TWI786271B - Phosphorus-containing phenoxy resin, resin composition thereof, and cured product thereof - Google Patents

Abstract

The present invention provides a phosphorus containing phenoxy resin having excellent safety, flame retardancy, adhesion, processability and heat resistance, and a resin composition using the same.

The phosphorus containing phenoxy resin of the present invention is represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000.

Wherein, X is a divalent group containing a group (X1) represented by the formula (2), Y is independantly 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 the formula (3).

Description

Phosphorus-containing phenoxy resin, resin composition of phosphorus-containing phenoxy resin, and cured product

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

Epoxy resins are widely used mainly as electrical insulating materials because of their excellent electrical insulating properties, electrical properties, adhesiveness, mechanical properties of cured products, and the like. From the viewpoint of safety, such electrical insulating materials are required to have high flame retardancy, and they are made flame-retardant by using a halogen-based flame retardant, an antimony compound, or a phosphorus-based flame retardant in combination. However, in recent years, regulations on materials used in such flame retardants have gradually increased in terms of environmental pollution and toxicity. Among them, the toxicity and carcinogenicity of organic halogen substances such as dioxin have become problems, and the reduction and elimination of halogen-containing substances are strongly required. In addition, from the viewpoint of the carcinogenicity of antimony, there is an increasing demand for reduction and removal of antimony compounds. Under such circumstances, phosphorus-based flame retardants are being proposed and reviewed for replacement.

Also, in some applications, epoxy resins are increased in molecular weight by various methods to impart film-forming properties, and are used as phenoxy resins. In particular, flame retardancy, high heat resistance, and the like are listed as performances required of phenoxy resins for use in electrical insulating materials. For environmental problems, halogens are not used and flame retardancy is exhibited. Although phenoxy resins containing phosphorus atoms are disclosed in some documents, they are water-absorbent, and solvent solubility is poor due to limitations in solvents for dissolving them. . (Patent Documents 1, 2). Also, methods for improving water absorption and solvent solubility have been disclosed, but since aliphatic skeletons are used in large amounts, flame retardancy cannot be ensured unless the content of phosphorus atoms is increased (Patent Documents 3 and 4).

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-310939

[Patent Document 2] Japanese Unexamined Patent Publication No. 2002-3711

[Patent Document 3] Japanese Patent Laid-Open No. 2015-196719

[Patent Document 4] Japanese Patent Laid-Open No. 2015-196720

The object of the present invention is to provide a phosphorus-containing phenoxy resin that solves the above-mentioned problems and can be applied to the electrical/electronic field with excellent flame retardancy, high heat resistance, and excellent low water absorption, and a phosphorus-containing phenoxy resin using the phosphorus-containing phenoxy resin. Resin composition of oxygen resin, material for circuit board, and cured product thereof. In addition, the purpose of the present invention is to provide flame retardancy, high heat resistance and low water absorption with good balance and low linear expansion. Phosphorus-containing phenoxy resins with good swelling, elongation, high thermal conductivity, solvent solubility, low dielectric constant, low dielectric loss tangent, etc.

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

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

In formula (2), A is an aromatic ring group selected from benzene ring, naphthalene ring, anthracene ring or phenanthrene ring. These aromatic ring groups may have alkyl groups with 1 to 8 carbons, Alkoxy, cycloalkyl with 5 to 8 carbons, aryl with 6 to 10 carbons, aralkyl with 7 to 11 carbons, aryloxy with 6 to 10 carbons, or aryloxy with 7 to 11 carbons Any of aralkyloxy groups is used as a substituent. Z is a phosphorus-containing group represented by the following formula (3).

In formula (3), R ¹ and R ² are hydrocarbon groups with 1 to 20 carbon atoms which may have heteroatoms, and may be different or the same, and may be linear, branched, or cyclic. In addition, R ¹ and R ² may also be bonded to form a ring structure site. k1 and k2 are 0 or 1 independently.

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

In formulas (3a) and (3b), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 11 carbons. m1 is an integer of 0 to 4 each independently, and m2 is an integer of 0 to 5 each independently.

The above-mentioned X preferably contains the above-mentioned group (X1), and contains a phosphorus-free group (X2) that does not contain phosphorus in a range of 25 to 75 mol% with respect to the total molar number of X.

The above-mentioned phosphorus-free group (X2) preferably contains at least one of any of the divalent groups represented by the following formulas (4a) to (4c).

In formula (4a), R ⁵ is a direct bond or 2 selected from hydrocarbon groups with 1 to 20 carbons, -CO-, -O-, -S-, -SO ₂ - and -C(CF ₃ ) ₂ - price base.

In formulas (4a) to (4c), R ⁶ , R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 11 carbons. 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% by mass.

In addition, the present invention is a resin composition in which a curable resin component is blended into the above-mentioned phosphorus-containing phenoxy resin. The curable resin component is preferably at least one selected from epoxy resin, acrylate resin, melamine resin, isocyanate resin and phenol resin.

In addition, the present invention is a material for a circuit board obtained from the above-mentioned resin composition, and is a cured product of the resin composition.

Although the phosphorus-containing phenoxy resin of the present invention is halogen-free, it still exhibits good flame retardancy and high heat resistance, and can have solvent solubility, low linear expansion, elongation, and high thermal conductivity in a well-balanced manner depending on the application. , Low water absorption, low dielectric constant, low dielectric loss tangent and other characteristics. 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 types of adhesives, coatings, civil construction materials, electrical/electronic parts insulation materials, etc. Various fields, especially used as insulating injection molding materials, laminated materials, sealing materials, etc. in the electrical/electronic field.

Embodiments of the present invention will be described in detail below. The phosphorous-containing phenoxy resin of the present invention is represented by the above formula (1) and has a weight average molecular weight (Mw) of 10,000 to 200,000, preferably 20,000 to 150,000 as determined by gel permeation chromatography (GPC). , more preferably 25,000 to 100,000, and more preferably 30,000 to 80,000. When the Mw is low, the film forming properties and elongation of the film are poor, and when the Mw is too high, the handleability of the resin is remarkably deteriorated. Furthermore, the measurement method of GPC is based on the conditions described in the examples.

In formula (1), X is a divalent group, and contains the group (X1) represented by said formula (2) 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.

If X contains the above-mentioned oxygen-containing group (X1), there is no special limitation, but it is preferred to have both an oxygen-containing group (X1) and a phosphorus-free group (X2) that does not contain phosphorus. In terms of the phosphorus-free group (X2) , the groups represented by the above-mentioned formulas (4a) to (4c) etc. can be mentioned. In addition, a P-containing group (X3) other than the above-mentioned group (X1) may be contained as a phosphorus-containing group.

Y are each independently a hydrogen atom or a glycidyl group.

n is the number of repetitions and its average value is 25 to 500, preferably 40 to 400, more preferably 50 to 350, and more preferably 70 to 300. n is related to the above Mw.

In the above 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 ring groups may have an alkyl group having 1 to 8 carbons, an alkoxy group having 1 to 8 carbons, a cycloalkyl group having 5 to 8 carbons, an aryl group having 6 to 10 carbons, a carbon number Any one of 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 is used as a substituent. For example, the alkyl group with 1 to 8 carbons includes methyl, ethyl, propyl, isopropyl, n-butyl, tertiary butyl, hexyl, etc. For the aryl group or aryloxy group having 6 to 10 carbon atoms, phenyl, naphthyl, phenoxy, naphthyloxy, etc. can be mentioned, and for the aryl group or aryloxy group having Examples of the aralkyl group or aralkyloxy group include benzyl group, phenethyl group, 1-phenylethyl group, benzyloxy group, naphthylmethyloxy group and the like. Preferred A is: benzene ring, methyl substituent of benzene ring, 1-phenylethyl substituent of benzene ring, naphthalene ring, methyl substituent of naphthalene ring, or 1-phenylethyl of naphthalene ring Substitutes. For purposes that require more solvent solubility, benzene rings, methyl substitutions of benzene rings, and 1-phenylethyl substitutions of benzene rings are preferred; for purposes that require more flame retardancy and heat resistance , preferably a naphthalene ring, a methyl substituent of the naphthalene ring, or a 1-phenylethyl substituent of the naphthalene ring.

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

In formula (3), R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom, and may be different or the same, and may be linear, branched, or cyclic. In addition, R ¹ and R ² may also be bonded to form a ring structure site. The most preferred is an aromatic ring group. When R ¹ and R ² are aromatic ring groups, they may have alkyl groups with 1 to 8 carbons, alkoxy groups with 1 to 8 carbons, cycloalkyl groups with 5 to 8 carbons, and aromatic groups with 6 to 10 carbons. group, aralkyl group having 7 to 11 carbons, aryloxy group having 6 to 10 carbons or aralkyloxy group having 7 to 11 carbons as substituents. As the heteroatom, there are exemplified oxygen atoms and the like, 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.

Examples of the phosphorus-containing group represented by the formula (3) include groups represented by the above-mentioned formula (3a) or (3b).

In formula (3a) and formula (3b), R ³ and R ⁴ are independently a hydrocarbon group with 1 to 11 carbons, specifically methyl, ethyl, tertiary butyl, cyclohexyl, phenyl, toluene Base, benzyl, methyl, cyclohexyl, phenyl, tolyl, benzyl, preferably methyl, phenyl, benzyl.

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

Other preferable examples of the phosphorus-containing group represented by the above formula (3) include phosphorus-containing groups represented by the following formulas (a1) to (a10).

The above group (X1) imparts a phosphorus-containing phenoxy resin excellent in flame retardancy and heat resistance. Compared with the structure of the phosphorus atom skeleton in the conventional phosphorus-containing phenoxy resin (such as the structure shown in the formula (5) described later), the chemical structure of the group (X1) has higher rigidity and can be Molecular movement is more restrained, so the heat resistance is improved, and the volume is larger, hydrophobic and rigid, so it is speculated that heat resistance can be improved and water absorption can be reduced. On the other hand, although it is appropriate to introduce structures other than phosphorus-containing groups to improve other properties, since even a small amount of group (X1) can still exert the desired effect, more other structures can be introduced, and other properties can be easily imparted.

In formula (1), at least a part of X is a group (X1). Relative to all X, the base (X1) is 1 to 100 mol%, preferably 2 to 75 mol%, more preferably 5 to 50 mol%, more preferably 10 to 40 mol%, especially The best is 15 to 35 mole%. In addition, it has one or more groups (X1) on average in one molecule.

As for the preferable structure of the above-mentioned group (X1), structures represented by the following formulas (2a) to (2f) can be cited, but not limited thereto. Particularly preferred are structures represented by the following formulas (2a') to (2f').

In addition, X may contain a P-containing group (X3) containing a phosphorus atom other than the group (X1). As the P-containing group (X3), preferably, a divalent group represented by the following formula (5) having one of the aforementioned Zs can be mentioned.

In the above formula (5), A and Z have the same meaning as A and Z in the above formula (2), respectively.

In addition, X in formula (1) may contain a phosphorus-free group (X2) that does not contain a phosphorus atom. As for the phosphorus-free group (X2), it is preferable to include the above-mentioned formulas (4a) to (4c) The 2 valence base.

