TW202142584A - Phosphorus-containing phenoxy resin, resin composition, cured product, laminated plate for electric/electronic circuits, and method for producing phosphorus-containing phenoxy resin - Google Patents

Abstract

Provided are a phosphorus-containing phenoxy resin having excellent fire-resistance and solubility, a resin composition containing said phosphorus-containing phenoxy resin and a curing agent, a cured product thereof having excellent heat resistance and strength, and a laminated plate for electric/electronic circuits. This phosphorus-containing phenoxy resin is represented by formula (1), and has a weight average molecular weight of 10,000-200,000 and a percentage content of phosphorus of 1-6 mass%. In the formula, X represents a divalent group represented by formula (2), and Y represents a hydrogen atom, an acyl group, or a glycidyl group. Z represents an acyl group or a hydrogen atom, and the acyl group accounts for 5 mol% or more of all of said Z. "A" represents a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. W represents a phosphorus-containing group represented by formula (3).

Description

Phosphorus-containing phenoxy resin, resin composition, cured product, laminated board for electric and electronic circuits, and method for manufacturing phosphorus-containing phenoxy resin

The present invention relates to a phosphorus-containing phenoxy resin with excellent flame retardancy and solvent solubility. In addition, it relates to a resin composition containing the phosphorus-containing phenoxy resin and a curing agent, a cured product of the resin composition having excellent flame retardancy and strength, and electrical and electronic circuits containing the resin composition Laminated board.

Epoxy resins have excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, and electrical properties, so they are widely used in fields such as coatings, civil engineering, adhesives, and electrical material applications. In addition, film-forming properties are imparted by high molecular weight by various methods. This high molecular weight epoxy resin is called phenoxy resin. In particular, bisphenol A type phenoxy resins are mainly used as base resins for varnishes for paints and base resins for film formation, or are used for the following purposes: adding to epoxy resin varnishes to adjust fluidity or Improve the toughness and adhesiveness of hardened products. In addition, those having a phosphorus atom or a bromine atom in the skeleton are used as a flame retardant compounded in an epoxy resin composition or a thermoplastic resin.

Phenoxy resins used for electrical materials such as laminates for electrical and electronic circuits are required to have flame retardancy and solvent solubility.

Therefore, for the flame-retarding of epoxy resins, halogen-free flame-retarding technologies using phosphorus compounds have been studied. Patent Documents 1 to 3 disclose phosphorus-containing compounds obtained by reacting specific phosphorus compounds with epoxy resins. Flame-retardant epoxy resin. Patent Document 1 and Patent Document 2 disclose combining 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide with epoxy resin in a predetermined molar ratio. Phosphorus-containing flame-retardant epoxy resin obtained by the reaction. In addition, Patent Document 3 discloses that 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide reacts with epoxy resin in a predetermined ratio. Phosphorus flame-retardant epoxy resin. However, the phosphorus-containing flame-retardant epoxy resins obtained by these methods have poor solubility in epoxy resins and solvents. [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 04-11662 [Patent Document 2] Japanese Patent Laid-Open No. 2000-309623 [Patent Document 3] Japanese Patent Laid-open No. 11-279258

The subject of the present invention is to provide a phosphorus-containing phenoxy resin excellent in flame retardancy and solubility. In addition, the resin composition containing the phosphorus-containing phenoxy resin is cured to provide a cured product excellent in flame retardancy and strength.

In order to solve the problem, the present inventors conducted intensive studies on phosphorus-containing phenoxy resins. As a result, they found that phosphorus-containing phenoxy resins having a specific structure are excellent in flame retardancy and solubility. The cured product formed by curing the resin composition of the phenoxy resin is excellent in flame retardancy and strength, thereby completing the present invention.

式中，X獨立地為含有下述式（2）所表示的二氧基的二價基，Y分別獨立地為氫原子、具有碳數1～20的烴基的醯基、或縮水甘油基，Z為具有碳數1～20的烴基的醯基或氫原子，且5莫耳%以上為所述醯基，n是重覆數的平均值，為15以上且500以下。That is, the present invention is a phosphorus-containing phenoxy resin represented by the following formula (1), a weight average molecular weight of 10,000 to 200,000, and a phosphorus content of 1% by mass to 6% by mass. [化1]

In the formula, X is independently a divalent group containing a dioxy group represented by the following formula (2), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, or a glycidyl group, Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms, and 5 mol% or more is the acyl group, and n is the average value of the number of repetitions, which is 15 or more and 500 or less.

式中，A是碳數6～20的三價芳香族烴基，W是由式（3）表示的含磷的基。R¹ 及R² 分別獨立地為可含有雜元素的碳數1～20的烴基，可為直鏈狀、支鏈狀、環狀，並且R¹ 與R² 可鍵結而形成環狀結構，k1及k2分別獨立地為0或1。[化2]

In the formula, A is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and W is a phosphorus-containing group represented by formula (3). R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbons that may contain a hetero element, which may be linear, branched, or cyclic, and R ¹ and R ² may be bonded to form a cyclic structure, k1 and k2 are independently 0 or 1, respectively.

The epoxy equivalent of the phosphorus-containing phenoxy resin is preferably 2000 g/eq. to 50000 g/eq.

In addition, the present invention is a resin composition containing the phosphorus-containing phenoxy resin and a hardener. With respect to 100 parts by mass of the solid content of the phosphorus-containing phenoxy resin, the resin composition may contain a curing agent in an amount of 0.1 to 100 parts by mass in terms of solid content.

The resin composition contains the phosphorus-containing phenoxy resin, epoxy resin and hardener, and the mass ratio of the solid content of the phosphorus-containing phenoxy resin to the epoxy resin may be 99/1 to 1/ 99. The resin composition may contain 0.1 parts by mass to 100 parts by mass of the curing agent in terms of solid content with respect to 100 parts by mass of the total solid content of the phosphorus-containing phenoxy resin and epoxy resin.

As the hardener formulated in the resin composition, there are selected from acrylic resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, At least one of the group consisting of organic phosphines, polyisocyanate compounds, blocked isocyanate compounds, and active ester hardeners.

In addition, the present invention is a cured product obtained by curing the resin composition. In addition, the present invention is a laminate for electric and electronic circuits obtained by using the resin composition.

