the thermoplastic resin, for example: phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, polymethyl methacrylate resins, polycarbonate resins, polyacetal resins, cyclic polyolefin resins, polyamide resins, thermoplastic polyimide resins, polyamideimide resins, polytetrafluoroethylene resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyether sulfone resins, polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, polyvinyl formal resins, and the like. Phenoxy resins are preferred from the viewpoint of compatibility, and polyphenylene ether resins and modified polyphenylene ether resins are preferred from the viewpoint of low dielectric characteristics.

The resin composition of the present invention may be formulated with a coupling agent. By blending the coupling agent, the adhesion to the substrate and the adhesion between the matrix resin and the inorganic filler can be improved. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent. These coupling agents may be used alone or in combination of 2 or more. The amount of the coupling agent to be blended is preferably about 0.1 to 2.0% by mass based on the total solid content of the resin composition. When the amount of the coupling agent to be blended is too small, the effect of improving the adhesion between the matrix resin and the inorganic filler by blending the coupling agent cannot be sufficiently obtained, while when the amount of the coupling agent to be blended is too large, the coupling agent may bleed out from the cured product obtained.

As the silane coupling agent, there may be mentioned, for example: an epoxy silane such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, an aminosilane such as gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, a mercaptosilane such as 3-mercaptopropyltrimethoxysilane, a vinylsilane such as p-vinyltrimethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, a vinylsilane such as vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, an epoxy silane, an amine silane, a vinyl polymer silane, etc.

As the titanate coupling agent, for example: isopropyltriisostearoyltitanate, isopropyltris (N-aminoethyl/aminoethyl) titanate, diisopropylbis (dioctyl phosphate) titanate, tetraisopropylbis (dioctyl phosphite) titanate, tetraoctylbis (ditridecyl phosphite) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, and the like.

As other additives, mention may be made of: organic pigments such as quinacridone, azo and phthalocyanine pigments; inorganic pigments such as titanium oxide, metal foil pigments, and rust-proof pigments; hindered amine-based, benzotriazole-based, and diphenyl ketone-based ultraviolet absorbers; antioxidants such as hindered phenol type, phosphorus type, sulfur type, and hydrazide type; release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and the like; leveling agent, rheological control agent, pigment dispersing agent, shrinkage prevention agent, defoaming agent and other additives. The blending amount of these other additives is preferably in the range of 0.01 to 20% by mass relative to the total solid content in the resin composition.

The resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components. The resin composition containing the phosphorus-containing phenoxy resin, the curable resin component, and, if necessary, various additives can be easily made into a cured product by the same method as a conventionally known method. The cured product may be a molded cured product such as a laminate, an injection molded product, a molded product, an adhesive layer, an insulating layer, or a film. As a method for obtaining a cured product, the same method as that of a conventional resin composition can be employed, and it is possible to suitably use: injection molding, potting, dipping, drop coating, transfer molding, compression molding, etc., or a method of laminating a resin sheet, a resin-coated copper foil, a prepreg, etc., and heating and pressure-curing the laminate to obtain a laminate. The curing method of the resin composition varies depending on the formulation components and the blending amount of the resin composition, but the curing temperature is usually 80 to 300 ℃ and the curing time is usually 10 to 360 minutes. The heating is preferably performed in a two-stage treatment of a primary heating at 80 to 180 ℃ for 10 to 90 minutes and a secondary heating at 120 to 200 ℃ for 60 to 150 minutes, and in addition, in a formulation in which the glass transition temperature (Tg) exceeds the temperature of the secondary heating, it is preferable to further perform a tertiary heating at 150 to 280 ℃ for 60 to 120 minutes. By performing such secondary heating and tertiary heating, curing failure can be reduced. In the production of a semi-cured resin such as a resin sheet, a resin-coated copper foil, or a prepreg, a curing reaction of the resin composition is generally performed to such an extent that the shape is maintained by heating or the like. When the resin composition contains a solvent, most of the solvent is usually removed by a method such as heating, pressure reduction, or air drying, but 5 mass% or less of the solvent may remain in the semi-cured resin.