In formula (4a), R ⁵ is a direct bond or 2 selected from hydrocarbon groups with 1 to 20 carbons, -CO-, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - price base. Examples of the above-mentioned hydrocarbon groups include: -CH ₂ -, -CH(CH ₃ )-, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, cyclohexylene, cyclododecyl, cyclosubene Pentyl, methylcyclopentylene, trimethylcyclopentylene, cyclohexylene, methylcyclohexylene, trimethylcyclohexylene, tetramethylcyclohexylene, cyclooctylene, cyclodecylene Diyl, bicyclo[4.4.0]decyl, bicyclohexylene, phenylene, xylylene, phenylmethylene, diphenylmethylene, 9H-oxa-9-ylidene, Or extended norbornyl, extended adamantyl, extended tetrahydrodicyclopentadienyl, extended tetrahydrotricyclopentadienyl, with norbornane structure, tetrahydrodicyclopentadiene structure, tetrahydrotricyclic The divalent group of pentadiene structure. Among these, direct bonding, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CO-, -O-, -S-, -SO ₂ - are preferred. , cyclohexylene, trimethylcyclohexylene, cyclooctylene, cyclododecylene, bicyclohexylene, 9H-oxa-9-ylidene or divalent groups with tetrahydrodicyclopentadiene structure , more preferably a direct bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, trimethylcyclohexylene, 9H-oxa-9-ylidene or with tetrahydro Dicyclopentadiene structure divalent group.

When R ⁵ is a direct bond, the biphenyl skeleton can be 2,2'-biphenyl skeleton, 2,3'-biphenyl skeleton, 2,4'-biphenyl skeleton, 3,3'-biphenyl skeleton , 3,4'-biphenyl skeleton, and 4,4'-biphenyl skeleton, but preferably 4,4'-biphenyl skeleton. In addition, when R ⁵ is other than a direct bond, the bonding position relative to the aromatic ring can be 2,2', 2,3', 2,4', 3,3', 3, Any of the 4' position and the 4,4' position, but preferably the 4,4' position.

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

In formula (4b) and formula (4c), R ⁷ and R ⁸ are the same as the description of R ⁶ above. 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.

In X of the formula (1), by introducing a phosphorus-free group (X2), it contributes to properties other than flame retardancy such as solvent solubility, low linear expansion, elongation, high thermal conductivity, low dielectric constant, Improvements such as low dielectric loss tangent, heat resistance, and low water absorption are further improved, so it is better to determine the amount of introduction according to the purpose. Relative to the total moles of X, the content of the non-phosphorous group (X2) is preferably 25 to 75 moles.

Hereinafter, the "phosphorus-free group (X2)" is sometimes simply referred to as the group (X2), and the "P-containing group" is simply referred to as the group (X3).

X may have group (X1), group (X2) and group (X3), but group (X1) must be present and one molecule or more of group (X1) is contained. From another point of view, it may contain more than 1 mol%.

The base (X3) improves the flame retardancy similarly to the base (X1), but since the base (X1) has a greater effect than the base (X3), a small amount shows a sufficient effect. However, there is a commercially available product for the introduction of the base (X3), so there is an advantage of easy acquisition.

Base (X2) enhances properties different from those possessed by bases (X1) and bases (X3). Depending on the application, the phenoxy resin should preferably have the above-mentioned properties, so the desired properties can be imparted by the type and amount of the group (X2). If the effect of the group (X1) and the group (X3) can be exerted in a small amount, the group (X2) can be contained sufficiently to impart sufficient desired properties.

For example, when a thermoplastic resin is used as a flame retardant, it is preferable not to contain a phosphorus-free group (X2) but only a group (X1) and a group (X3). From the viewpoint of flame retardancy, it is preferable to use There is only the group (X1), but from the viewpoint of productivity, a mixture of the group (X1) and the group (X3) is preferable.

In addition, in conventional phosphorus-containing phenoxy resins that do not contain phosphorus groups (X2) and groups (X3), it is necessary to add groups (X2) in order to impart new properties and improve certain properties. When there is no room for flame retardancy, so far there is no other way but to give up the characteristics of phenoxy resin itself and to make other preparations to deal with it. In this case, by setting part or all of base (X3) as base (X1) Since there is room for flame retardancy, the group (X2) can be introduced, and the phenoxy resin itself can have the necessary characteristics.

The structure without phosphorus group (X2) can be selected according to the properties to be imparted. For example, in order to further improve heat resistance, a divalent group having a norbornyl group, an adamantyl group, or the like, or a 9H-terrene-9-ylidene group, etc. may be mentioned. For the improvement of solvent solubility, biphenylene, methylenebisylyl, methylenebisylyl, etc. which have a methyl substituent are mentioned. As far as the improvement of dielectric properties is concerned, divalent groups having a tetrahydrodicyclopentadiene structure, a tetrahydrotricyclopentadiene structure, etc., or trifluoromethyl, benzyl substituents, 1- A divalent group such as a phenylethyl substituent. As for the improvement of the hygroscopic property, a divalent group having a trifluoromethyl group or a 9H-oxa-9-ylidene group may be mentioned.

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

Although the content of phosphorus-free group (X2) varies depending on the application, it is 0 to 99 mol%, preferably in the above range, more preferably 45 to 55 mol%.

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

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

The phenoxy resin of the present invention can adopt epoxy-terminated, phenolic hydroxyl-terminated, or mixed forms thereof. Usually, phenoxy resin does not consider the reaction of epoxy groups, so it is not necessary to define the epoxy equivalent (g/eq.), but it can be more than 5,000. When it is less than 5,000, the film-forming properties and elongation of the film are poor, which is unfavorable. In addition, when it becomes a phenolic hydroxyl group terminal, the epoxy group concentration will become 0, so the epoxy equivalent will become an infinite value. Therefore, the definition of the upper limit of the epoxy equivalent has no critical significance in essence. However, from the viewpoint of improving operability, it is preferably at most 100,000, more preferably at most 50,000, still more preferably at most 30,000, and most preferably at most 20,000.

There are one-stage method (direct method) and two-stage method (indirect method) as shown below in the method for producing the phosphorus-containing phenoxy resin of the present invention, but it is not limited to these.

The one-stage method makes epihalohydrins such as epichlorohydrin or epibromohydrin and phenolic compounds containing phosphorus-containing 2-functional phenolic compounds represented by the following formula (6a) react in alkalis such as sodium hydroxide or potassium hydroxide. A method of reacting in the presence of metal hydroxides. In addition to the above-mentioned phosphorus-containing 2-functional phenolic compound, the phenolic compound of the raw material may also include a phosphorus-free 2-functional phenolic compound represented by the following formula (6b), and other phosphorus-containing phenolic compounds represented by the following formula (6c). 2 functional phenolic compounds.

HX ¹ -H (6a)

HX ² -H (6b)

HX ³ -H (6c)

Here, X ¹ , X ² , and X ³ are synonymous with the above-mentioned group (X1), group (X2), and group (X3), respectively.

The two-stage method is a method of reacting a bifunctional phenolic compound and a bifunctional epoxy resin usually in the presence of a catalyst.

As the bifunctional phenolic compound and the bifunctional epoxy resin, one or more phenolic compounds or epoxy resins having the above-mentioned group (X1), group (X2) or group (X3) can be used. In this case, at least one of the bifunctional phenol compound and the bifunctional epoxy resin contains the above group (X1).

Examples of bifunctional phenolic compounds include phenolic compounds represented by the above formulas (6a) to (6c). Bifunctional epoxy resins include epoxy resins obtained by epoxidizing the phenol compounds represented by the above formulas (6a) to (6c). The above-mentioned bifunctional epoxy resin and phenol compound may simultaneously contain two or more kinds of groups (X1), groups (X2) or groups (X3) in the molecule.

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

The Mw and epoxy equivalent of phosphorus-containing phenoxy resin can be produced in the target range by adjusting the feed molar ratio of epihalohydrin and 2-functional phenolic compound in the one-stage method, and can be produced in the two-stage method by Adjust the feed molar ratio of bifunctional epoxy resin and bifunctional phenolic compound to produce the target range. Although the phosphorus-containing phenoxy resin of the present invention can be obtained by any production method, generally speaking, compared with the one-stage method, the two-stage method is easier to obtain the phenoxy resin, so it is better to use two stage method.

The method for producing the phosphorus-containing bifunctional phenolic compound represented by the above formula (6a) is not particularly limited, but preferably relative to 1 mole of the organophosphorus compound represented by the following formula (7), The quinone compound is used in the range of 0.5 mole or more and less than 1.0 mole, and in an organic solvent with 0.05 to 0.5 mole of water relative to 1 mole of the organophosphorus compound, the reaction temperature is 100 to 200 ° C, relatively It is preferable to carry out the production method of the reaction under the reflux state.

In formula (7), R ¹ , R ² , k1 and k2 have the same meaning as R ¹ , R ² , k1 and k2 in formula (3), respectively.

In the above reaction, a phosphorus compound having a structure represented by the above formula (5) is by-produced. In order to isolate the target phosphorus-containing bifunctional phenolic compound, after the reaction is completed, the reaction product can be mixed with a good solvent, and while the target phosphorus-containing bifunctional phenolic compound is dissolved, the by-product phosphorus compound can be used as removal of insoluble components. Existing in the solution after solid content separation Most of them are phosphorus-containing bifunctional phenolic compounds that belong to the target product, but sometimes a small amount of by-product phosphorus compounds remains, so it is better to further refine for high purity. In the purification method, the above-mentioned solution is mixed with a poor solvent to precipitate the crystals of the phosphorus-containing bifunctional phenolic compound which is the target product. Also, by-products and the like are dissolved in the poor solvent solution. In addition, purification operations such as extraction, washing, distillation, etc. may be performed as other purification methods. Furthermore, since the phosphorus compound having the structure represented by the above formula (5) will donate the group (X3), it can also be used as a useful component that can exert flame retardancy, and the mixture can be used as it is without isolating part or all of it. .

Examples of organic solvents that can be used in the above reaction include: alcohols such as 1-methoxy-2-propanol, acetates such as diethylene glycol monoethyl ether acetate, methyl benzoate, etc. Parabens, cellosolves such as methyl cellosolve, carbitols such as butyl carbitol, ethers such as diethylene glycol diethyl ether, aromatic hydrocarbons such as toluene, N , Amides such as N-dimethylformamide (DMF), dimethylsulfide, acetonitrile, N-methylpyrrolidone, etc., but not limited thereto. These organic solvents can be used individually or in mixture of 2 or more types.

The quinone compounds that can be used in the above reaction can be used without problems as long as the purity is 90% or higher as an industrial product.

When A in formula (2) becomes a benzene ring, the quinone compound used can be, for example: benzoquinone, methylbenzoquinone, ethylbenzoquinone, butylbenzoquinone, dimethylbenzoquinone, diethylbenzoquinone Quinone, dibutylbenzoquinone, methylisopropylbenzoquinone, diethoxybenzoquinone, methylmethoxybenzoquinone, phenylbenzoquinone, tolylbenzoquinone, ethoxybenzoquinone, di Phenylbenzoquinone, etc.

When A in formula (2) becomes a naphthalene ring, the quinone compound used can be, for example: naphthoquinone, menaquinone, cyclohexylnaphthoquinone, methoxynaphthoquinone, ethoxynaphthoquinone, dimethyl Naphthoquinone, dimethylisopropylnaphthoquinone, methylmethoxynaphthoquinone, etc.

When A in formula (2) becomes an anthracycline, the quinone compound used can be, for example: anthraquinone, methylanthraquinone, ethylanthraquinone, methoxyanthraquinone, dimethoxyanthraquinone, diphenyl oxyanthraquinone, etc.

When A in formula (2) becomes a phenanthrene ring, the quinone compounds used can be, for example: phenanthrenequinone, methylphenanthrenequinone, isopropylphenanthrenequinone, methoxyphenanthrenequinone, butoxyphenanthrenequinone, dimethylphenanthrenequinone, Oxyphenanthrenequinone, etc.