式中，X¹ 獨立地為含有所述式（2）所表示的二氧基的二價基，式（4）及式（5）的X¹ 中整體含有式（2）所表示的二氧基。 Z¹ 為具有碳數1～20的烴基的醯基或氫原子，5莫耳%以上為所述醯基。此處，式（5）所表示的化合物可為選自Z¹ 的兩者為醯基的化合物、一者為醯基的化合物及兩者為氫原子的化合物的兩種以上的混合物。 m是重覆數的平均值，為0以上且6以下。In addition, the present invention is a method for producing the phosphorus-containing phenoxy resin, characterized by reacting a difunctional epoxy resin represented by the following formula (4) with a compound represented by the following formula (5). [化3]

In the formula, X ^{1 is} independently a divalent group containing the dioxy group represented by the formula (2), and X ¹ in the formula (4) and formula (5) contains the dioxy group represented by the formula (2) as a whole base. Z ¹ is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbons, and 5 mol% or more is the acyl group. Here, the compound represented by the formula (5) may be ^{a mixture of two or more compounds selected from the group consisting of compounds in which two of Z 1} are acyl groups, one of which is an acyl group, and compounds in which both are hydrogen atoms. m is the average value of the number of repetitions, and is 0 or more and 6 or less.

式中，X² 獨立地為含有所述式（2）所表示的二氧基的二價基，Y² 分別獨立地為氫原子或縮水甘油基。n是重覆數的平均值，為15以上且500以下。The present invention is further a method for producing the phosphorus-containing phenoxy resin, characterized in that the alcoholic hydroxyl group of the phosphorus-containing phenoxy resin (a) represented by the following formula (6) is adjusted to the alcoholic hydroxyl group The equivalent is 1 mol, and the reaction is carried out at 0.05 mol or more and 2.0 mol or less. [化4]

In the formula, X ^{2 is} independently a divalent group containing the dioxy group represented by the formula (2), and Y ^{2 is} each independently a hydrogen atom or a glycidyl group. n is the average value of the number of repetitions, and is 15 or more and 500 or less.

According to the present invention, it is possible to provide a phosphorus-containing phenoxy resin excellent in flame retardancy and solubility. In addition, by using the resin composition of the phosphorus-containing phenoxy resin, a cured product excellent in flame retardancy and strength can be provided.

Regarding the phosphorus-containing phenoxy resin of the present invention, the weight average molecular weight (Mw) represented by the formula (1) is 10,000 to 200,000, the phosphorus content is 1 mass% to 6% by mass, and it has the formula ( 2) The phosphorus-containing dioxy group represented, and further has a structure in which part or all of the hydrogen atoms in the hydroxyl group are substituted with acyl groups (Z). Here, if Mw is less than 10,000, film-forming properties and mechanical properties (especially folding resistance) may decrease, which is not preferable. If the Mw is greater than 200,000, the compatibility may decrease, and it may be difficult to handle the resin, which is not good. Mw is preferably 15,000 to 160,000, more preferably 20,000 to 120,000, and still more preferably 20,000 to 120,000. Furthermore, the Mw of the phosphorus-containing phenoxy resin can be measured by the gel permeation chromatography (GPC (gel permeation chromatography, GPC) GPC method) described in the examples.

The phosphorus-containing phenoxy resin of the present invention has a structure in which a hydrogen atom in a hydroxyl group is substituted with an acyl group, so that it has low polarity, and low hygroscopicity or solubility becomes good. In addition, the effect of excellent dielectric properties is obtained.

The phenoxy resin of the present invention can be advantageously obtained by the production method of the present invention. In this specification, the phosphorus-containing phenoxy resin obtained by the production method of the present invention may be referred to as the "phosphorus-containing phenoxy resin of the present invention", and the resin composition of the present invention may be hardened. The resultant cured product is referred to as the "cured product of the present invention", and the method for producing the phosphorus-containing phenoxy resin of the present invention is referred to as the "production method of the present invention".

In the formula (1), X is independently a divalent group containing the dioxy group represented by the formula (2). That is, it is a dioxy group represented by Formula (2), or a group containing this dioxy group and other divalent groups other than this. The group represented by the formula (2) has oxygen atoms at both ends, so it is called a dioxy group. The divalent group is any one of the dioxy group represented by the formula (2) and other divalent groups other than the dioxy group, and includes the dioxy group represented by the formula (2). Examples of divalent groups other than the above-mentioned dioxy groups include divalent groups represented by -O-Ar-O-, and examples of Ar include those obtained by removing two hydroxyl groups from a difunctional phenol compound that can be used in combination as described later. The residues and so on. The number of moles of the dioxy group represented by the formula (2) in the entire X is determined by the structure of the phosphorus-containing group represented by W or the target phosphorus content.

The dioxy group represented by the formula (2) is a residue obtained by removing two hydroxyl groups from the phosphorus-containing difunctional phenol compound (p1) described later. This phosphorus-containing bifunctional phenol compound (p1) is obtained by the reaction of an organophosphorus compound (p2) and a quinone compound.

In formula (2), A is a trivalent aromatic hydrocarbon group having 6 to 20 carbons derived from a quinone compound. The aromatic hydrocarbon group includes, for example, an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and the like, and a benzene ring group or a naphthalene ring group is preferred. Furthermore, these aromatic ring groups may have alkyl groups having 1 to 8 carbons, alkoxy groups having 1 to 8 carbons, cycloalkyl groups having 5 to 8 carbons, aryl groups having 6 to 10 carbons, and Any one of an aralkyl group having 7 to 12, an aryloxy group having 6 to 10 carbon atoms, or an aralkoxy group having 7 to 12 carbon atoms is used as a substituent.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, etc.; examples of the alkoxy group include those derived from these alkyl groups. Cycloalkyl groups having 5 to 8 carbon atoms include cyclohexyl, etc.; examples of aryl or aryloxy groups having 6 to 10 carbon atoms include phenyl, naphthyl, phenoxy, Naphthyloxy and the like; examples of the aralkyl or aralkoxy having 7 to 11 carbons include benzyl, phenethyl, 1-phenylethyl, benzyloxy, naphthylmethoxy, and the like. As preferred A, it is a benzene ring, a methyl substituent of a benzene ring, a 1-phenylethyl substituent of a benzene ring, a naphthalene ring, a methyl substituent of a naphthalene ring, or a 1-phenylethyl substituent of a naphthalene ring Substituents. In applications that require more solubility, benzene ring, methyl substituted benzene ring, and 1-phenylethyl substituted benzene ring are preferred. In applications where flame retardancy or heat resistance is more required, preferred It is a naphthalene ring, a methyl substituent of a naphthalene ring, or a 1-phenylethyl substituent of a naphthalene ring.