The resin composition of the present invention can be used in various fields such as a material for a circuit board, a sealing material, a molding material, a conductive paste, an adhesive, and an insulating material, and can be used in an insulating molding, a laminating material, a sealing material, and the like in the electric and electronic fields. Examples of the applications include, but are not limited to, printed wiring boards, flexible wiring boards, laminates for electrical/electronic circuits such as capacitors, resin-coated metal foils, film-like adhesives, adhesives such as liquid adhesives, semiconductor sealing materials, underfill materials, 3D-LSI inter-chip fillers, circuit board insulating materials, insulating sheets, prepregs, heat dissipating substrates, and resist inks.

Among these various applications, the insulating material for a printed circuit board material, an insulating material for a circuit board, and an adhesive film for build-up are used as an insulating material for a so-called electronic component-embedded substrate in which passive components such as a capacitor and active components such as an IC chip are embedded in a substrate. Among these, materials for circuit boards (laminate boards) and semiconductor sealing materials such as printed circuit board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, and the like are preferably used from the viewpoint of high flame retardancy, high heat resistance, solvent solubility, and other properties.

When the resin composition is formed into a sheet such as a laminate, the filler used is preferably in a fibrous form, and more preferably a glass cloth, a glass mat (glass mat), or a glass roving cloth, from the viewpoints of dimensional stability, bending strength, and the like.

The resin composition can be impregnated into a fibrous reinforcing base material to prepare a prepreg used for a printed wiring board or the like. For the fibrous reinforcing base material, for example, there can be used: inorganic fibers such as glass, or organic fibers such as polyester resins, polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyamide resins, but not limited thereto.

The method for producing a prepreg from a resin composition is not particularly limited, and for example, the prepreg can be obtained by preparing a resin varnish having an appropriate viscosity by further mixing a varnish-like resin composition containing the organic solvent with an organic solvent, impregnating the fibrous substrate with the resin varnish, and then heating and drying the impregnated fibrous substrate to half-cure (B-stage) the resin component. The heating temperature is preferably 50 to 200 ℃ and more preferably 100 to 170 ℃ depending on the kind of the organic solvent used. The heating time is adjusted depending on the kind of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. In this case, the mass ratio of the resin composition to be used to the reinforcing base material is not particularly limited, but it is generally preferable to adjust the resin content in the prepreg to 20 to 80 mass%.

The resin composition of the present invention can be formed into a sheet or film shape and used. In this case, the film can be formed into a sheet or a film by a conventional method. The method for producing the resin sheet is not particularly limited, but examples thereof include: (A) An extrusion molding method in which the resin composition is kneaded by an extruder, extruded, and molded into a sheet shape using a T die, a round die, or the like; (B) A cast molding method in which a resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast to form a sheet; and (C) other conventional sheet forming methods. The film thickness of the resin sheet is not particularly limited, but is, for example, 10 to 300. Mu.m, preferably 25 to 200. Mu.m, and more preferably 40 to 180 μm. When used in the build-up process, it is most preferably from 40 to 90 μm. If the film thickness is 10 μm or more, insulation properties can be obtained, and if it is 300 μm or less, the circuit distance between the electrodes does not become longer than necessary. The solvent content of the resin sheet is not particularly limited, but is preferably 0.01 to 5% by mass based on the entire resin composition. When the solvent content in the film is 0.01% by mass or more based on the whole resin composition, adhesiveness and adhesiveness are easily obtained when the film is laminated on a circuit board, and when the solvent content is 5% by mass or less, flatness after heat curing is easily obtained.