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

As for the organophosphorus compound represented by the above formula (7), for example: dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, diphenylphosphine oxide Phosphine oxide, cyclooctyl phosphine oxide, tolyl phosphine oxide, bis(methoxyphenyl) phosphine oxide, etc.; phenyl phosphinate, ethyl phenyl phosphinate, tolyl Cresyl phosphonite, benzyl benzyl phosphonite, etc.; 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-tritertiary butyl-9,10-dihydro-9-oxo Hetero-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.; diphenyl phosphite , Dicresyl phosphite, diphenylmethyl phosphite, 5,5-dimethyl-1,3,2-dioxaphosphorinane, etc. These organic phosphorus compounds can be used individually or in combination of 2 or more types.

Examples of the above-mentioned good solvent include ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetate, and benzoate. These solvents can be used individually or in mixture of 2 or more types. Among these solvents, acetate is preferred, and benzyl acetate is more preferred.

Methanol, ethanol, butanol, acetone, etc. are mentioned as said poor solvent. These solvents can be used individually or in mixture of 2 or more types. Among these solvents, methanol, ethanol, and acetone are preferable, and methanol and ethanol are more preferable. These solvents may contain water, and in this case, water may be contained up to 100 parts by mass with respect to 100 parts by mass of the solvent.

The phosphorus-containing bifunctional phenolic compound represented by the formula (6a) is essential for the bifunctional phenolic compound used in the production of the above-mentioned one-stage method and two-stage method, but other bifunctional phenolic compounds may be used in combination.

For example, a phosphorus-free bifunctional phenol compound represented by the above formula (6b), such as a phenol compound having a divalent group represented by the formulas (4a) to (4c), or a bifunctional phenol compound represented by the formula (3) can be used in combination. The phosphorus-containing phenolic compound shown is the phosphorus-containing bifunctional phenolic compound shown in formula (6c).

A phosphorus-containing bifunctional phenolic compound having one phosphorus-containing group represented by formula (3) can be obtained by reacting an organophosphorus compound represented by formula (7) with a quinone compound using a conventional synthesis method. As far as the synthesis method is concerned, although there are, for example, Japanese Patent Application Publication No. 60-126293, Japanese Patent Application Publication No. 61-236787, zh.Obshch.Khim, 42(11), pages 2415-2418 (1972) methods shown, but not limited to these methods.

As for the phosphorus-free bifunctional phenolic compound that can be used in combination, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, bisphenol Bisphenols such as acetophenone and bisphenol boraxone; dihydroxy compounds with norbornane structure, tetrahydrodicyclopentadiene structure, tetrahydrotricyclopentadiene structure or adamantane structure; biphenols; ortho Monocyclic bifunctional phenols such as quinone, resorcinol, and hydroquinone; dihydroxynaphthalene, etc.

In terms of phosphorus-containing bifunctional phenolic compounds that can be used together, for example: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter ,Referred to as DOPO-HQ), 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-NQ), diphenylphosphine Hydroquinone, Diphenylphenylphosphino-1,4-dioxynaphthalene, 1,4-Cyclooctylphosphino-1,4-Phenyldiol, 1,5-Cyclooctane Phosphonyl-1,4-phenyldiol, etc.

In addition, these may be substituted with substituents such as alkyl groups and aryl groups without adverse effects. These bifunctional phenolic compounds can use plural types together.

First, the one-stage method will be described.

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 alkali metal hydroxide with respect to 1 mol of the bifunctional phenolic compound. Reaction in a non-reactive solvent in the presence of the compound, the epihalohydrin is consumed, and the condensation reaction is carried out so that the Mw becomes 10,000 or more, thereby obtaining a phosphorus-containing phenoxy resin. Furthermore, after the reaction, by-product salts must be removed by filtration or washing with water.

The 2-functional phenolic compound represented by the formula (6a) used as a raw material is preferably 1 to 100 mole % in the raw material 2-functional phenolic compound, more preferably 2 to 75 mole %, and more preferably 5 to 75 mole %. 50 mole%, the best is 10 to 40 mole%, and the best is 15 to 35 mole%.

Although the bifunctional phenolic compound represented by formula (6b) is used to impart properties other than flame retardancy, it is preferably 0 to 75 mol%, more preferably 25 to 75 mol%, and more preferably 45 to 75 mol%. 55 mole %.

Although the bifunctional phenol compound represented by the formula (6c) is used in combination to impart flame retardancy, it is preferably 0 to 50 mol%, more preferably 10 to 40 mol%. When using the bifunctional phenol compound represented by formula (6c) in combination, it is generally advantageous to use it as a mixture without isolating the bifunctional phenol compound represented by formula (6a).

This reaction can be carried out under normal pressure or reduced pressure. Usually, when the reaction is performed under normal pressure, the reaction temperature is preferably 20 to 200°C, more preferably 30 to 170°C, more preferably 40 to 150°C, and most preferably 50 to 100°C. When reacting under reduced pressure, it is preferably from 20 to 100°C, more preferably from 30 to 90°C, and still more preferably from 35 to 80°C. 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. In addition, when it is necessary to remove the heat of reaction, it is usually carried out by the evaporation/condensation/reflux method using a solvent due to the reaction heat, the indirect cooling method, or a combination of these methods.

烷、四氫呋喃等醚類；乙醇、異丙醇、丁醇等醇類；甲基賽路蘇、乙基賽路蘇等賽路蘇類；乙二醇二甲基醚等二醇醚類等，但不特別限於此等，此等溶劑可單獨使用或混合2種以上而使用。 In terms of non-reactive solvents, for example: aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dibutyl ether, di

Ethers such as alkane and tetrahydrofuran; alcohols such as ethanol, isopropanol, butanol; However, it is not particularly limited thereto, and these solvents may be used alone or in combination of two or more.

Additionally, catalysts may be used. In terms of catalysts that can be used, for example: quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; benzyldimethylamine, 2,4,6-paraffin (dimethyl Aminomethyl) phenol and other tertiary amines; 2-ethyl-4-methylimidazole, 2-phenylimidazole and other imidazoles; ethyl triphenylphosphonium iodide and other phosphonium salts; triphenylphosphine and other phosphines class etc. These catalysts can be used individually or in combination of 2 or more types.

Next, the two-stage method will be described.

For the bifunctional epoxy resin that will be the raw material epoxy resin in the two-stage method, it is preferable to react the phosphorus-free bifunctional phenolic compound represented by the above formula (6b) with epihalohydrin. A bifunctional epoxy resin represented by formula (8). Furthermore, in the case of phosphorus-containing bifunctional epoxy resins, X2 in ^formula ( ⁸ ) is substituted with X1 or ^X3 .

In formula (8), X ² is synonymous with X ² in formula (6b), and is preferably a divalent group shown in formulas (4a) to (4c) above. G is glycidyl. J is the number of repetitions and its average value is 0-6, preferably 0-3, more preferably 0-1.

In the reaction of the 2-functional phenolic compound and epihalohydrin used to obtain the raw material epoxy resin in the two-stage method, relative to the functional group in the 2-functional phenolic compound, use 0.8 to 1.2 times the mole (preferably 0.85 to 1.05 times mole) of sodium hydroxide, potassium hydroxide and other alkali metal hydroxides. If it is less than this range, the amount of remaining hydrolyzable chlorine will increase, which is not preferable. Metal hydroxides are used in aqueous solution, alcoholic solution or solid state.

In the epoxidation reaction, an excess amount of epihalohydrin is used relative to the bifunctional phenolic compound. Generally, 1.5 to 15 moles of epihalohydrin is used, preferably 2 to 10 moles, and more preferably 5 to 8 moles, relative to 1 mole of functional groups in the bifunctional phenolic compound. If it is more than this range, the production efficiency will decrease, and if it is less than this range, the amount of high molecular weight body of epoxy resin will increase and it will become unsuitable as a raw material for phosphorus-containing phenoxy resin.

The epoxidation reaction is usually carried out at a temperature below 120°C. During the reaction, when the temperature is high, the amount of so-called poorly hydrolyzable chlorine increases, making it difficult to achieve high purity. The temperature is preferably below 100°C, more preferably below 85°C.

In terms of the bifunctional epoxy resin that will become the raw material of the two-stage method, it is preferably a bifunctional epoxy resin shown in formula (8), more preferably a divalent group with the above formulas (4a) to (4c) of epoxy resin. In addition, these epoxy resins may be substituted with substituents such as alkyl groups and aryl groups without adverse effects. In addition, bifunctional epoxy resins, such as an alkylene glycol type epoxy resin and an aliphatic cyclic epoxy resin, can be used within the range which does not impair the object of this invention.

The usage ratio (molar ratio) of the raw materials is preferably 0.95 to 1.10, more preferably 1.00 to 1.05 in the form of bifunctional epoxy resin/bifunctional phenolic compound.

In the case of the two-stage method, a catalyst may be used, and any compound may be used as long as it is a compound having a catalytic ability to accelerate the reaction between an epoxy group and a phenolic hydroxyl group. Examples thereof include alkali metal compounds, organophosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like. These catalysts can be used individually or in combination of 2 or more types.

Examples of alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide, alkali metals such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride. Salt, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal phenoxides, sodium hydride, lithium hydride, etc., alkali metal salts of organic acids such as sodium acetate and sodium stearate.

As far as organic phosphorus compounds are concerned, examples include: tri-n-propylphosphine, tri-n-butylphosphine, tri-tertiary-butylphosphine, triphenylphosphine, tricresylphosphine, trimethoxyphenylphosphine, tricyclohexyl Phosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride , Trimethylphenylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylphosphonium bromide Ethylphosphonium, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, and the like.

Tertiary amines include, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, and the like. In terms of quaternary ammonium salts, for example: tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, bromide Tetraethylammonium chloride, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride Benzyltrimethylammonium, Benzyltrimethylammonium Bromide, Benzyltrimethylammonium Hydroxide, Benzyltributylammonium Chloride, Benzyltrimethylammonium Chloride, etc.

As far as imidazoles are concerned, for example: 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, etc.

(嗎啉)、N-甲基嗎啉、N,N-二甲基胺基吡啶(DMAP)等。 For cyclic amines, examples include: 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-

(morpholine), N-methylmorpholine, N,N-dimethylaminopyridine (DMAP), etc.

The catalyst is usually used in an amount of 0.001 to 1% by mass relative to the solid content of the reaction. When an alkali metal compound is used as a catalyst, the phosphorus-containing phenoxy resin will leave an alkali metal component, which will deteriorate the insulation properties of electronic/electrical parts and printed circuit boards using the catalyst, so phosphorus-containing phenoxy resins The total content of alkali metals such as lithium, sodium, and potassium in the phenoxy resin is preferably at most 100 ppm, more preferably at most 60 ppm, and even more preferably at most 50 ppm.

In addition, when organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles, etc. are used as catalysts, they will also remain in the phosphorus-containing phenoxy resin in the form of catalyst residues, and will The same as the residue of alkali metal components, it will deteriorate the insulation properties of electronic/electrical parts and printed circuit boards. Therefore, the content of phosphorus atoms or nitrogen atoms in phosphorus-containing phenoxy resins is preferably less than 300ppm, more preferably 200ppm Below, more preferably below 100ppm.

In 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. For example Aromatic hydrocarbons, ketones, ester solvents, ether solvents, amide solvents, glycol ether solvents, etc. These solvents can be used individually or in mixture of 2 or more types.

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

In terms of ketones, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, acetyl Acetone, etc.

In terms of ester solvents, for example: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone, etc. .

烷等。 In terms of ether solvents, for example: diethyl ether, dibutyl ether, tertiary butyl methyl ether, tetrahydrofuran, di

alkanes etc.

For amide-based solvents, for example: formamide, N-methylformamide, DMF, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2 - pyrrolidone, N-methylpyrrolidone and the like.

In terms of glycol ether solvents, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether Base ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, etc.

Although the amount of the solvent used can be properly selected according to the reaction conditions, for example, in the case of two-stage method production, the solid content concentration is preferably 35 to 95% by mass. In addition, when a highly viscous product is generated during the reaction, the reaction may be continued by adding a solvent during the reaction. After completion|finish of reaction, a solvent may be removed by distillation etc. as needed, and a solvent may be added further.