In the formula (2), W is the residue of the organophosphorus compound (p2) described later. In the formula (3), R ¹ and R ² are a C 1-20 hydrocarbon group which may have a hetero atom, and may be different or the same, and may be linear, branched, or cyclic. In addition, R ¹ and R ² may be bonded to form a cyclic structure. As the hetero atom, an oxygen atom or the like can be exemplified, and it may be contained between or at the end of the carbon constituting the hydrocarbon chain or the hydrocarbon ring. Examples of the hydrocarbon group having 1 to 20 carbons include: alkyl groups having 1 to 12 carbons, cycloalkyl groups having 5 to 12 carbons, alkoxy groups having 1 to 8 carbons, and cycloalkanes having 5 to 8 carbons. An oxy group, an aryl group with 6 to 12 carbons, an aralkyl group with 7 to 12 carbons, an alkynyl group with 2 to 12 carbons, an aryloxy group with 6 to 10 carbons, or an aralkyloxy group with 7 to 11 carbons Group and the like, particularly preferably aromatic ring groups such as a benzene ring.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, n-pentyl, and isopentyl. Base, neopentyl, tertiary pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. Examples of the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, cyclooctyl, trimethylcyclohexyl, cyclodecyl, and cyclododecyl. Base etc.

Examples of the alkoxy group having 1 to 8 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, and tertiary butoxy Group, n-pentyloxy, isopentyloxy, neopentyloxy, tertiary pentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy , N-undecyloxy, n-dodecyloxy, etc. Examples of the cycloalkoxy group having 5 to 8 carbon atoms include cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, methylcyclohexyloxy, cyclooctyloxy, and trimethylcyclohexyl. Oxy, cyclodecyloxy, cyclododecyloxy and the like.

Examples of the aryl group having 6 to 12 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, iso Propyl phenyl, mesitylene, ethynyl phenyl, naphthyl, vinyl naphthyl, etc.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, 1-phenylethyl Group, 2-phenylisopropyl, etc.

Examples of the alkynyl group having 2 to 12 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and 1 , 3-Butadiynyl, phenylethynyl, naphthaleneethynyl, etc.

Examples of the aryloxy group having 6 to 10 carbon atoms include: phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, ethylphenoxy group, xyloxy group, n-propylphenoxy group Group, isopropylphenoxy, mesityleneoxy, ethynylphenoxy, naphthyloxy, etc.

Examples of aralkyloxy groups having 7 to 11 carbon atoms include benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, naphthylmethoxy, and phenethoxy. , 2-Phenylisopropoxy and so on.

In addition, when R ¹ and R ² are aromatic cyclic groups, they may have an alkyl group with 1 to 8 carbons, an alkoxy group with 1 to 8 carbons, and a cycloalkane with 5 to 8 carbons as the substituent. Group, an aryl group having 6 to 10 carbons, an aralkyl group having 7 to 12 carbons, an aryloxy group having 6 to 10 carbons, or an aralkoxy group having 7 to 12 carbons.

式中，R³ 及R⁴ 分別獨立地可為碳數1～11的烴基，具體而言，可列舉甲基、乙基、第三丁基、環己基、苯基、甲苯基、苄基等，較佳為甲基、環己基、苯基、甲苯基、或苄基，更佳為甲基、苯基、或苄基。其中，存在於一個苯環上的4個R³ 的合計碳數為14以下，存在於一個苯環上的5個R⁴ 的合計碳數為14以下。As W, a phosphorus-containing group represented by the following formula (3a) or (3b) is preferred. [化5]

In the formula, R ³ and R ^{4 may} each independently be a hydrocarbon group having 1 to 11 carbon atoms, specifically, methyl, ethyl, tertiary butyl, cyclohexyl, phenyl, tolyl, benzyl, etc. , Preferably methyl, cyclohexyl, phenyl, tolyl, or benzyl, more preferably methyl, phenyl, or benzyl. Among them, ^{the total carbon number of four R 3s} present on one benzene ring is 14 or less, and the total carbon number of five R ⁴ presents on one benzene ring is 14 or less.

Moreover, as preferable W other than the said formula (3a) or formula (3b), the phosphorus containing group represented by following formula (a1)-(a10) is mentioned. [化6]

In the formula (1), Y is each independently a hydrogen atom, an acyl group or a glycidyl group having a hydrocarbon group having 1 to 20 carbon atoms. When Y is a hydrogen atom, a hydroxyl group is provided to the terminal, and when it is an acyl group, an ester group is provided to the terminal, and when it is a glycidyl group, an epoxy group is provided to the terminal. Therefore, the ratio can be controlled according to the application. The hydrocarbon group having 1 to 20 carbons is preferably an alkyl group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, or an aralkyl group having 7 to 13 carbons. Specific examples of these include the above-mentioned examples.的基。 The base. Among these, more preferred is an acyl group having a hydrocarbon group having 1 to 7 carbon atoms, further preferred is an acetyl group, a propionyl group, a butyryl group, a benzyl group, and a methylbenzyl group, and particularly preferably an acetyl group. , Benzoyl. In addition, an acetyl group is understood as an acyl group having a hydrocarbon group with a carbon number of 1.

In the formula (1), Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms. More than 5 mol% of Z is an acyl group, and the remainder is a hydrogen atom. Preferably, 10 mol% or more of Z, more preferably 50 mol% or more, and still more preferably 70 mol% or more are the above-mentioned acetone groups. In addition, the upper limit is preferably 100 mol%, but substantially 95 mol%. Specific examples of the acyl group having a hydrocarbon group having 1 to 20 carbons are the same as the acyl group exemplified in Y, and the preferred acyl group is also the same.

When all of Z (100 mol%) is an acyl group, the phosphorus-containing phenoxy resin of the present invention does not contain secondary hydroxyl groups, which can further improve dielectric properties and moisture resistance. On the other hand, for example, when fine-tuning the adhesion to metal, a part of Z remains as a hydrogen atom. Therefore, it can be used within a range that does not greatly affect other physical properties such as moisture resistance. The phosphorus-containing phenoxy resin of the present invention deliberately has an appropriate amount of secondary hydroxyl groups.