More specifically, the method for producing the adhesive sheet may be a method in which a varnish-like resin composition containing the organic solvent is applied to a supporting base film that is not dissolved in the organic solvent using a coater such as a reverse roll coater, a comma coater (comma coater), or a die coater, and then heated and dried to form the resin component B in a stage. Further, if necessary, a separate supporting base film may be stacked on the coated surface (pressure-sensitive adhesive layer) as a protective film and dried to obtain a pressure-sensitive adhesive sheet having release layers on both sides of the pressure-sensitive adhesive layer.

The supporting base film includes a metal foil such as a copper foil, a polyolefin film such as a polyethylene film or a polypropylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, a silicon film, a polyimide film, and the like, and among these, a polyethylene terephthalate film which is free from defects such as particles, excellent in dimensional accuracy, and excellent in cost is preferable. Further, a metal foil which facilitates multilayering of the laminate is preferable, and a copper foil is particularly preferable. The thickness of the support base film is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm, from the viewpoint of having strength as a support and hardly causing lamination failure.

The thickness of the protective film is not particularly limited, but is usually 5 to 50 μm. Further, in order to easily peel off the molded adhesive sheet, it is preferable to apply a surface treatment in advance using a release agent. Further, the thickness of the coating resin varnish is preferably 5 to 200 μm, more preferably 5 to 100 μm after drying.

The heating temperature is preferably 50 to 200 ℃ and more preferably 100 to 170 ℃ depending on the kind of the organic solvent used. The heating time is adjusted depending on the kind of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.

The resin sheet thus obtained is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet may be obtained by mixing a resin composition with a metal having conductivity or fine particles coated with the metal. Further, the supporting base film is peeled after being laminated on a circuit board or after being hardened by heating to form an insulating layer. When the support base film is peeled off after the adhesive sheet is heat-cured, adhesion of dust and the like in the curing step can be prevented. Here, the insulating adhesive sheet is also an insulating sheet.

A metal foil to which a resin obtained from the resin composition of the present invention is added will be described. As the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like can be used. Preferably, a metal foil having a thickness of 9 to 70 μm is used. The method for producing a resin-coated metal foil from a flame-retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil is not particularly limited, and for example, the resin-coated metal foil can be obtained by applying a resin varnish prepared by adjusting the viscosity of the phosphorus-containing resin composition with a solvent to one surface of the metal foil using a roll coater or the like, and then heating and drying the resin varnish to half-cure (B-stage) the resin component to form a resin layer. When the resin component is semi-cured, it may be dried by heating at 100 to 200 ℃ for 1 to 40 minutes, for example. Here, the thickness of the resin portion of the resin-attached metal foil is preferably formed to be 5 to 110 μm.

In addition, in order to cure the prepreg or the insulating adhesive sheet, a method of curing a laminate in the case of manufacturing a printed wiring board can be used, but the method is not limited thereto.

For example, when a laminated plate is formed using prepregs, a laminated plate can be obtained by laminating one or more prepregs, disposing a metal foil on one side or both sides to form a laminate, and pressing and heating the laminate to cure the prepregs and integrate them. As the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like can be used.

The conditions for heating and pressing the laminate may be appropriately adjusted to conditions under which the resin composition is cured, and heating and pressing may be performed, but if the amount of pressing is too low, bubbles may remain in the interior of the resulting laminate and the electrical characteristics may be degraded, and it is preferable to apply pressure under conditions that satisfy moldability. The heating temperature is preferably 160 to 250 deg.C, more preferably 170 to 220 deg.C. The pressurization pressure is preferably 0.5 to 10MPa, more preferably 1 to 5MPa. The heating and pressurizing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. When the heating temperature is low, the curing reaction may not proceed sufficiently, and when the heating temperature is high, the cured product may be thermally decomposed. When the pressing pressure is low, bubbles remain in the resulting laminated sheet and the electrical characteristics are degraded, and when the pressing pressure is high, the resin may flow out before curing and a laminated sheet having a desired thickness may not be obtained. In addition, when the heating and pressing time is short, the curing reaction may not proceed sufficiently, and when the heating and pressing time is long, the cured product may be thermally decomposed.