The reaction temperature in the two-stage method is carried out within a temperature range in which the catalyst used does not decompose. When the reaction temperature is too high, there is a risk that the resulting phosphorus-containing phenoxy resin will deteriorate. When it is too low, there exists a possibility that reaction may not progress and a target molecular weight may not be reached. Therefore, the reaction temperature is preferably from 50 to 230°C, more preferably from 120 to 200°C. In addition, the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When low-boiling-point solvents such as acetone and methyl ethyl ketone are used, the reaction temperature can be secured by performing the reaction under high pressure using an autoclave. In addition, when it is necessary to remove the heat of reaction, it is usually carried out by the evaporation/condensation/reflux method using a solvent due to the reaction heat, the indirect cooling method, or a combination of these methods.

The phosphorus-containing phenoxy resin of the present invention has flame retardancy and is a flexible thermoplastic resin and can be used alone. When most of X in the formula (1) is the group (X1), the phosphorus content becomes higher, so it can be used as a flame retardant for thermoplastic resins such as polycarbonate resins.

In addition, a curable resin component can also be prepared as a thermosetting resin composition. In this case, by introducing a non-phosphorous group (X2) into part of X, a flame-retardant phenoxy resin having properties required for the resin composition in advance can be produced.

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

The resin composition of the present invention is prepared by blending a curable resin component into the above-mentioned phosphorus-containing phenoxy resin.

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

Examples of the curable resin component include: a resin composition that hardens an epoxy resin with a hardener, a resin composition that hardens an acrylate resin with a radical polymerization initiator, and a phenol resin Resin components that self-polymerize by heat, such as resin, melamine resin, isocyanate resin, etc. It is understood that when a curing agent, a catalyst, an accelerator, etc. are required for curing the curable resin, the curable resin component contains them.

The blending amount of the curable resin component is preferably 1/99 to 99/1, more preferably 10/90 to 90/10 in terms of phosphorus-containing phenoxy resin/hardenable resin component (mass ratio), Even better is 25/75 to 75/25. By formulating curable resin components, materials with more excellent heat resistance can be obtained.

When the curable resin component is an epoxy resin, conventionally known epoxy resins can be used. Furthermore, the epoxy resin refers to an epoxy resin having at least one epoxy group, but preferably an epoxy resin having two or more epoxy groups, and more preferably a ring having three or more epoxy groups. oxygen resin. Specifically, a polyglycidyl ether compound, a polyglycidylamine compound, a polyglycidyl ester compound, an alicyclic epoxy compound, other modified epoxy resin, etc. are mentioned. These epoxy resins may be used alone, or two or more epoxy resins of the same series may be used in combination, and epoxy resins of different series may be used in combination.

The polyglycidyl ether compound specifically includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, biphenol type epoxy resin, Hydroquinone type epoxy resin, bisphenol terpene type epoxy resin, naphthalene diphenol type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin Resin, resorcinol type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolac type epoxy resin, bisphenol Novolac epoxy resin, naphthol novolac epoxy resin, β-naphthol aralkyl epoxy resin, naphthalene diphenol aralkyl epoxy resin, α-naphthol aralkyl epoxy resin , biphenyl aralkylphenol type epoxy Resin, trihydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin, etc. .

As polyglycidylamine compounds, specifically, diaminodiphenylmethane type epoxy resins, m-xylylenediamine type epoxy resins, 1,3-bisaminomethylcyclohexane Type epoxy resin, isocyanate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, aminophenol type epoxy resin, etc.

Specific examples of the polyglycidyl ester compound include dimer acid-type epoxy resins, hexahydrophthalic acid-type epoxy resins, trimellitic acid-type epoxy resins, and the like.

As an alicyclic epoxy compound, aliphatic cyclic epoxy resins, such as CELLOXIDE 2021 (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned.

唑啶酮環之環氧樹脂、環氧改質聚丁二烯橡膠衍生物、羧基末端丁二烯腈橡膠(CTBN)改質環氧樹脂、聚乙烯基芳烴多氧化物(例如，二乙烯基苯二氧化物、三乙烯基萘三氧化物等)、含磷之環氧樹脂等。 As far as other modified epoxy resins are concerned, specific examples include: urethane modified epoxy resins,

Epoxy resins with pyroxazidone rings, epoxy modified polybutadiene rubber derivatives, carboxyl-terminated butadiene nitrile rubber (CTBN) modified epoxy resins, polyvinyl aromatic polyoxides (such as divinyl benzene dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resin, etc.

In the case of formulating epoxy resins, hardeners are included. The hardener refers to a substance that facilitates the cross-linking reaction and/or chain length extension reaction between the epoxy groups of the epoxy resin.

With respect to 100 parts by mass of epoxy resin, the amount of curing agent used is 0.1 to 100 parts by mass as needed, preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, and more preferably 10 to 60 parts by mass share.

化合物、四苯基硼酸鹽、有機酸二醯肼、鹵化硼胺錯合物、聚硫醇系硬化劑、異氰酸酯系硬化劑、封端異氰酸酯系硬化劑等。此等硬化劑可單獨使用，亦可併用2種以上同種類者，亦可組合其他種類並使用。 The curing agent is not particularly limited, and generally known epoxy resin curing agents can be used. From the viewpoint of improving heat resistance, preferred examples include phenolic curing agents, amide curing agents, and imidazoles. In addition, from the viewpoint of reducing water absorption, active ester-based curing agents are preferred. In addition, amine-based hardeners, acid anhydride-based hardeners, organic phosphines, phosphonium salts, benzo

compound, tetraphenyl borate, organic acid dihydrazine, boron halide amine complex, polythiol-based hardener, isocyanate-based hardener, blocked isocyanate-based hardener, etc. These curing agents may be used alone, or two or more of the same type may be used in combination, or other types may be used in combination.

Examples of phenolic hardeners include bisphenol A, bisphenol F, dihydroxydiphenylmethane, dihydroxydiphenyl ether, bis(hydroxyphenoxy)benzene, and dihydroxydiphenyl sulfide , dihydroxydiphenyl ketone, dihydroxydiphenyl ketone, bisphenol, hydroquinone, resorcinol, catechol, tertiary butylcatechol, tertiary butylhydroquinone Dihydric phenol compounds such as phenol, dihydroxynaphthalene, and dihydroxymethylnaphthalene; phenol novolac, bisphenol A novolac, cresol novolac, xylenol novolac, parahydroxyphenylmethane novolac, dicyclopentadiene Phenols, naphthol novolaks, styrenated phenol novolacs, terpene phenols, heavy oil modified phenols, phenol aralkyls, naphthol aralkyls, polyhydroxystyrene, phloroglucinol, pyrogallol Phenol, tertiary butylpyrogallol, glucinol, trihydroxynaphthalene, trihydroxybenzophenone, trihydroxyacetophenone and other phenolic compounds with more than 3 yuan; 10-(2,5-dihydroxyphenyl Phosphorus-containing phenolic compounds such as )-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Those obtained by addition-reacting these phenolic compounds with aromatic compounds such as indene and styrene can also be used as hardeners. The phenolic hardener is preferably used with a molar ratio of active hydroxyl groups in the hardener to epoxy groups in the epoxy resin in the range of 0.8 to 1.5.

The amide-based curing agent may, for example, be dicyandiamide and its derivatives, polyamide resin, or the like. The amide-based curing agent is preferably used in the range of 0.1 to 25 parts by mass relative to 100 parts by mass of the entire epoxy resin component.

、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-對稱三

、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-對稱三

三聚異氰酸加成物、2-苯基咪唑三聚異氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、及環氧樹脂與上述咪唑類之加成物等。相對於全部環氧樹脂成分100質量份，咪唑類較佳係以0.1至25質量份之範圍使用。再者，咪唑類具有觸媒能力，故通常也被分類為後述之硬化促進劑，但在本發明中分類為硬化劑。 For imidazoles, for example: 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, trimellitic acid 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl - Symmetry three

, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric tri

, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric tri

Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles, etc. It is preferable to use imidazoles in the range of 0.1-25 mass parts with respect to 100 mass parts of all epoxy resin components. In addition, since imidazoles have catalytic ability, they are also generally classified as hardening accelerators described later, but are classified as hardening agents in the present invention.

As for the active ester hardener, it is preferable to have two or more ester groups with high reactivity in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. Among them, more preferred are phenolic esters prepared by reacting polyfunctional phenolic compounds with aromatic carboxylic acids as described in Japanese Patent No. 5152445. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromeltaric acid. In terms of aromatic compounds with phenolic hydroxyl groups, for example: catechol, dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol , Glycinol, dicyclopentadienyl diphenol, phenol novolac, etc. Commercially available products include EPICLON HPC-8000-65T (manufactured by DIC Co., Ltd.), but are not limited thereto. The active ester-based hardener is preferably used so that the molar ratio of the active ester group in the hardener to the epoxy group in the resin composition is in the range of 0.2 to 2.0.

In terms of amine hardeners, examples include: diethylenetriamine, triethylenetetramine, m-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenyl Acids and polyamines such as dicyandiamide, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-paraffin (dimethylaminomethyl)phenol, dicyandiamide, and dimer acid Amine compounds such as polyamide amine and other condensates. The amine-based hardener is preferably used so that the molar ratio of active hydrogen groups in the hardener to epoxy groups in the resin composition ranges from 0.5 to 1.5.

As for acid anhydride hardeners, examples include: methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, burnt honey Lithic anhydride, phthalic anhydride, trimellitic anhydride, methylnadic anhydride, maleic anhydride, etc. The acid anhydride hardener is preferably used so that the molar ratio of the acid anhydride groups in the hardener to the epoxy groups in the resin composition is in the range of 0.5 to 1.5.

Furthermore, the active hydrogen group refers to a functional group having an active hydrogen reactive to an epoxy group (including a functional group having a potential active hydrogen that can generate active hydrogen due to hydrolysis, etc., and a functional group that exhibits the same hardening effect. ), specifically acid anhydride groups, carboxyl groups, amino groups, phenolic hydroxyl groups, and the like. In addition, regarding the active hydrogen group, the carboxyl group (—COOH) and the phenolic hydroxyl group (—OH) were calculated as 1 mole, and the amino group (—NH ₂ ) was calculated as 2 moles. In addition, when the active hydrogen group is unclear, the active hydrogen equivalent can be obtained by measurement. For example, it can be obtained by reacting a monoepoxy resin whose epoxy equivalent is known such as phenylglycidyl ether with a hardener whose active hydrogen equivalent is unknown, and measuring the amount of consumed monoepoxy resin. The active hydrogen equivalent of the hardener used.

In addition, when preparing an epoxy resin, a hardening accelerator may be used as needed. Examples of hardening accelerators include imidazole derivatives, tertiary amines, phosphorus compounds such as phosphines, gold Genus compounds, Lewis acids, amine zirconium salts, etc. These hardening accelerators can be used individually or in combination of 2 or more types.

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. For example: 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole , 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole and other alkyl-substituted imidazole compounds; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1 -(2'-cyanoethyl)imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and other imidazoles substituted by hydrocarbon groups containing ring structures such as aryl or aralkyl compounds etc.

In terms of tertiary amines, for example: 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, 1,8-diazepine - Bicyclo[5.4.0]-7-undecene (DBU) and the like.

Phosphines include, for example, triphenylphosphine, tricyclohexylphosphine, triphenylphosphinetriphenylborane, and the like.

As a metal compound, tin octylate etc. are mentioned, for example.

As far as amine complex salts are concerned, for example: boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, trifluoride Boron trifluoride complexes such as boron chlorophenylamine complexes, boron trifluoride benzylamine complexes, boron trifluoride aniline complexes, or mixtures thereof, etc.