In formula (1), n is the number of repetitions and is the average value. The value range is 15 or more and 500 or less. From the viewpoint of formability and handleability, it is preferably 17 or more and 400 or less, and more preferably 20 or more and 300 or less. The n number can be calculated based on the number average molecular weight (Mn) obtained by the GPC method.

The phosphorus content of the phosphorus-containing phenoxy resin of the present invention is 1% by mass to 6% by mass, preferably 2% by mass to 5.5% by mass, and more preferably 3% by mass to 5% by mass. If the phosphorus content is less than 1% by mass, the flame retardancy may be insufficient. If the phosphorus content exceeds 6% by mass, the solvent solubility may be significantly deteriorated.

The epoxy equivalent of the phosphorus-containing phenoxy resin of the present invention is not particularly limited, but is preferably in the range of 2,000 g/eq. to 50,000 g/eq. If it is in this range, the phosphorus-containing phenoxy resin of the present invention itself participates in the hardening reaction and can be incorporated into the crosslinked structure.

The phosphorus-containing phenoxy resin of the present invention is obtained by partial or complete acylation of secondary hydroxyl groups, and can be obtained by various methods. As a preferable manufacturing method, for example, there are the following manufacturing methods. (A): A manufacturing method of reacting the difunctional epoxy resin represented by the formula (4) with the diester compound and/or the bifunctional phenol compound represented by the formula (5). Hereinafter, it may be referred to as a manufacturing method (A). (B): Phosphorus-containing phenoxy resin represented by the formula (6) (in order to distinguish it from the phosphorus-containing phenoxy resin of the present invention, it may be referred to as phosphorus-containing phenoxy resin (a) ) A manufacturing method that reacts with acid components (acylating agents) such as anhydrides of organic acids, halides of organic acids, and esters of organic acids. Hereinafter, it may be referred to as manufacturing method (B). The phosphorus-containing phenoxy resin obtained by the production methods (A) and (B) is the phosphorus-containing phenoxy resin of the present invention, and is represented by the same formula (1).

The production method (A) is a method of reacting the difunctional epoxy resin represented by the formula (4) with the compound represented by the formula (5). In the formula (4), G is a glycidyl group, m is the number of repetitions, and the average value thereof is 0 or more and 6 or less. In formula (5), ^{5 mol% or more of Z 1} is an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, and the remainder is a hydrogen atom. Here, the compound represented by formula (5) may be a compound selected from the group consisting of compounds ^{in which two of Z 1} are acyl groups, a compound in which one is an acyl group and the other is a hydrogen atom, and a compound in which both are hydrogen atoms A mixture of two or more. When ^{both of Z 1} are acyl groups, they are diesters, and when both of Z 1 are hydrogen atoms, they are diphenols. The compound represented by formula (5) is referred to as a diester compound. The diester compound may be a compound ^{in which both of Z 1} are acyl groups, or a compound (mixture) in which the main component (50% or more) is the compound.

^{X 1} in equations (4) and (5) is selected to give X in equation (1). ^{Therefore, any one of X 1 in} formula (4) and formula (5) must contain the dioxy group represented by formula (2). ^{For example, when X 1} of one of formula (4) or formula (5) includes the dioxy group, the other may include the dioxy group, or may not include the dioxy group.

The phosphorus-containing phenoxy resin of the present invention must contain the dioxy group represented by the formula (2). As long as this condition is satisfied, the dioxy group represented by the formula (2) may be contained in the difunctional epoxy resin as a raw material, In either of the diester compound and the bifunctional phenol compound, the ratio is not limited. ^{In addition, as X 1} in the formula (4) or formula (5), when the dioxy group represented by the formula (2) is not included, other divalent groups may be introduced into X ¹ .

The bifunctional epoxy resin used in the production method (A) of the present invention is the epoxy resin represented by the above formula (4), and for example, the bifunctional epoxy resin represented by the following formula (8) can be exemplified in the presence of an alkali metal compound Epoxy resin obtained by reacting functional phenol compound with epihalohydrin, etc.

As an epihalohydrin, epichlorohydrin, epibromohydrin, etc. are mentioned, for example. Examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal salts of organic acids such as sodium acetate and sodium stearate; alkali metal phenates, sodium hydride, lithium hydride, etc.

In the reaction of the difunctional phenol compound used to obtain the raw material epoxy resin with epihalohydrin, the functional group in the difunctional phenol compound is used in a range of 0.80 times mol to 1.20 times mol, preferably 0.85 times mol ~1.05 times moles of alkali metal compounds. If it is less than this, the amount of remaining hydrolyzable chlorine will increase, which is not preferable. As an alkali metal compound, it is used in the state of an aqueous solution, an alcohol solution, or a solid.

In the epoxidation reaction, an excess of epihalohydrin is used relative to the bifunctional phenol compound. Generally, 1.5 to 15 times mol of epihalohydrin is used relative to 1 mol of the functional group in the bifunctional phenol compound, preferably 2 times to 10 times mol, more preferably 5 times mol. Ear ~ 8 times mole. If it is more than this, the production efficiency is lowered, and if it is less than this, the production amount of the high molecular weight epoxy resin increases, and it is not suitable for the raw material of the phosphorus-containing phenoxy resin.

The epoxidation reaction is usually carried out at a temperature below 120°C. During the reaction, if the temperature is high, the amount of so-called hardly hydrolyzable chlorine increases, making it difficult to achieve high purity. Preferably it is 100 degrees C or less, More preferably, it is 85 degrees C or less temperature.

式中，X¹ 與所述式（4）或式（5）的X¹ 同樣。[化7]

Wherein, X ¹ and X in the formula (4) or (5) of ^a same.

When the bifunctional phenol compound represented by the formula (8) is reacted with epihalohydrin, m is usually greater than zero. In order to make m equal to 0, there are methods such as distillation, crystallization, etc. to highly refine the epoxy resin produced by a known method, or the allylation of the bifunctional phenol compound represented by the formula (8), and then the olefin Partial oxidation and epoxidation method.

In addition, the diester compound used in the production method (A) of the present invention converts the difunctional compound represented by the formula (8) by condensation reaction with an anhydride of an organic acid, a halide of an organic acid, or an organic acid. The phenol compound is obtained by acylation.