The single-layer laminated sheet thus obtained can be used as an inner layer material to produce a multilayer sheet. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is treated with an acid solution and blackened to obtain an inner layer material. The multilayer board is formed by forming an insulating layer with a prepreg, a resin sheet, an insulating adhesive sheet, or a metal foil with resin on one or both circuit-formed surfaces of the inner layer material, and forming a conductor layer on the surface of the insulating layer.

When the insulating layer is formed using a prepreg, a single prepreg is disposed on the circuit formation surface of the inner layer material, or a plurality of prepregs are stacked, and a metal foil is further disposed on the outer side of the prepreg to form a laminate. Then, the laminate is heated and pressed to be integrally molded, whereby a cured product of the prepreg is formed as an insulating layer and a metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal foil as that used for the laminate sheet used as the inner layer sheet can be used. The heat and pressure molding may be performed under the same conditions as the molding of the inner layer material. The surface of the multilayer laminated board thus formed may be subjected to via hole formation and circuit formation by additive or subtractive processes, thereby molding a printed circuit board. Further, a multilayer board can be further formed by repeating the above-described process using the printed wiring board as an inner layer material.

For example, when the insulating layer is formed of an insulating adhesive sheet, the insulating adhesive sheet is disposed on the circuit-formed surface of the inner layer material to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit-formed surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally molded, whereby the cured product of the insulating adhesive sheet is formed into an insulating layer and the inner layer material is formed into a plurality of layers. Alternatively, an inner layer material and a metal foil as a conductor layer are formed and a cured product of the insulating adhesive sheet is formed as an insulating layer. Here, as the metal foil, the same metal foil as that used for the laminate sheet used as the inner layer material can be used. The heat and pressure molding may be performed under the same conditions as the molding of the inner layer material.

In addition, when the resin composition is applied to the laminate to form the insulating layer, the resin composition is preferably applied to a thickness of 5 to 100 μm, and then dried by heating at 100 to 200 ℃ (preferably 150 to 200 ℃) for 1 to 120 minutes (preferably 30 to 90 minutes) to form a sheet. Formed in a process commonly referred to as casting. The thickness after drying is preferably 5 to 150. Mu.m, preferably 5 to 80 μm. Further, the viscosity of the resin composition is preferably 10 to 40000 mPas at 25 ℃, and more preferably 200 to 30000 mPas, from the viewpoint of obtaining a sufficient film thickness and preventing coating unevenness or streaks from being generated. The surface of the multilayer laminated board thus formed may be subjected to via formation or circuit formation by additive or subtractive methods to form a printed wiring board. Further, a multilayer laminated board can be further formed by repeating the above-described process using the printed wiring board as an inner layer material.

The sealing material obtained by using the resin composition of the present invention is suitably used for tape (tape) type semiconductor wafers, sealing type liquid sealing, underfill, interlayer insulating films for semiconductors, and the like. For example, as for the molding of semiconductor packages, there is a method in which a resin composition is molded by using an injection molding machine, a transfer molding machine, an injection molding machine or the like, and heated at 50 to 200 ℃ for 2 to 10 hours to obtain a molded product.

In order to prepare the resin composition into a semiconductor encapsulating material, there is a method of mixing a compounding agent such as an inorganic filler and additives such as a coupling agent and a releasing agent, which are blended as necessary, in the resin composition in advance, and then sufficiently melt-mixing them until they are uniform by using an extruder, a kneader, a roll, or the like. In this case, the inorganic filler is preferably blended in the resin composition in such a ratio that the inorganic filler is 70 to 95 mass%.