Among these hardening accelerators, when used for build-up materials or circuit boards, 2-dimethylene is preferred from the viewpoint of excellent heat resistance, dielectric properties, and solder resistance. Aminopyridine, 4-dimethylaminopyridine, imidazoles. In addition, sealed with semiconductor When used as a material, triphenylphosphine and DBU are preferable from the standpoint of excellent curability, heat resistance, electrical characteristics, and moisture resistance reliability.

The compounding amount of the hardening accelerator can be appropriately selected according to the purpose of use, but relative to 100 parts by mass of the epoxy resin component in the resin composition, 0.01 to 15 parts by mass, preferably 0.01 to 10 parts by mass are used as needed , more preferably 0.05 to 8 parts by mass, more preferably 0.1 to 5 parts by mass. By using a hardening accelerator, the hardening temperature can be lowered or the hardening time can be shortened.

The resin composition which hardens the acrylate resin which is a curable resin component with a radical polymerization initiator includes a thermosetting resin composition and a photocurable resin composition of a (meth)acrylate compound. The (meth)acrylate-based compound is an acrylate having at least one (meth)acryl group in the molecule used as a viscosity adjusting and curing component. Part of the (meth)acrylate compound preferably has two or more (meth)acryloyl groups. The resin composition at this time contains (meth)acrylate compound, thermal polymerization initiator, photopolymerization initiator or both as essential components.

Such (meth)acrylate compounds include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) Dicyclopentenyloxyethyl acrylate, dicyclopentanyl (meth)acrylate, acryl morpholine, 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, Tetrahydrofurylmethyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Phenyl polyethoxy (meth)acrylate, 2-Hydroxy-3-phenyloxypropyl (meth)acrylate , o-phenylphenol monoethoxy (meth)acrylate, o-phenylphenol polyethoxy (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, (methyl ) isocamphoryl acrylate, (methyl) Tribromophenyloxyethyl acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. base) acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate Acrylates, Bisphenol A Polyethoxy Di(meth)acrylate, Bisphenol A Polyethoxy Di(meth)acrylate, Bisphenol F Polyethoxy Di(meth)acrylate, Ethylene Glycol Di(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, ginseng(2-hydroxyethyl)isocyanate tri(meth)acrylate, neopentylthritol tri(meth)acrylate base) acrylate, neopentylthritol tetra(meth)acrylate, diperythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, ginseng (acryloxyethyl ) trimeric isocyanate, neopentylthritol tetra (meth) acrylate, dipentyl pentaerythritol penta (meth) acrylate, trineopentylthritol hexa (meth) acrylate, trineopentylthritol penta ( Meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Trimethylolpropane Polyethoxytri(meth)acrylate Polyfunctional ( Meth)acrylates, urethane (meth)acrylates obtained by reacting polyol compounds with polyisocyanate compounds and (meth)acrylates, and epoxy compounds reacted with (meth)acrylates Epoxy acrylate, etc. These (meth)acrylate type compounds can be used individually or in combination of 2 or more types.

In addition, as a compound that can be used as a polymerization initiator of a (meth)acrylate compound, as long as it can generate radicals by heating, irradiation of active energy rays, etc., it can be used without particular limitation. . As for the polymerization initiator, for example, when it is hardened by heating, if it is azo-based or peroxide-based initiators such as azobisisobutyronitrile and benzoyl peroxide, it can be used in general free radicals. All thermal polymerizers can be used. In addition, free radical polymerization by photopolymerization In radical polymerization, if it is benzoin, acetophenone, anthraquinone, thioxanthone, ketal, diphenyl ketone, phosphine oxide, etc., it can be used in ordinary photoradical polymerization can be used. These polymerization photoinitiators may be used alone or as a mixture of two or more. Furthermore, the radical photopolymerization initiator can also be used in combination with accelerators such as tertiary amine compounds and ethyl N,N-dimethylaminobenzoate.

In addition, the resin composition of the present invention can use organic solvents or reactive diluents for viscosity adjustment. These organic solvents or reactive diluents may be used alone or in combination of two or more.

烷、四氫呋喃、乙二醇單甲基醚、二甲氧基二乙二醇、乙二醇二乙基醚、二乙二醇二乙基醚、三乙二醇二甲基醚等醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；甲醇、乙醇、1-甲氧基-2-丙醇、2-乙基-1-己醇、苯甲醇、乙二醇、丙二醇、丁基二醇、松油等醇類；乙酸乙酯、乙酸丁酯、乙酸甲氧基丁酯、甲基賽路蘇乙酸酯、賽路蘇乙酸酯、乙基二醇乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯、苯甲醇乙酸酯等乙酸酯類；苯甲酸甲酯、苯甲酸乙酯等苯甲酸酯類；甲基賽路蘇、賽路蘇、丁基賽路蘇等賽路蘇類；甲基卡必醇、卡必醇、丁基卡必醇等卡必醇類；苯、甲苯、二甲苯等芳香族烴類；二甲亞碸等亞碸類；己烷、環己烷等烷烴類；乙腈、N-甲基吡咯啶酮等，但不限於此等。 As far as organic solvents are concerned, for example: amides such as DMF and N,N-dimethylacetamide;

Alkanes, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and other ethers; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, Ethylene glycol, propylene glycol, butyl glycol, pine oil and other alcohols; Glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate and other acetates; methyl benzoate and ethyl benzoate and other benzoates; methyl benzoate Cyrusol, cylusol, butyl cylusol and other cerbitols; methyl carbitol, carbitol, butyl carbitol and other carbitols; benzene, toluene, xylene and other aromatic hydrocarbons ; Alkene such as dimethylsulfene; Alkanes such as hexane and cyclohexane; Acetonitrile, N-methylpyrrolidone, etc., but not limited to these.

In terms of reactive diluents, for example: allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl Glycidyl ether and other monofunctional glycidyl ethers; Resorcinol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether Ether, 1,4-Butanediol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Cyclohexanedimethanol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether Difunctional glycidyl ethers such as ethers; glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, Polyfunctional glycidyl ethers such as oxypropyl ether; glycidyl esters such as glycidyl neodecanoate; Propylamines, but not limited to these.

The organic solvent is preferably used alone or in combination of several types in a non-volatile content of 20 to 90% by mass, and the appropriate type and usage amount are appropriately selected according to the application. For example, in the application of printed circuit boards, polar solvents such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol with a boiling point below 160°C are preferred, and the amount used is preferably calculated as non-volatile matter 40 to 80% by mass. In addition, for adhesive film applications, it is preferable to use, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone etc., its usage amount is preferably 30 to 60% by mass when calculated as non-volatile matter.

Reactive diluents are mainly used when reducing viscosity and adjusting gel time in solvent-free systems. When the amount used is large, the hardening reaction may not proceed sufficiently, and unreacted components may seep out of the hardened product, or the physical properties of the hardened product such as mechanical strength may be reduced, so it is preferable not to use more than necessary amount. Therefore, it is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass in the epoxy resin.

The resin composition of the present invention aims to improve the flame retardancy of the obtained hardened product, and various non-halogen flame retardants that do not substantially contain halogen atoms can be used within the range that does not lower reliability. In terms of non-halogen flame retardants that can be used, for example, phosphorus flame retardants, nitrogen flame retardants, polysiloxane flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. . and so on There are no restrictions on the use of non-halogen flame retardants, and they can be used alone or in combination of two or more flame retardants of the same type, and can also be used in combination of different types of flame retardants.

The phosphorus-containing phenoxy resin of the present invention is excellent in flame retardancy, so it is unnecessary or greatly reduced to prepare a flame retardant.

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

In addition, red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis, etc. In terms of surface treatment methods, for example: (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, A method of coating treatment with inorganic compounds such as bismuth oxide, bismuth hydroxide, bismuth nitrate or their mixtures; A method of coating with a mixture of hardening resins; (3) coating the coating of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, and titanium hydroxide twice with a thermosetting resin such as phenol resin method etc.

In terms of organophosphorus compounds, for example: phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, hypophosphorous compounds, phosphine oxide compounds, phosphonane compounds, etc. Compounds, metal salts of hypophosphite, etc., and phosphorus compounds (such as DOPO, diphenylphosphine oxide, etc.) or phosphorus-containing phenolic compounds (such as DOPO-HQ, DOPONQ, diphenylphosphinohydroquinone, diphenylphosphino-1,4-dioxynaphthalene, 1,4-cyclooctylphosphono-1,4-phenyldiol, 1,5-stretch Organophosphorus compounds such as cyclooctylphosphonyl-1,4-phenyldiol, etc.), derivatives obtained by reacting these organophosphorus compounds with compounds such as epoxy resins or phenol resins, etc.

In addition, in terms of the reactive phosphorus compound used in the phosphorus-containing epoxy resin and phosphorus-containing hardener, it is preferable to have one or two phosphorus-containing groups represented by the formula (3). A bifunctional phenolic compound and an organophosphorus compound represented by formula (7).

In terms of phosphorus-containing epoxy resins, it is disclosed in Japanese Patent Application Publication No. 04-11662, Japanese Patent Application Publication No. 05-214070, Japanese Patent Application Publication No. 2000-309624, Japanese Patent Application Publication No. 2002-265562, etc. . As for the specific examples of phosphorus-containing epoxy resins, for example: Epotohto FX-305, Epotohto FX-289B, Epotohto FX-1225, YDFR-1320, TX-1328 (above, Nippon Steel Sumitomo Metal Chemical Co., Ltd. system), etc., but not limited to these.

The epoxy equivalent (g/eq.) of these phosphorus-containing epoxy resins is preferably from 200 to 800, more preferably from 300 to 780, and still more preferably from 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 most preferably 3 to 5% by mass.

化合物。 As far as the phosphorus-containing curing agent is concerned, in addition to the above-mentioned phosphorus-containing 2-functional phenolic compound, it is also possible to use the production method disclosed in Japanese Patent Application No. 3008-501063 and Japanese Patent No. 4548547 to have the formula (3) Phosphorus compound of the shown structure reacts with aldehydes and phenolic compounds to obtain phosphorus-containing phenolic compounds. At this time, the phosphorus compound having the structural part represented by the formula (3) is incorporated into the molecule through condensation addition of 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, by further reacting with aromatic carboxylic acids, a phosphorus-containing active ester can be obtained from a phosphorus compound phenol compound having a structure represented by formula (3). compound. In addition, in the production method disclosed in Japanese Patent Publication No. WO2008/010429, a phosphorus-containing benzo

compound.

The compounding quantity of the phosphorus compound used together is selected suitably according to the kind and phosphorus content rate of phosphorus compound, the component of a resin composition, and the degree of flame retardancy desired. When the phosphorus compound is a reactive phosphorus compound (i.e. phosphorus-containing epoxy resin, phosphorus-containing hardener), relative to all phosphorus-containing phenoxy resins, curable resin components, flame retardants, and other fillers or additives, etc. The total solid content in the prepared resin composition (generally, the total solid content in the resin composition refers to the total of the components in the resin composition except the solvent), and the phosphorus content is preferably 0.2 to 6% by mass , more preferably 0.4 to 4% by mass, more preferably 0.5 to 3.5% by mass, and most preferably 0.6 to 3.0% by mass. When the phosphorus content is small, it may be difficult to ensure flame retardancy, and when it is too large, there may be a bad influence on heat resistance and solvent solubility. Therefore, relative to the total solid content in the resin composition, when red phosphorus is used, the actual blending amount is preferably in the range of 0.1 to 2% by mass, and when organophosphorus compounds are used, the actual blending amount is preferably 0.1 to 10% by mass The range of 0.5 to 6% by mass is more preferable.