By using an epoxy resin in which m is 0 in formula (4) as a raw material, the phosphorus-containing phenoxy resin of the present invention does not contain secondary hydroxyl groups, and the dielectric properties and moisture resistance can be further improved. In addition, for example, when finely adjusting the adhesion to metal, an epoxy resin with an appropriate number of m is used. Therefore, the present invention may be used in the present invention within a range that does not greatly affect other physical properties such as moisture resistance. The phosphorus-containing phenoxy resin has a moderate amount of secondary hydroxyl groups deliberately.

The difunctional epoxy resin or diester-based compound used in the production method (A) of the present invention contains the dioxy group represented by the formula (2). The total phosphorus content of the difunctional epoxy resin and diester compound as the raw material, and the difunctional phenol compound used in combination as necessary becomes the phosphorus content of the phosphorus-containing phenoxy resin of the present invention. Therefore, according to the required phosphorus What is necessary is just to adjust the kind or compounding quantity of the difunctional epoxy resin, a diester compound, and a difunctional phenol compound used for content rate adjustment.

Regarding the usage amount of the difunctional epoxy resin and the diester compound, the ester group and/or the hydroxyl group are preferably 0.8 equivalent to 1.0 equivalent relative to 1 equivalent of the epoxy group. If it is this equivalent ratio, it is easy to perform high molecular weight in the state which has an epoxy group at a molecular terminal, and it is preferable. In addition, it is also possible to substitute a part of the diester-based compound with the bifunctional phenol compound represented by the above-mentioned formula (8). Thereby, as described above, by deliberately presenting an appropriate amount of secondary hydroxyl groups in the phosphorus-containing phenoxy resin of the present invention, fine adjustment of physical properties can be achieved. In the manufacturing method (A), a polymerization reaction and a transesterification reaction occur, Mw increases to generate a phenoxy resin, and part of the hydroxyl groups of the phenoxy resin is esterified.

In the production method (A), a catalyst can be used, and as the catalyst, any compound may be used as long as it has a catalyst function that promotes the reaction between an epoxy group and an ester group. For example, tertiary amines, cyclic amines, imidazoles, organophosphorus compounds, quaternary ammonium salts, etc. can be cited. In addition, these catalysts can be used alone or in combination of two or more.

Examples of tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol Etc., but not limited to these.

Examples of cyclic amines include: 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo[5,4,0]undecene- 7(DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), N-methylmorpholine, pyridine, N,N-dimethylaminopyridine (DMAP) Etc., but not limited to these.

Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Butylimidazole, 1-benzyl-2-phenylimidazole, etc. are not limited to these.

As the organophosphorus compound, for example, tri-n-propyl phosphine, tri-n-butyl phosphine, diphenyl methyl phosphine, triphenyl phosphine, tris (p-tolyl) phosphine, tricyclohexyl phosphine, tris( Tertiary butyl)phosphine, tris(p-methoxyphenyl)phosphine, p-methylphosphine, 1,2-bis(dimethylphosphine)ethane, 1,4-bis(diphenylphosphine)butane Phosphines; tetramethyl phosphonium bromide, tetramethyl phosphonium iodide, tetramethyl phosphonium hydroxide, tetrabutyl phosphonium hydroxide, trimethyl cyclohexyl phosphonium chloride, trimethyl cyclohexyl phosphonium bromide, Trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethyl chloride Phosphonium salts such as phosphonium, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc., but not limited to these .

Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, and tetraethyl Ammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethyl Benzyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl trimethyl ammonium hydroxide, benzyl tributyl ammonium chloride, phenyl trimethyl ammonium chloride, etc., but are not limited to these.

Among the above-listed catalysts, 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5 ,4,0]Undecene-7,1,5-diazabicyclo[4,3,0]nonene-5,2-ethyl-4-methylimidazole, tris(p-tolyl)phosphine, Tricyclohexylphosphine, tris(tertiary butyl)phosphine, tris(p-methoxyphenyl)phosphine, particularly preferably 4-(dimethylamino)pyridine, 1,8-diazabicyclo[5, 4,0] Undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, 2-ethyl-4-methylimidazole.

Although the amount of the catalyst used is usually 0.001% by mass to 1% by mass in the solid content of the reaction, when these compounds are used as the catalyst, the catalyst remains in the obtained phosphorus-containing benzene as a residue. In the oxy resin, the insulating properties of the printed wiring board may be deteriorated or the pot life of the composition may be shortened. Therefore, the content of catalyst-derived nitrogen in the phosphorus-containing phenoxy resin is preferably 0.5% by mass or less , More preferably 0.3% by mass or less. In addition, the content of catalyst-derived phosphorus in the phosphorus-containing phenoxy resin is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

In the production method (A) of the present invention, a solvent for reaction can be used, and as the solvent, any solvent may be used as long as it dissolves the phosphorus-containing phenoxy resin. For example, aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, ester solvents, etc. are mentioned. In addition, only one type of these solvents may be used, or two or more types may be used in combination.

As an aromatic solvent, benzene, toluene, xylene, etc. are mentioned, for example.

Examples of ketone-based solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, Acetylacetone, dioxane, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone, etc.

Examples of amide-based solvents include formamide, N-methyl formamide, N,N-dimethyl formamide (N,N-dimethyl formamide, DMF), acetamide, and N-methyl formamide. Acetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, etc.

As the glycol ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monomethyl ether Ethylene glycol dialkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, and propylene glycol monomethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether ; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol two Polyethylene glycol dialkyl ethers such as butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, etc. Propylene glycol dialkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether and other polypropylene glycol dialkyl ethers; B Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether ethyl Polyethylene glycol monoalkyl ether acetates such as acid esters; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, and butyl butyrate. , Valerolactone, butyrolactone, etc.

In addition, as other solvents, for example, dimethylsulfene, cyclobutene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like can be cited.

In the production method (A), the solid content concentration during the reaction is preferably 35% by mass to 95% by mass. In addition, when a highly viscous product is produced in the middle of the reaction, a solvent may be additionally added to continue the reaction. After the completion of the reaction, the solvent may be removed as needed, and may be further added.