When the resin composition thus obtained is used as a tape-shaped sealing material, there is a method in which the resin composition is heated to prepare a semi-cured sheet, a sealing material tape is prepared, the sealing material tape is placed on a semiconductor wafer, the semiconductor wafer is heated to 100 to 150 ℃ to be softened and molded, and the semiconductor wafer is completely cured at 170 to 250 ℃. When used as a sealing type liquid sealing material, the obtained resin composition may be dissolved in a solvent as necessary, applied to a semiconductor wafer or an electronic component, and cured as it is.

In addition, the resin composition of the present invention can also be used as a resist ink. In this case, the following are listed: a method for preparing a resist ink composition by blending a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent in a resin composition, adding a pigment, talc and a filler, coating the resulting resist ink composition on a printed board by screen printing, and then forming a cured resist ink. The curing temperature in this case is preferably in the range of about 20 to 250 ℃.

The cured product obtained from the resin composition of the present invention has excellent heat resistance and flame retardancy, and therefore, a skeleton for imparting various characteristics to the phosphorus-containing phenoxy resin can be easily introduced. Therefore, the resin composition is particularly useful as a multilayer printed wiring board, a film adhesive, an underfill material, an insulating sheet, a prepreg, and the like, which are required to have specific properties such as flame retardancy, dielectric properties, low water absorption, and solvent solubility at the same time.

[ examples ]

The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to these examples as long as the scope of the present invention is not beyond the gist thereof. Unless otherwise specified, "part" represents part by mass, and "%" represents mass%.

The analysis method and the measurement method are shown below.

(1) Epoxy equivalent:

measured according to JIS K7236 standard, and the unit is g/eq.

From the nonvolatile fraction, a numerical value was calculated as a solid content conversion value.

(2) Weight average molecular weight (Mw):

determined by GPC measurement. Specifically, the column temperature was 40 ℃ using a chromatograph equipped with a column (TSKgel SuperH-H, superH2000, superHM-H, and SuperHM-H, manufactured by TOSOH Co., ltd.) in series with a main body (HLC-8320 GPC, manufactured by TOSOH Co., ltd.). The elution solution used DMF (containing 20mM lithium bromide) was passed through an RI detector at a flow rate of 0.3 mL/min. As the measurement sample, 20. Mu.L of "a sample dissolved in 0.1g of solid content in 10mL of DMF and filtered through a 0.45 μm microfilter" was used. Mw was calculated by conversion from a calibration curve obtained from a standard polyethylene oxide (SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150, manufactured by TOSOH Co., ltd.). Further, GPC-8020 model II version 6.00 manufactured by TOSOH corporation was used for data processing.

(3) Phosphorus content:

sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, and wet ashing was performed by heating, whereby all phosphorus atoms were used as orthophosphoric acid. The metavanadate and molybdate were reacted in an acidic sulfuric solution, and the absorbance at 420nm of the resulting phosphovanadomolybdic acid complex was measured, and the phosphorus content determined from a calibration curve prepared in advance was expressed as% of phosphorus.

(4) Glass transition temperature (Tg):

measured according to IPC-TM-650.4.25. C. Specifically, the extrapolated glass transition onset temperature (Tig) of the DSC chart obtained in the second cycle of differential scanning calorimetry is used as a representation. The differential scanning calorimetry apparatus used was "EXSTAR6000DSC6200" manufactured by SII NanoTechnology, inc. For the measurement sample, a resin film was pressed (punching), laminated, and packed in an aluminum capsule. The measurement was performed in two cycles from room temperature to 240 ℃ at a temperature rising rate of 10 ℃/min.

(5) Flame retardancy:

the evaluation was carried out in accordance with UL94VTM (safety certification Specification by Underwriters Laboratories Inc.) by the vertical method. The evaluation is described as VTM-0, VTM-1, VTM-2. The flame retardancy is optimally varied in VTM-0 and becomes poor in the order of VTM-1 and VTM-2. But completely combusted is described as X.