In addition, in the resin composition of the present invention, for example, hydrotalcite, magnesium hydroxide, boron compound, zirconia, calcium carbonate, zinc molybdate, etc. can be used together as flame retardant additives.

In the present invention, when a flame retardant is used in combination, it is preferable to use a phosphorus-based flame retardant, but the flame retardants described below may also be used in combination.

化合物、三聚氰酸化合物、三聚異氰酸化合物、啡噻

等，較佳係三

化合物、三聚氰酸化合物、三聚異氰酸化合物。氮系阻燃劑之調配量雖依氮系阻燃劑種類、樹脂組成物之其他成分、所期望之阻燃性的程度而適當地選擇，但例如較佳係相對於樹脂組成物中之全固形份，以0.05至10質量%之範圍調配，特佳係以0.1 至5質量%之範圍調配。另外，使用氮系阻燃劑時，可併用金屬氫氧化物、鉬化合物等。 As far as nitrogen-based flame retardants are concerned, for example three

compound, cyanuric acid compound, isocyanuric acid compound,

etc., preferably three

Compounds, cyanuric acid compounds, cyanuric acid compounds. Although the blending amount of nitrogen-based flame retardants is properly selected according to the type of nitrogen-based flame retardants, other components of the resin composition, and the degree of desired flame retardancy, for example, it is preferably relative to the total amount of nitrogen-based flame retardants in the resin composition. The solid content is formulated in the range of 0.05 to 10% by mass, and the range of Tejia is formulated in the range of 0.1 to 5% by mass. In addition, when using a nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone-based flame retardant can be used without particular limitation if it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. Although the compounding amount of polysiloxane flame retardant is properly selected according to the type of polysiloxane flame retardant, other components of the resin composition, and the desired degree of flame retardancy, for example, it is preferably relative to the resin composition The total solid content in the product is formulated in the range of 0.05 to 20% by mass. In addition, when a silicone-based flame retardant is used, a molybdenum compound, alumina, or the like may be used in combination.

Examples of inorganic flame retardants include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. The blending amount of the inorganic flame retardant is properly selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy, but for example, relative to the phenoxy resin, hardened The total solid content of the resin composition, which has been formulated with permanent resin components, flame retardants, and other fillers or additives, is formulated in the range of 0.05 to 20% by mass, and is optimally formulated in the range of 0.5 to 15% by mass. .

In terms of organometallic salt-based flame retardants, for example: ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonate metal salts, metal atoms and aromatic compounds or Compounds formed by ionic bonding or coordination bonding of heterocyclic compounds, etc. Although the compounding amount of the organometallic salt-based flame retardant is properly selected according to the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, for example, it is preferably relative to phenoxy The total solid content of the resin composition in which the base resin, curable resin component, flame retardant, and other fillers or additives have all been formulated is formulated in the range of 0.005 to 10% by mass.

In addition, the resin composition may contain fillers, thermoplastic resins, thermosetting resins other than epoxy resins, coupling agents, antioxidants, release agents, defoamers, emulsifiers, Other additives such as thixotropy-imparting agents, smoothing agents, and pigments.

As fillers, examples include: fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, diaspore, talc , mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon and other inorganic fillers; carbon fiber, glass fiber, oxide Aluminum fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber and other fibrous fillers; microparticle rubber, etc.

Among them, those that are not decomposed or dissolved by oxidizing compounds such as the aqueous permanganate solution used for roughening the surface of hardened products are preferred. Fused silicon oxide and crystalline silicon oxide are easy to obtain fine particles. For the best. In addition, it is preferable to use fused silica especially when the compounding amount of the filler is increased. Fused silica can be used either in crushed or spherical form, but in order to increase the blending amount of fused silica and at the same time suppress the increase in the melt viscosity of the molding material, it is more preferable to use mainly spherical ones. In order to further increase the blending amount of spherical silicon oxide, it is preferable to properly adjust the particle size distribution of spherical silicon oxide. Furthermore, the filler can also be treated with silane coupling agent, organic acid such as stearic acid. In general, the reasons for using fillers include the effect of improving the impact resistance of cured products and the reduction of linear expansion of cured products. In addition, when metal hydroxides such as aluminum hydroxide, diaspore, and magnesium hydroxide are used, they function as flame retardant additives to improve flame retardancy. When improving thermal conductivity, aluminum oxide, silicon nitride, boron nitride, aluminum nitride, fused silicon oxide, and crystalline silicon oxide are preferred, and aluminum oxide, boron nitride, fused silicon oxide, and crystalline silicon oxide are more preferred. When used for conductive paste, etc., conductive fillers such as silver powder and copper powder can be used.

In consideration of the low linear expansion and flame retardancy of the hardened product, it is better to have a higher amount of filler compounded. Relative to the total solid content in the resin composition, it is preferably 1 to 98% by mass, more preferably 3 to 90% by mass, still more preferably 5 to 80% by mass, and most preferably 10 to 60% by mass. When the compounding amount is large, there is a possibility that the adhesiveness required for the laminated board application will be lowered, and the cured product may be fragile, and sufficient mechanical properties may not be obtained. Moreover, when the compounding quantity is small, there exists a possibility that the compounding effect of a filler, such as the improvement of the impact resistance of hardened|cured material, cannot be exhibited.

Also, when the particle size of the inorganic filler is too large, voids tend to remain in the cured product, and if it is too small, the particle size tends to aggregate and deteriorate the dispersibility. The average particle diameter is preferably from 0.01 to 5 μm, more preferably from 0.05 to 1.5 μm, and still more preferably from 0.1 to 1 μm. If the average particle diameter of the inorganic filler is within the range, good fluidity of the resin composition will be maintained. In addition, the average particle diameter can be measured with the particle size distribution measuring apparatus.

In the resin composition of the present invention, thermoplastic resins other than the phosphorus-containing phenoxy resin of the present invention may be used in combination. As for thermoplastic resins, for example: phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyester resins, Vinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamide imide resin, poly Tetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether resin, polyethene resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin etc. In terms of compatibility, phenoxy resins are preferred, and in terms of low dielectric properties, polyphenylene ether resins and modified polyphenylene ether resins are preferred.

The resin composition of the present invention can be formulated with a coupling agent. By formulating a coupling agent, the adhesion to the base material and the adhesion between the matrix resin and the inorganic filler can be improved. As far as couplers are concerned, it can be listed Examples include silane coupling agents, titanate coupling agents, and the like. These coupling agents can be used alone or in combination of two or more. Furthermore, the compounding amount of the coupling agent is preferably about 0.1 to 2.0% by mass relative to the total solid content in the resin composition. When the amount of the coupling agent is too small, the effect of improving the adhesion between the matrix resin and the inorganic filler cannot be fully obtained. On the other hand, when the amount of the coupling agent is too large, the coupling agent will be removed from the obtained hardened product Risk of seepage.

As far as silane coupling agents are concerned, examples include: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxy Epoxysilanes such as cyclohexyl)ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and other aminosilanes, 3-mercapto Propyl trimethoxysilane and other mercaptosilanes, p-styryl trimethoxysilane, vinyl trichlorosilane, vinyl ginseng (β-methoxyethoxy) silane, vinyl trimethoxysilane, vinyl trimethoxysilane Ethoxysilane, γ-methacryloxypropyl trimethoxysilane and other vinyl silanes, as well as epoxy-based, amino-based, vinyl-based polymer silanes, etc.

As far as titanate coupling agents are concerned, for example: isopropyl triisostearyl titanate, isopropyl tris(N-aminoethyl/aminoethyl) titanate, diisopropyl Dioctyl bis(dioctyl phosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetrakis(2, 2-diallyloxymethyl-1-butyl) bis(di-tridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis( Dioctyl pyrophosphate) ethylidene titanate, etc.

Examples of other additives include organic pigments such as quinacridone-based, azo-based, and phthalocyanine-based pigments; inorganic pigments such as titanium oxide, metal foil pigments, and anti-rust pigments; hindered amine-based, benzotriazole-based pigments, etc. , diphenyl ketone series and other ultraviolet absorbers; hindered phenol series, phosphorus series, sulfur series, hydrazine series Antioxidants such as stearic acid, palmitic acid, zinc stearate, calcium stearate and other release agents; additives such as leveling agent, rheology control agent, pigment dispersant, anti-shrinkage agent, defoamer, etc. Relative to the total solid content of the resin composition, the blending amount of these other additives is preferably in the range of 0.01 to 20% by mass.

The resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components. A resin composition containing a phosphorus-containing phenoxy resin, a curable resin component and, if necessary, various additives can be easily formed into a cured product by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, injection molded products, molded products, adhesive layers, insulating layers, and films. In terms of the method used to obtain the hardened product, the same method as the conventional resin composition can be used, and it can be suitably used: injection molding, injection, potting, dipping, drip coating, transfer molding, compression Molding, etc., or laminated in the form of resin sheets, resin-coated copper foil, prepregs, etc., and heated and pressurized to make laminates. Although the curing method of the resin composition varies with the blending ingredients and blending amount in the resin composition, usually the curing temperature is 80 to 300°C, and the curing time is 10 to 360 minutes. This heating is preferably carried out in a two-stage process of primary heating at 80 to 180°C for 10 to 90 minutes, and secondary heating at 120 to 200°C for 60 to 150 minutes. In addition, at the glass transition temperature (Tg) In the compounding system exceeding the temperature of the second heating, it is preferable to further perform three times of heating at 150 to 280° C. for 60 to 120 minutes. By performing such secondary heating and tertiary heating, poor hardening can be reduced. When making resin sheets, resin-coated copper foils, prepregs, and other resin semi-cured products, the resin composition is usually hardened by heating to maintain its shape. When the resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., but less than 5% by mass of the solvent may remain in the semi-cured resin.

In terms of applications using the resin composition of the present invention, it can be applied to various fields such as circuit board materials, sealing materials, injection molding materials, conductive pastes, adhesives, insulating materials, etc. Insulation injection molding, laminate materials, sealing materials, etc. in the field of sex/electronics. Examples of applications include printed wiring boards, flexible wiring boards, laminates for electric/electronic circuits such as capacitors, metal foil with resin, adhesives such as film adhesives, and liquid adhesives, Semiconductor sealing materials, underfill materials, inter-wafer fillers for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat sink substrates, resist printing inks, but not limited to these.

Among these various applications, printed circuit board materials, insulating materials for circuit boards, and adhesive films for build-up can be used as so-called electronic components that have passive components such as capacitors and active components such as IC chips embedded in the substrate. Insulating materials for built-in substrates. Among these, it is preferable to be used as a printed circuit board material, a resin composition for a flexible wiring board, and an interlayer insulation material for a buildup board in view of properties such as high flame retardancy, high heat resistance, and solvent solubility. Materials for circuit boards (laminates) and semiconductor sealing materials.

When the resin composition is made into a plate shape such as a laminate, the filler used is preferably in the form of fibers, more preferably glass cloth, glass mat, Glass yarn cloth.

The resin composition can be made into a prepreg used for printed circuit boards and the like by impregnating the fibrous reinforcing base material. For the fibrous reinforcing base material, for example, inorganic fibers such as glass, or organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin can be used. Or non-woven, but not limited to.

There is no particular limitation on the method of producing the prepreg from the resin composition, for example, the varnish-like resin composition containing the above-mentioned organic solvent can be prepared by further blending an organic solvent A resin varnish adjusted to an appropriate viscosity is produced, and the resin varnish is impregnated into the fibrous base material, and then heated and dried to semi-harden the resin component (B-staged). The heating temperature is preferably from 50 to 200°C, more preferably from 100 to 170°C, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg, preferably 1 to 40 minutes, more preferably 3 to 20 minutes. At this time, the mass ratio of the resin composition to be used and the reinforcing base material is not particularly limited, but usually it is preferably adjusted so that the resin content in the prepreg becomes 20 to 80% by mass.