The reaction temperature is performed within the temperature range to the extent that the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the produced phosphorus-containing phenoxy resin may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and may not reach the target molecular weight. Therefore, the reaction temperature is preferably 50°C to 230°C, more preferably 120°C to 200°C. In addition, the reaction time is usually 1 hour to 12 hours, preferably 3 hours to 10 hours. In the case of using a low-boiling solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by using an autoclave to perform the reaction under high pressure. In addition, when the heat of reaction needs to be removed, it is usually performed by the evaporation/condensation/reflux method using a solvent using the heat of reaction, indirect cooling method, or a combination of these.

Next, the manufacturing method (B) of the present invention will be described. The production method (B) is to make the acylating agent and the phosphorus-containing phenoxy resin (a) represented by the formula (6) have an alcoholic hydroxyl equivalent of 1 mol relative to the phosphorus-containing phenoxy resin (a) 0.05 mol or more and 2.0 mol or less are reacted to obtain the phosphorus-containing phenoxy resin represented by formula (1) with a weight average molecular weight of 10,000 to 200,000, that is, the phosphorus-containing phenoxy resin of the present invention method.

The phosphorus-containing phenoxy resin (a) as a raw material must contain the dioxy group represented by the formula (2) ^{in X 2 of the formula (6).} The phosphorus-containing phenoxy resin (a) can be obtained by a previously known method. For example, a method of producing a bifunctional phenol compound and epihalohydrin in the presence of an alkali metal compound (hereinafter referred to as a one-stage method) can be cited, wherein the bifunctional phenol compound will have the formula (2 ) Represented by a dioxy difunctional phenol compound (sometimes called a phosphorus-containing difunctional phenol compound) as an essential component; or make at least one of the difunctional epoxy resins and difunctional phenol compounds A method in which a dioxy difunctional epoxy resin represented by the formula (2) and a difunctional phenol compound are reacted in the presence of a catalyst to produce (hereinafter, referred to as a two-stage method). The phosphorus-containing phenoxy resin (a) can be obtained by any manufacturing method. Generally, the two-stage method is easier to obtain the phosphorus-containing phenoxy resin than the one-stage method, so it is preferable to use the two-stage method.

Regarding the weight average molecular weight or epoxy equivalent of the phosphorus-containing phenoxy resin (a), in the one-stage method, the molar ratio of the epihalohydrin and the bifunctional phenol compound can be adjusted appropriately to produce the one in the target range. In the two-stage method, the molar ratio of the bifunctional epoxy resins and the bifunctional phenol compounds can be adjusted appropriately to produce those in the target range.

The bifunctional phenol compound used in the production of the one-stage method and the two-stage method is preferably a phosphorus-containing bifunctional phenol compound (p1) represented by the following formula (10). The phosphorus-containing bifunctional phenol compound (p1) can be obtained by reacting an organophosphorus compound (p2) represented by the following formula (9) with a quinone compound using a known synthesis method. As a synthesis method, for example, in Japanese Patent Laid-Open No. 60-126293, Japanese Patent Laid-Open No. 61-236787, zh. Obshch. Khim (Russian Journal of General Chemistry), 42(11), pages 2415-2418 (1972) etc., but it is not limited to these methods.

式中，和式（2）或式（3）共同的符號與所述為相同含義。[化8]

In the formula, the symbols common to the formula (2) or (3) have the same meaning as described above.

In addition, as long as the purpose of the present invention is not impaired, difunctional phenol compounds other than these may be used in combination. Examples of bifunctional phenol compounds that can be used in combination include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol acetophenone, bisphenol fluorene, dihydroxy diphenyl ether, and Bisphenols such as hydroxybiphenyl sulfide; biphenols; monocyclic difunctional phenols such as catechol, resorcinol, and hydroquinone; 1,4-dihydroxynaphthalene, 1,5-dihydroxyl Dihydroxy naphthalenes such as naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; 1,1-bin-2-naphthol, etc. In addition, these may be substituted with substituents that have no adverse effects, such as alkyl groups and aryl groups. Moreover, these bifunctional phenol compounds can also use multiple types together.

First, the one-paragraph method will be explained. In the case of the one-stage method, the epihalohydrin is 0.985 mol to 1.015 mol, preferably 0.99 mol to 1.012 mol, and more preferably 0.995 mol to 1.01 mol relative to 1 mol of the bifunctional phenol compound. In the presence of an alkali metal compound, the reaction is carried out in a non-reactive solvent to consume epihalohydrin, and the condensation reaction is carried out so that the weight average molecular weight is 10,000 or more, whereby the phenoxy resin (a) can be obtained. Furthermore, after the reaction is completed, it is necessary to remove the by-produced salt by filtration or washing with water. As the alkali metal compound, the same alkali metal compound used in the production of the bifunctional epoxy resin represented by the formula (4) used in the production method (A) of the present invention can be exemplified.

The reaction can be carried out under normal pressure or under reduced pressure. The reaction temperature is usually in the case of the reaction under normal pressure, preferably 20°C to 200°C, more preferably 30°C to 170°C, still more preferably 40°C to 150°C, particularly preferably 50°C to 100°C. In the case of the reaction under reduced pressure, it is preferably 20°C to 100°C, more preferably 30°C to 90°C, and still more preferably 35°C to 80°C. If 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 atmospheric pressure. In addition, when the heat of reaction needs to be removed, it is usually carried out by an evaporation/condensation/reflux method using a solvent, an indirect cooling method, or a combination of these using the heat of reaction.

As the reactive solvent, in addition to the reaction solvent exemplified in the production method (A) of the present invention, alcohols such as ethanol, isopropanol, and butanol may also be used. Only one type may be used, or two or more types may be used in combination.

Next, the two-stage method will be described. For the difunctional epoxy resin as the raw material epoxy resin of the two-stage method, the same resin as the difunctional epoxy resin represented by the formula (4) used in the production method (A) of the present invention is used .

The difunctional epoxy resin as a raw material of the two-stage method is preferably the difunctional epoxy resin represented by the formula (4), but as long as the purpose of the present invention is not impaired, other than that can be used in combination Difunctional epoxy resin. Examples of bifunctional epoxy resins that can be used in combination include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, and diphenyl sulfide. Bisphenol type epoxy resins such as ether type epoxy resins, diphenyl ether type epoxy resins, and bisphenol fluorenone type epoxy resins; monocyclic difunctional phenols such as biphenol type epoxy resins and hydroquinone type epoxy resins Glycidyl ether, dihydroxynaphthalene type epoxy resin, diphenyldicyclopentadiene type epoxy resin, alkanediol type epoxy resin, aliphatic cyclic epoxy resin, etc. These epoxy resins can be substituted with substituents that have no adverse effects such as alkyl and aryl groups. These epoxy resins can also use multiple types together.