(6) Water absorption:

the resin film was cut into test pieces of 50mm × 50mm square using 5 pieces for measurement. The mass was measured immediately after drying the test piece at 100 ℃ for 10 minutes in an air atmosphere using a hot air circulation oven, and the test piece was immersed in warm water at 50 ℃ to determine the water absorption from the mass increase after 48 hours.

Synthesis example 1

In a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen gas inlet, a cooling tube, and a water separator, 200 parts of propylene glycol monomethyl ether acetate, 108 parts of DOPO, and 4.2 parts of water (molar ratio of water to DOPO = 0.47) were fed at room temperature, and the temperature was raised to 70 ℃ in a nitrogen atmosphere to completely dissolve the propylene glycol monomethyl ether acetate. Therein, it took 30 minutes to feed NQ78.9 parts (molar ratio NQ/DOPO = 0.999). After the completion of the feeding, the temperature was raised to 145 ℃ from the start of the reflux, and the reaction was continued for 5 hours while maintaining the reflux temperature.

The resulting product was cooled to room temperature and filtered by suction filtration. After 2500 parts of benzyl acetate was added to the residue and heated to be completely dissolved, the mixture was cooled to room temperature and left to stand for 1 day, and the resulting precipitate was filtered by suction filtration. The filtrate was poured into 39% aqueous methanol, and the resulting precipitate was filtered by suction to obtain a phosphorus-containing 2-functional phenol compound represented by the following formula (9) (purity: 99% or more) as a residue.

Synthesis example 2

In the same apparatus as in synthesis example 1, 108 parts of DOPO, 53 parts of BQ (BQ/DOPO molar ratio = 0.98), 1.8 parts of water (water/DOPO molar ratio = 0.20), and 200 parts of PMA were fed at room temperature, and the reaction was continued for 3 hours while the temperature was raised to 145 ℃ at the start of reflux in a nitrogen atmosphere.

The resulting product was cooled to room temperature and filtered by suction filtration. After 2500 parts of benzyl acetate was added to the residue and heated to completely dissolve it, it was cooled to room temperature and left standing for 1 day, and the resulting precipitate was filtered by suction filtration. The filtrate was poured into 39% aqueous methanol, and the resulting precipitate was filtered by suction to obtain a phosphorus-containing 2-functional phenol compound represented by the following formula (10) (purity: 99% or more) as a residue.

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

[2 functional epoxy resin ]

(A-1): bisphenol A type liquid epoxy resin (product name: YD-8125, manufactured by Nissi iron Tokyo chemical Co., ltd., product name: 172, epoxy equivalent: 172, repetition number j of the formula (8): approximately 0.01)

(A-2): epoxy resin of 3,3', 5' -tetramethyl-4, 4' -biphenol (product name: YX-4000, epoxy equivalent: 186, j ≈ 0.06, mitsubishi Chemical corporation)

(A-3): 4,4' - (3, 5-trimethylcyclohexylidene) bisphenol (product name: TX-1468, epoxy equivalent: 218, j ≈ 0.04) manufactured by Nippon iron Tokyo chemical Co., ltd.)

(A-4): bisphenol F type liquid epoxy resin (product name: YDF-170, epoxy equivalent: 169, manufactured by Xinri iron Tokyo chemical Co., ltd.)

(A-5): phenol novolac type epoxy resin (product name: YDPN-638, epoxy equivalent: 177, manufactured by Xinri iron-to-gold chemical Co., ltd.)

[ 2-functional phenol Compound ]

(B-1): synthesis of the phosphorus-containing 2-functional phenol Compound obtained in example 1 (hydroxyl equivalent: 294, phosphorus content 10.5%)

(B-2): synthesis of the phosphorus-containing 2-functional phenol Compound obtained in example 2 (hydroxyl equivalent: 269, phosphorus content: 11.5%)

(B-3): phosphorus-containing Compound, DOPO-HQ (product name: HCA-HQ, hydroxyl equivalent: 162, phosphorus content: 9.5% by Sanphotochemical Ltd.)