The resin composition of the present invention can be molded into a sheet or film and used. At this time, it can be formed into a sheet or a film using a conventionally known method. The method of manufacturing the resin sheet is not particularly limited, but examples include: (A) extruding the resin composition after kneading in an extruder, and forming it into a sheet using a T-die, a circular die, etc. Forming method; (B) casting method of dissolving or dispersing the resin composition in solvent such as organic solvent, and then casting it into a sheet; and (C) other conventionally known sheet forming methods, etc. Moreover, although the film thickness of a resin sheet is not specifically limited, For example, it is 10-300 micrometers, Preferably it is 25-200 micrometers, More preferably, it is 40-180 micrometers. When used in the build-up method, the optimum range is 40 to 90 μm. If the film thickness is 10 μm or more, insulation can be obtained, and if it is 300 μm or less, the circuit distance between electrodes will not be longer than necessary. Furthermore, although the solvent content of the resin sheet is not particularly limited, it is preferably 0.01 to 5% by mass relative to the entire resin composition. When the solvent content in the film is 0.01% by mass or more relative to the entire resin composition, it is easy to obtain adhesion and adhesion when laminated to a circuit board, and it is easy to obtain flatness after heating and curing when it is 5% by mass or less.

In terms of a more specific method for producing an adhesive sheet, the varnish-like resin composition containing the above-mentioned organic solvent can be coated using a reverse roll coater, a comma coater, a die coater, or the like. Spreading machine and coating on the support base film that will not dissolve in organic solvents Thereafter, it is obtained by heating and drying to B-stage the resin component. In addition, if necessary, another supporting base film may be laminated on the coated surface (adhesive layer) as a protective film, and dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer.

Examples of the supporting base film include metal foils such as copper foil, polyolefin films such as polyethylene films and polypropylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, silicon films, polyester films, etc. Among the imide films and the like, a polyethylene terephthalate film free of defects such as particles, excellent in dimensional accuracy, and also excellent in cost is preferable. Moreover, it is preferable that it is a metal foil which can easily multilayer a laminated board, and it is especially preferable that it is a copper foil. The thickness of the supporting base film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, since it has strength as a support and hardly causes lamination failure.

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

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

The resin sheet obtained in this way is usually an insulating adhesive sheet with insulation, but a conductive adhesive sheet can also be obtained by mixing conductive metal or metal-coated fine particles in the resin composition. In addition, the above-mentioned supporting base film is peeled off after being laminated on the circuit board or after heating and hardening to form an insulating layer. If the supporting base film is peeled off after heating and hardening the adhesive sheet, adhesion of dust and the like during the hardening step can be prevented. Here, the above-mentioned insulating bonding sheet is also an insulating sheet.

Metal foil with resin obtained from the resin composition of the present invention will be described. As the metal foil, single, alloy, or composite metal foils such as copper, aluminum, brass, and nickel can be used. It is preferable to use a metal foil with a thickness of 9 to 70 μm. There is no particular limitation on the method of manufacturing the metal foil with the resin from the flame-retardant resin composition and the metal foil containing the epoxy resin containing phosphorus, for example, the metal foil can be coated with a solvent by using a roll coater or the like. A resin varnish obtained by adjusting the viscosity of the phosphorus-containing resin composition is applied on one side of the metal foil, and then heated and dried to semi-harden the resin component (B-staged) to form a resin layer. When semi-curing the resin component, it can heat-dry at 100-200 degreeC for 1-40 minutes, for example. Here, the thickness of the resin portion of the resin-coated metal foil is preferably formed to be 5 to 110 μm.

In addition, in order to harden the prepreg and the insulating adhesive sheet, it is possible to use the usual hardening method of laminated boards in the manufacture of printed circuit boards, but it is not limited thereto.

For example, when using a prepreg to form a laminate, one or more prepreg bulk layers can be placed, and metal foils can be placed on one or both sides to form a laminate, and the laminate can be pressurized and heated to harden the prepreg , and integrate it to obtain a laminate. Here, as the metal foil, single, alloy or composite metal foils such as copper, aluminum, brass, and nickel can be used.

As for the conditions for heating and pressing the laminate, it is sufficient to adjust the conditions under which the resin composition will harden and heat and press. However, if the pressure is too low, air bubbles will remain inside the resulting laminate. And in the case of lower electrical properties, it is advisable to press to meet the conditions of formability. The heating temperature is preferably from 160 to 250°C, more preferably from 170 to 220°C. The pressing pressure is preferably from 0.5 to 10 MPa, more preferably from 1 to 5 MPa. The heating and pressing 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, thermal decomposition of the cured product may be caused. When pressurized pressure is low, there will be If air bubbles remain inside the laminate and the electrical characteristics are lowered, if the applied pressure is high, the resin may flow out before hardening and a laminate of desired thickness may not be obtained. Also, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if the heating and pressing time is long, thermal decomposition of the cured product may occur.

In addition, the single-layer laminate obtained in this way can be used as an inner layer material to produce a multi-layer board. In this case, firstly, a circuit is formed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution and blackened to obtain an inner layer material. On the circuit forming surface of one or both sides of the inner layer material, an insulating layer is formed with prepreg or resin sheet, insulating adhesive sheet or metal foil with resin, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board .

In addition, when using a prepreg to form an insulating layer, one prepreg or a plurality of prepregs are placed on the circuit formation surface of the inner layer, and a metal foil is further placed on the outside to form a laminate. Then, the laminate is integrally molded by heating and pressing, whereby the cured product of the prepreg is formed as an insulating layer and the outer metal foil is formed as a conductor layer. Here, as the metal foil, the same one as that used for the laminated board used as the inner layer board can be used. In addition, heat and pressure molding can be performed under the same conditions as inner layer molding. Through-hole formation and circuit formation can be further performed on the surface of the multi-layer laminate formed in this way by an additive method or a subtractive method, so that the printed circuit board can be formed. In addition, a multi-layer multi-layer board can be further formed by using a printed circuit board as an inner layer material and repeating the above-mentioned process.

For example, when an insulating layer is formed with an insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit formation surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is placed between the circuit-forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is integrally molded by heating and pressing, whereby the cured product of the insulating adhesive sheet is formed as an insulating layer and an inner layer material is formed. layered. Alternatively, an inner layer material and a metal foil serving as a conductor layer may be formed, and a cured product of an insulating adhesive sheet may be formed as an insulating layer. Here, as the metal foil, the same one as that used for the laminate used as the inner layer material can be used. In addition, heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

In addition, when coating a resin composition on a laminate to form an insulating layer, it is preferable to apply the resin composition to a thickness of 5 to 100 μm, and then heat and dry it at 100 to 200° C. (preferably 150 to 200° C.) 1 to 120 minutes (preferably 30 to 90 minutes) to form a sheet. It belongs to those formed by the method usually called casting method. The thickness after drying is preferably 5 to 150 μm, preferably 5 to 80 μm. Furthermore, from the viewpoint of sufficient film thickness and less chance of uneven coating or streaks, the viscosity of the resin composition is preferably 10 to 40,000 mPa‧s at 25°C, and more preferably 200 to 30,000 mPa‧s. A printed circuit board can be formed by further forming through-holes and circuits on the surface of the thus formed multilayer laminate by additive or subtractive methods. In addition, by using the printed circuit board as an inner layer material and repeating the above-mentioned process, a multi-layer laminate can be further formed.

As for the sealing material obtained by using the resin composition of the present invention, there are tape (tape)-shaped semiconductor wafers, package-type liquid sealing, underfill, semiconductor interlayer insulating films, etc., which can be suitably used here. Wait. For example, for semiconductor encapsulation molding, a method of molding a resin composition using an injection molding machine, a transfer molding machine, an injection molding machine, etc., and heating at 50 to 200° C. for 2 to 10 hours to obtain a molded product can be mentioned.

In order to prepare the resin composition as a semiconductor sealing material, it is possible to use an extruder or a kneader after mixing a compounding agent such as an inorganic filler and other additives such as a coupling agent and a release agent in the resin composition if necessary. , rolls, etc., are fully melted and mixed until uniform Law. At this time, silicon oxide is usually used as an inorganic filler, but in this case, it is preferable to mix it in the resin composition so that the ratio of the inorganic filler may be 70 to 95% by mass.

When using the resin composition obtained in this way as a tape-shaped sealing material, the resin composition can be heated to produce a prepreg, and after making a sealing material tape, the sealing material tape is placed on a semiconductor wafer and heated at 100 to 150°C. It is a method of softening and forming by heating, and completely hardening at 170 to 250 °C. In addition, when used as an encapsulation-type liquid sealing material, the obtained resin composition may be dissolved in a solvent if necessary, and then 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 resist printing ink. At this time, it can be listed as follows: blending a vinyl monomer with an ethylenically unsaturated double bond in the resin composition, a cationic polymerization catalyst as a hardener, and adding pigments, talc and fillers to make a resist printing ink After the composition is coated on the printed substrate by screen printing, it is a method of making a hardened resist printing ink. The curing temperature at this time is preferably in the temperature range of about 20 to 250°C.

Since the cured product obtained from the resin composition of the present invention is excellent in heat resistance and flame retardancy, it is easy to introduce a skeleton for imparting various properties to the phosphorus-containing phenoxy resin. Therefore, it can be used especially for multilayer printed wiring boards, film adhesives, underfill materials, insulating sheets, prepregs, etc. that must have specific properties such as flame retardancy and dielectric properties, low water absorption, and solvent solubility.

[Example]

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these in the range which does not deviate from the summary. Unless otherwise specified, "parts" represent parts by mass, and "%" represent % by mass.

Analysis methods and measurement methods are shown below.

(1) Epoxy equivalent:

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

From the non-volatile matter, calculate the value as the conversion value of the solid content.

(2) Weight average molecular weight (Mw):

Determined by GPC measurement. Specifically, when the main body (manufactured by TOSOH Co., Ltd., HLC-8320GPC) is equipped with a column (manufactured by TOSOH Co., Ltd., TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H) in series, the tube The column temperature was set at 40°C. In addition, DMF (containing 20 mM lithium bromide) was used for the eluent, the flow rate was set at 0.3 mL/min, and an RI detector was used as the detector. As the measurement sample, 20 μL of “those dissolved in 10 mL of DMF with a solid content of 0.1 g and filtered through a 0.45 μm microfilter” were used. The amount obtained from standard polyethylene oxide (manufactured by TOSOH Co., Ltd., SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150) Line to convert and find Mw. In addition, GPC-8020 model H version 6.00 manufactured by TOSOH Co., Ltd. was used for data processing.

(3) Phosphorus content:

Sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, heated and wet-ashed, and all the phosphorus atoms were regarded as orthophosphoric acid. React metavanadate and molybdate in acidic sulfuric acid solution, measure the absorbance at 420nm of the phosphovanadate molybdate complex produced, and express the phosphorus content obtained from the previously prepared calibration curve in %.

(4) Glass transition temperature (Tg):

Measured according to IPC-TM-650 2.4.25.c. Specifically, the glass transition initiation temperature (Tig) is extrapolated from the DSC chart obtained in the second cycle of differential scanning calorimetry. The differential scanning calorimetry device used was manufactured by SII NanoTechnology Co., Ltd. "EXSTAR6000DSC6200". As a measurement sample, resin films were punched, laminated, and packaged in aluminum capsules. The measurement was carried out in 2 cycles from room temperature to 240°C at a heating rate of 10°C/min.

(5) Flame retardancy:

According to UL94VTM (Underwriters Laboratories Inc.'s safety certification specification), it is evaluated by vertical method. Evaluation lines are described as VTM-0, VTM-1, and VTM-2. VTM-0 is the most excellent in flame retardancy, and it becomes worse in the order of VTM-1 and VTM-2. But the complete burner is recorded as X.