In the case of the two-stage method, a catalyst may be used, and any compound may be used as long as it has a catalyst function that promotes the reaction between an epoxy group and a phenolic hydroxyl group. For example, the same catalyst as the catalyst exemplified in the manufacturing method (A) of the present invention can be cited. In addition, the alkali metal compound used when manufacturing the bifunctional epoxy resin represented by the said formula (4) can also be used. These catalysts can be used alone, or two or more of them can be used in combination. In addition, the usage amount is also the same as the usage amount exemplified in the production method (A) of the present invention.

In the case of the two-stage method, a solvent can be used. As the solvent, any solvent may be used as long as it dissolves the phosphorus-containing phenoxy resin and does not adversely affect the reaction. For example, the same solvent as the solvent exemplified in the production method (A) of the present invention can be exemplified. Only one type of these solvents may be used, or two or more types may be used in combination.

The amount of the solvent used can be appropriately selected according to the reaction conditions. For example, in the case of the two-stage method, the solid content concentration is preferably 35% by mass to 95% by mass. In addition, when a highly viscous product is produced during the reaction, a solvent may be added in the middle of the reaction to continue the reaction. After the reaction, the solvent may be removed by distillation or the like as needed, and it may be further added.

The reaction temperature is performed within the temperature range to the extent that the catalyst used does not decompose. If the reaction temperature is too high, there is a possibility that the catalyst decomposes and the reaction stops, or the produced phosphorus-containing phenoxy resin may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently and may not reach the target molecular weight. Therefore, the reaction temperature is preferably 50°C to 230°C, more preferably 100°C to 210°C, and still more preferably 120°C to 200°C. In addition, the reaction time is usually 1 hour to 12 hours, preferably 3 hours to 10 hours. In the case of using a low-boiling solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by using an autoclave to perform the reaction under high pressure. In addition, when the heat of reaction needs to be removed, it is usually performed by the evaporation/condensation/reflux method using a solvent using the heat of reaction, indirect cooling method, or a combination of these.

The phosphorus-containing phenoxy resin of the present invention is obtained by acylating the hydroxyl group in the phosphorus-containing phenoxy resin (a) represented by the formula (6) thus obtained. Not only can the acylation be directly esterified, but also methods such as transesterification can be used.

As the acid component used in the acylation, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, octanoic acid, caprylic acid, lauric acid, stearic acid, oil can be used. Acid, benzoic acid, tertiary butyl benzoic acid, hexahydrobenzoic acid, phenoxyacetic acid, acrylic acid, methacrylic acid and other organic acids; anhydrides of organic acids; halides of organic acids; esters of organic acids, etc. Among these acylating agents, an acid anhydride represented by the following formula (7) is preferred.

式中，Z² 為具有碳數1～20的烴基的醯基。[化9]

In the formula, Z ² is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms.

As an acid anhydride of an organic acid, acetic anhydride, benzoic anhydride, phenoxyacetic anhydride, etc. are mentioned, for example. Examples of ester products of organic acids include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, and the like. As the halide of an organic acid, for example, acetyl chloride, benzyl chloride, phenoxy acetyl chloride, etc. may be mentioned. In the sense of not requiring water washing after esterification and avoiding the mixing of undesirable halogens in the application of electrical materials, acid anhydrides such as acetic anhydride and benzoic anhydride are more preferred.

As the compound used for esterification, halides of organic acids such as acetyl chloride, benzyl chloride, and phenoxyacetyl chloride, acid halides such as acetic anhydride, benzoic anhydride, and phenoxyacetic anhydride, or organic acids are preferred. The acid anhydride is more preferably acetic anhydride, benzoic anhydride, etc., in the sense that it does not require water washing after esterification and avoids mixing of undesirable halogens in the application of electrical materials.

The organic acid, the acid anhydride of the organic acid, the halide of the organic acid, the esterification of the organic acid and other acid components used in the esterification of the hydroxyl group of the phosphorus-containing phenoxy resin (a) and the phenoxy resin ( a) The input ratio during the reaction can be the same as the target esterification ratio. In the case of low reactivity, the acid component can be excessively added to the hydroxyl group to react to the target esterification ratio and then removed Unreacted acid components.

In the case of direct esterification with acid components, for example, acid catalysts such as p-toluenesulfonic acid and phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, and dioctyl oxide can be used. Various esterification catalysts such as metal catalysts such as tin and zinc chloride are dehydrated at the same time. Generally, it is performed under a nitrogen atmosphere, preferably at 100°C to 250°C, more preferably 130°C to 230°C.

In the case of using acid halide or acid anhydride in the esterification, in order to remove the generated acid, a method of filtering the salt after neutralization with a basic compound or a method of washing with water after neutralization with a basic compound can be used. Either the method of neutralizing and washing with water, the method of removing by distillation, adsorption, etc., can also be used together. In the case of removing an acid having a lower boiling point than the reaction solvent, it is preferably removed by distillation.

In the case of esterification of phosphorus-containing phenoxy resin (a) by transesterification, it is desirable to use, for example, dibutyltin oxide, dioctyltin oxide, and stannoxane catalysts under a nitrogen atmosphere. , Tetraisopropyl titanate, tetrabutyl titanate, lead acetate, zinc acetate, antimony trioxide and other organic metal catalysts; acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, and sulfonic acid; lithium hydroxide, sodium hydroxide, etc. A well-known esterification catalyst such as an alkaline catalyst is carried out while dealcoholizing.

In the production method (B) of the present invention, a solvent for reaction can be used. As the solvent, any solvent may be used as long as it dissolves the phosphorus-containing phenoxy resin. For example, the solvent etc. illustrated in the manufacturing method (A) of this invention are mentioned. These solvents may be the same as or different from the solvent used in the preparation of the phosphorus-containing phenoxy resin (a). In addition, only one type may be used, or two or more types may be used in combination.

The resin composition of the present invention is a resin composition containing at least the phosphorus-containing phenoxy resin of the present invention and a curing agent. In addition, in the resin composition of the present invention, various additives such as epoxy resins, inorganic fillers, coupling agents, and antioxidants can be appropriately blended as necessary. The resin composition of the present invention provides a cured product that sufficiently satisfies various physical properties required for various applications.