(B-4): phosphorus-containing Compound, DOPO-NQ (product name: HCA-NQ, hydroxyl equivalent: 187, phosphorus content: 8.3%, manufactured by Sanoto chemical Co., ltd.)

(B-5): bisphenol A (hydroxyl equivalent: 114 manufactured by Nissi iron Tokko Chemicals Co., ltd.)

[ catalyst ]

(C-1): 2-Ethyl-4-methylimidazole (product name: CUREZOL2E4MZ, manufactured by Siguo Kasei Kogyo Co., ltd.)

(C-2): triphenylphosphine (reagent)

(C-3): three (2, 6-dimethoxyphenyl) phosphine (reagent)

[ hardening agent ]

DICY: dicyanodiamine (product name: DIHARD, active hydrogen equivalent 21, manufactured by CARBIDE INDUSTRIAL CO., LTD.)

Example 1

In a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen-introducing device and a cooling tube, (A-1) 561 parts, (B-2) 130 parts, (B-5) 309 parts and diethylene glycol dimethyl ether 430 parts were fed at room temperature, nitrogen was flowed, the temperature was raised to 145 ℃ while stirring, 0.1 part of (C-1) was added, and then the temperature was raised to 165 ℃ to carry out a reaction at the same temperature for 10 hours. 800 parts of methylsalic acid and 800 parts of cyclopentanone were diluted and mixed to obtain a resin varnish 1 of a phosphorus-containing phenoxy resin having a nonvolatile content of 33%. This resin varnish was applied to a release film (polyimide film) using a roll coater so that the thickness of the film after solvent drying became 60 μm, dried at 150 ℃ for 10 minutes, and then the dried film was peeled off from the release film. The 2 dried films were stacked and pressed for 60 minutes by a vacuum press under conditions of a degree of vacuum of 0.5kPa, a drying temperature of 180 ℃ and a pressing pressure of 2MPa to obtain a resin film having a thickness of 100. Mu.m. Further, spacers having a thickness of 100 μm are used for adjusting the thickness.

The epoxy equivalent and Mw were measured using a resin varnish, and the phosphorus content, tg, flammability, and water absorption were measured using a resin film, and the results are shown in table 1. The molar ratio in the table represents the molar ratio of (epoxy group of the raw epoxy resin)/(hydroxyl group of the raw 2-functional phenol compound). X1 (mol%) represents the ratio of the group (X1) in the total number of moles of X in formula (1) in mol%.

Examples 2 to 7

Resin varnishes 2 to 7 and resin films were obtained in the same manner as in example 1, using the same apparatus in accordance with the compounding ratios (parts) shown in Table 1. The results of measuring the epoxy equivalent, mw, phosphorus content, tg, flammability, and water absorption are shown in table 1.

Comparative examples 1 to 6

Resin varnishes H1 to H6 and resin films were obtained in the same manner as in example 1, using the same apparatus in accordance with the blending ratios (parts) described in table 2. The results of measuring the epoxy equivalent, mw, phosphorus content, tg, flammability, and water absorption are shown in table 2.

TABLE 1

TABLE 2

In examples 1 and comparative examples 1,2 and 2,5 and 4, and 7 and 6, the phosphorus-containing groups represented by formula (3) were contained and the phosphorus content, epoxy equivalent and Mw were almost the same, and the comparative examples were different in that they did not contain the group (X1). Further, it is understood from examples 5, 6 and 7 that the flame retardancy is excellent even if the kind of the group (X2) is changed.

In example 3, the phosphorus content was increased until the flame retardancy satisfied VTM-0, as compared with comparative example 3, and it was found that the example having the group (X1) was excellent in heat resistance and water resistance.

In example 4, the water absorption rate was the same as that in comparative example 3, and it was found that the example having the group (X1) was excellent in heat resistance and water resistance and the phosphorus content was increased.