(6) Water absorption:

The measurement was performed using 5 test pieces cut out of the resin film into a square of 50 mm x 50 mm. Use a hot-air circulation oven to dry the test piece at 100°C for 10 minutes in an air environment, then measure the mass immediately, then immerse the test piece in warm water at 50°C, and calculate the water absorption rate from the mass increase after 48 hours.

Synthesis Example 1

In the reaction device equipped with a stirring device, a thermometer, a nitrogen gas introduction device, a cooling pipe and a water separator, at room temperature, feed 200 parts of propylene glycol monomethyl ether acetate, 108 parts of DOPO, and 4.2 parts of water (The molar ratio of water/DOPO=0.47), the temperature was raised to 70° C. under nitrogen environment and dissolved completely. Therein, 78.9 parts of NQ (NQ/DOPO molar ratio=0.999) was fed in 30 minutes. After the feed was completed, the temperature was raised to 145° C. at the beginning of 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 adding 2500 parts of benzyl acetate to the filter residue and heating to dissolve it completely, cool to room temperature and let stand for 1 day, and filter the generated precipitate by suction filtration. Put the filtrate into 39% aqueous methanol, and the resulting precipitate The product was filtered by suction filtration, and a phosphorus-containing bifunctional phenolic compound represented by the following formula (9) (purity 99% or more) was obtained in the form of filter residue.

Synthesis example 2

In the same device as in Synthesis Example 1, at room temperature, feed 108 parts of DOPO, 53 parts of BQ (the mol ratio of BQ/DOPO=0.98), 1.8 parts of water (the mol ratio of water/DOPO =0.20), 200 parts of PMA, heated up to 145°C at the beginning of reflux under a nitrogen environment, and continued to react for 3 hours while maintaining the reflux state.

The resulting product was cooled to room temperature and filtered by suction filtration. After adding 2500 parts of benzyl acetate to the filter residue and heating to dissolve it completely, cool to room temperature and let stand for 1 day, and filter the generated precipitate by suction filtration. The filtrate was poured into 39% aqueous methanol, and the resulting precipitate was filtered by suction filtration to obtain a phosphorus-containing bifunctional phenolic compound represented by the following formula (10) in the form of filter residue (purity 99% or more).

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

[2-functional epoxy resin]

(A-1): Bisphenol A liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name: YD-8125, epoxy equivalent: 172, repetition number of formula (8) j≒0.01)

(A-2): Epoxy resin of 3,3',5,5'-tetramethyl-4,4'-biphenol (manufactured by Mitsubishi Chemical Co., Ltd., product name: YX-4000, epoxy equivalent: 186, j≒0.06)

(A-3): 4,4'-(3,3,5-trimethylcyclohexylene) bisphenol epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: TX-1468, cyclo Oxygen equivalent: 218, j≒0.04)

(A-4): Bisphenol F type liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., product name: YDF-170, epoxy equivalent: 169)

(A-5): Phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: YDPN-638, epoxy equivalent: 177)

[Bifunctional phenolic compound]

(B-1): Phosphorus-containing bifunctional phenolic compound obtained in Synthesis Example 1 (hydroxyl equivalent: 294, phosphorus content 10.5%)

(B-2): Phosphorus-containing bifunctional phenolic compound obtained in Synthesis Example 2 (hydroxyl equivalent: 269, phosphorus content 11.5%)

(B-3): Phosphorus-containing compound, DOPO-HQ (manufactured by Sanko Chemical Co., Ltd., product name: HCA-HQ, hydroxyl equivalent: 162, phosphorus content rate: 9.5%)

(B-4): Phosphorus-containing compound, DOPO-NQ (manufactured by Sanko Chemical Co., Ltd., product name: HCA-NQ, hydroxyl equivalent: 187, phosphorus content rate: 8.3%)

(B-5): Bisphenol A (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent: 114)

[catalyst]

(C-1): 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name: CUREZOL 2E4MZ)

(C-2): Triphenylphosphine (reagent)

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

[hardener]

DICY: Dicyandiamide (manufactured by CARBIDE Industry Co., Ltd., Japan, product name: DIHARD, active hydrogen equivalent 21)

Example 1

In the reaction device equipped with stirring device, thermometer, nitrogen introduction device and cooling pipe, at room temperature, feed (A-1) 561 parts, (B-2) 130 parts, (B-5) 309 parts, two 430 parts of ethylene glycol dimethyl ethers were heated up to 145° C. while stirring while flowing nitrogen gas, and after adding 0.1 part of (C-1), the temperature was raised to 165° C., and the reaction was carried out at the same temperature for 10 hours. Dilute and mix with 800 parts of methyl cylusol and 800 parts of cyclopentanone to obtain a resin varnish 1 of a phosphorus-containing phenoxy resin with a non-volatile content of 33%. Apply this resin varnish on a release film (made of polyimide film) using a roll coater so that the film thickness after solvent drying becomes 60 μm, dry at 150°C for 10 minutes, and peel off from the release film Dry film. Two pieces of dry film are stacked, and the vacuum pressure is 0.5kPa, the drying temperature is 180°C, It was pressed for 60 minutes at a pressing pressure of 2 MPa to obtain a resin film with a thickness of 100 μm. In addition, in order to adjust the thickness, a spacer with a thickness of 100 μm was used.

The epoxy equivalent and Mw were measured using the resin varnish, and the phosphorus content, Tg, flammability, and water absorption were measured using the resin film. Table 1 shows the results. In addition, the molar ratio in the table represents the molar ratio of (epoxy group of raw material epoxy resin)/(hydroxyl group of raw material 2-functional phenol compound). X1 (mole %) represents the ratio of the base (X1) in the X overall mole number of formula (1) in mole %.

Examples 2 to 7

Resin varnishes 2 to 7 and resin films were obtained by the same operation using the same apparatus as in Example 1 according to the compounding ratio (parts) described in Table 1. Table 1 shows the measurement results of epoxy equivalent, Mw, phosphorus content, Tg, flammability, and water absorption.

Comparative Examples 1 to 6

Resin varnishes H1 to H6 and resin films were obtained in the same manner using the same equipment as in Example 1 according to the blending ratio (parts) recorded in Table 2. Table 2 shows the measurement results of epoxy equivalent, Mw, phosphorus content, Tg, flammability and water absorption.

Embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, embodiment 5 and comparative example 4, embodiment 6 and comparative example 5 and embodiment 7 and comparative example 6, just all contain the formula (3) shown Comparing the case where the phosphorus group is contained and the phosphorus content, epoxy equivalent, and Mw are almost the same, it is different in that the comparative example does not have the group (X1), but it can be seen that in all cases, compared with the comparative example , The flame retardancy and heat resistance of the examples are excellent. In addition, from Example 5, Example 6, and Example 7, it can be seen that even if the type of the group (X2) is changed, the flame retardancy is still excellent.

Example 3 and Comparative Example 3 are compared with respect to increasing the phosphorus content until the flame retardancy meets VTM-0. It can be seen that the example with the group (X1) has better heat resistance and water resistance.

Example 4 and Comparative Example 3 are compared with the same water absorption rate. It can be seen that the example with the group (X1) has better heat resistance and water resistance, and can increase the phosphorus content.

From the above, it can be seen that the introduction range of the group (X2) becomes wider, that is, various properties can be imparted.

Example 8

Add 303 parts of the resin varnish 3 obtained in Example 3, 100 parts of (A-4) as epoxy resin, 6.2 parts of DICY as hardener, 0.2 part of (C-1) as hardening accelerator, As a solvent, 50 parts of methyl celuso and 50 parts of DMF were uniformly stirred and mixed to obtain a composition varnish. This composition varnish was applied to a release film using a roll coater so that the thickness of the dry film after solvent drying became 60 μm, and after drying at 150° C. for 10 minutes, the dry film was peeled off from the release film. Two dried films were stacked and pressed for 60 minutes using a vacuum press machine under the conditions of a vacuum degree of 0.5kPa, a heating temperature of 200°C, and a pressing pressure of 2 MPa to obtain a cured film with a thickness of 100 μm. In addition, in order to adjust the thickness, a spacer with a thickness of 100 μm was used.

Examples 9 to 11 Comparative Examples 7 to 8

According to the compounding ratio (part) recorded in Table 3, the epoxy resin composition varnish and cured film were obtained by the same operation as in Example 8. Tg, flammability, and water absorption were measured about the cured film, and the results are shown in Table 3.

It can be seen that although Example 8 and Comparative Example 7, and Example 9 and Comparative Example 8 were prepared in the same manner, the heat resistance and water absorption of the Examples were superior.

Claims (9)

A phosphorus-containing phenoxy resin represented by the following formula (1), whose weight average molecular weight is 10,000 to 200,000;

Wherein, X is a divalent group, but at least a part of X is the group X1 shown in the following formula (2), Y is independently a hydrogen atom or a glycidyl group, n is the number of repetitions and its average value is 25 to 500;

Among them, A is an aromatic ring group selected from benzene ring, naphthalene ring, anthracene ring or phenanthrene ring, and these aromatic ring groups may have an alkyl group with 1 to 8 carbons, an alkoxy group with 1 to 8 carbons, Cycloalkyl with 5 to 8 carbons, aryl with 6 to 10 carbons, aralkyl with 7 to 11 carbons, aryloxy with 6 to 10 carbons, or aralkyloxy with 7 to 11 carbons Any one of the groups is used as a substituent, and Z is a phosphorus-containing group shown in the following formula (3);

Among them, R ¹ and R ² are hydrocarbon groups with a carbon number of 1 to 20 that may have heteroatoms, and may be different or the same, and may be linear, branched, or cyclic, and R ¹ and R ² may also be bonded Knot and form a ring structure site, k1 and k2 are independently 0 or 1. Phosphorus-containing phenoxy resin as described in claim 1, wherein the phosphorus-containing group represented by the above formula (3) is a phosphorus-containing group represented by the following formula (3a) and/or (3b) ;

Wherein, R ³ and R ⁴ are each independently a hydrocarbon group with 1 to 11 carbons, m1 is each independently an integer of 0 to 4, and m2 is each independently an integer of 0 to 5. The phosphorus-containing phenoxy resin as described in item 1 or item 2 of the scope of the patent application, wherein the above-mentioned X contains the above-mentioned group X1, and is in the range of 25 to 75 mol% relative to the total mole number of X Phosphorus-free group X2 containing no phosphorus. Phosphorus-containing phenoxy resin as described in item 3 of the scope of the patent application, wherein the above-mentioned non-phosphorus group X2 contains at least one of the divalent groups shown in the following formulas (4a) to (4c) a foundation of foundations;

Wherein, R ⁵ is a direct bond or a divalent group selected from a hydrocarbon group with 1 to 20 carbons, -CO-, -O-, -S-, -SO ₂ - and -C(CF ₃ ) ₂ -, R ^6. R ⁷ and R ⁸ are each independently a hydrocarbon group with 1 to 11 carbons, m3 and m4 are each independently an integer of 0 to 4, and m5 is an integer of 0 to 6. The phosphorus-containing phenoxy resin described in claim 1 or claim 2, wherein the phosphorus content is 1 to 10% by mass. A resin composition, which is obtained by blending the phosphorous-containing phenoxy resin described in any one of the first to fifth claims of the patent application in the curable resin component. The resin composition according to claim 6, wherein the curable resin component is at least one resin selected from epoxy resin, acrylate resin, melamine resin, isocyanate resin and phenol resin. A material for circuit boards obtained by using the resin composition described in item 6 or item 7 of the patent application. A hardened product, which is obtained by hardening the resin composition described in item 6 or item 7 of the patent application.