As described above, the introduction range of the group (X2) is widened, and various properties can be imparted.

Example 8

303 parts of the resin varnish 1 obtained in example 1, 100 parts of (A-4) as an epoxy resin, 6.2 parts of DICY as a curing agent, 0.2 part of (C-1) as a curing accelerator, 50 parts of methylsulfinic acid as a solvent, and 50 parts of DMF were added thereto and mixed by stirring to obtain a varnish of a composition. The varnish composition was applied to a release film using a roll coater so that the thickness of the dried film after solvent drying became 60 μm, dried at 150 ℃ for 10 minutes, and then the dried film was peeled off from the release film. The 2 dried films were stacked and pressed by a vacuum press under conditions of a degree of vacuum of 0.5kPa, a heating temperature of 200 ℃ and a pressing pressure of 2MPa for 60 minutes to obtain a cured film having a thickness of 100 μm. Further, spacers having a thickness of 100 μm are used for adjusting the thickness.

Examples 9 to 11 comparative examples 7 to 8

Epoxy resin composition varnishes and cured films were obtained in the same manner as in example 8, except for the compounding ratios (parts) shown in Table 3. The cured film was measured for Tg, flammability, and water absorption, and the results are shown in table 3.

TABLE 3

It is understood that the examples 8 and comparative examples 7 and 9 and comparative examples 8 are prepared in the same manner, but the examples are excellent in heat resistance and water absorption.

Claims

1. A phosphorus-containing phenoxy resin represented by the following formula (1), having a weight average molecular weight of 10,000 to 200,000;

wherein X is a 2-valent group, at least a part of X is a group X1 represented by the following formula (2), Y is independently a hydrogen atom or a glycidyl group, n is the number of repetitions and has an average value of 25 to 500;

wherein A is an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, which may have, as a substituent, any one of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms, and Z is a phosphorus-containing group represented by the following formula (3);

wherein R is ¹ And R ² Is a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom, and may be different or the same, and may be linear, branched or cyclic, R ¹ And R ² Or may be bonded and form a cyclic structural moiety, and k1 and k2 are independently 0 or 1.

2. The phosphorus-containing phenoxy resin according to claim 1, wherein the phosphorus-containing group represented by formula (3) is a phosphorus-containing group represented by the following formula (3 a) and/or (3 b);

wherein R is ³ And R ⁴ Each independently a hydrocarbon group having 1 to 11 carbon atoms, m1 each independently an integer of 0 to 4, and m2 each independently an integer of 0 to 5.

3. The phosphorus-containing phenoxy resin according to claim 1 or 2, wherein the X contains the group X1 and a phosphorus-free group X2 containing no phosphorus in a range of 25 to 75 mol% relative to the number of moles of the whole X,

the phosphorus-free group X2 contains at least any one of 1 group having 2 valences represented by the following formulae (4 a) to (4 c);

wherein R is ⁵ Is a direct bond or is selected from C1-20 hydrocarbon group, -CO-, -O-, -S-, -SO ₂ -and-C (CF) ₃ ) ₂ A 2-valent radical of (A), R ⁶ 、R ⁷ And R ⁸ Each independently a hydrocarbon group having 1 to 11 carbon atoms, m3 and m4 each independently an integer of 0 to 4, and m5 an integer of 0 to 6.

4. The phosphorus-containing phenoxy resin according to claim 1 or 2, wherein the phosphorus content is 1 to 10 mass%.

5. A resin composition comprising the phosphorus-containing phenoxy resin according to any one of claims 1 to 4 and a curable resin component.

6. The resin composition according to claim 5, wherein the curable resin component is at least 1 resin selected from the group consisting of an epoxy resin, an acrylate resin, a melamine resin, an isocyanate resin, and a phenol resin.

7. A material for circuit boards, which is obtained by using the resin composition according to claim 5 or 6.

8. A cured product obtained by curing the resin composition according to claim 5 or 6.