A hardener can be blended in the phosphorus-containing phenoxy resin of the present invention to prepare a resin composition. In the present invention, the hardener means a substance that contributes to the crosslinking reaction and/or the chain length extension reaction of the phosphorus-containing phosphorus-containing phenoxy resin. Furthermore, in the present invention, even if it is generally called a "hardening accelerator", as long as it contributes to the crosslinking reaction and/or chain length extension reaction of the phosphorus-containing phenoxy resin, it is regarded as hardening. Agent.

The content of the hardener in the resin composition of the present invention is preferably 0.1 to 100 parts by mass in terms of solid content relative to 100 parts by mass of the solid content of the phosphorus-containing phenoxy resin of the present invention. In addition, it is more preferably 80 parts by mass or less, and still more preferably 60 parts by mass or less.

In the resin composition of the present invention, when the epoxy resin described later is contained, the weight ratio of the solid content of the phosphorus-containing phenoxy resin of the present invention to the epoxy resin is 99/1 to 1/99. In the present invention, "solid content" refers to a component after removing the solvent, and includes not only solid phosphorus-containing phenoxy resin or epoxy resin, but also semi-solid or viscous liquid. In addition, the "resin component" means the total of the phosphorus-containing phenoxy resin of the present invention and the epoxy resin described later.

The hardener used in the resin composition of the present invention is not particularly limited, and all hardeners generally known as epoxy resin hardeners can be used. From the viewpoint of improving heat resistance, preferred ones include phenolic curing agents, amide curing agents, imidazoles, active ester curing agents, and the like. These hardeners may be used alone, or two or more of them may be used in combination.

Examples of phenolic hardeners include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxy Phenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenyl sulfide, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphorus Phenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, polyp-hydroxystyrene, p-benzene Diphenol, resorcinol, catechol, tertiary butyl catechol, tertiary butyl hydroquinone, fluoroglycinol, pyrogallol, tertiary butyl catechol , Allylated gallic phenol, polyallylated gallic phenol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3 -Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene Hydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, the alkene of the dihydroxynaphthalene Propyl compound or polyallyl compound, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated gallic phenol, etc.

Examples of the amide-based curing agent include dicyandiamine and its derivatives, and polyamide resins.

Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]- Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-bis Amino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isotrimer acid adduct, 2-phenylimidazole isotrimer acid adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resin and the imidazoles, etc. Furthermore, imidazoles are generally classified as hardening accelerators described later because they have catalytic properties, and in the present invention, they are classified as hardening agents.

As the active ester curing agent, for example, phenolic esters, thiophenolic esters, N-hydroxylamine esters, or esters of heterocyclic hydroxy compounds, etc. having two or more highly reactive ester groups in one molecule are preferred. Among them, the compound is more preferably a phenol ester obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of aromatic compounds having a phenolic hydroxyl group include: catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, three Hydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc.

Examples of other hardeners that can be used in the resin composition of the present invention include amine hardeners, acid anhydride hardeners, tertiary amines, organic phosphines, phosphonium salts, tetraphenyl boron salts, and organic acid dihydrazide , Boron halide amine complexes, polythiol-based hardeners, isocyanate-based hardeners, blocked isocyanate-based hardeners, etc. Only one kind of these other hardeners may be used, or two or more kinds may be mixed and used in any combination and ratio.

The resin composition of the present invention may contain an epoxy resin. By using epoxy resin, insufficient physical properties can be made up or various physical properties can be improved. As the epoxy resin, an epoxy resin having two or more epoxy groups in the molecule is preferable, and an epoxy resin having three or more epoxy groups is more preferable. For example, a polyglycidyl ether compound, a polyglycidyl amine compound, a polyglycidyl ester compound, an alicyclic epoxy compound, other modified epoxy resins, etc. are mentioned. These epoxy resins can be used alone, or two or more epoxy resins of the same series can be used in combination, and epoxy resins of different series can also be used in combination.

As the polyglycidyl ether compound, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, Bisphenol fluorene type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, naphthalene type epoxy resin, hydroquinone type epoxy resin, resorcinol type epoxy resin, phenol Novolak type epoxy resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type Epoxy resin, phenol aralkyl epoxy resin, β-naphthol aralkyl epoxy resin, naphthalene diphenol aralkyl epoxy resin, α-naphthol aralkyl epoxy resin, biphenyl Aralkylphenol type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin And other various epoxy resins.

As the polyglycidylamine compound, for example, diaminodiphenylmethane type epoxy resin, meta-xylene diamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, Isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, aminophenol type epoxy resin, etc.

As a polyglycidyl ester compound, a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, a trimellitic acid type epoxy resin, etc. are mentioned, for example.

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

As other modified epoxy resins, for example, urethane modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy modified polybutadiene rubber derivatives, carboxyl-terminated butadiene Acrylonitrile rubber (CTBN) modified epoxy resin, polyvinyl aromatic polyoxide (for example, divinylbenzene dioxide, trivinyl naphthalene trioxide, etc.), phosphorus-containing phenoxy resin, etc.

When the phosphorus-containing phenoxy resin and epoxy resin of the present invention are used in the resin composition of the present invention, among all the components of the phosphorus-containing phenoxy resin and epoxy resin as solid components, the epoxy resin The blending amount of A is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 97% by mass, still more preferably 10% by mass to 95% by mass, and still more preferably 10% by mass to 90% by mass. With the epoxy resin in the above-mentioned compounding amount, when it is made into a cured product containing the resin composition of the present invention, heat resistance and mechanical strength can be improved.

In order to appropriately adjust the viscosity of the resin composition at the time of processing when forming a coating film, the resin composition of the present invention can be formulated with a solvent or a reactive diluent. In the resin composition of the present invention, a solvent or a reactive diluent is used to ensure handleability and workability in the molding of the resin composition, and the amount used is not particularly limited. Furthermore, in the present invention, the term "solvent" and the term "solvent" described above are used differently according to the form of use, but the same species may be used independently, or different species may be used.

Examples of solvents that can be included in the resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; Alcohol monomethyl ether and other ethers; N,N-dimethylformamide, N,N-dimethylacetamide and other amines; methanol, ethanol and other alcohols; hexane, cyclohexane and other alkanes ; Aromatics such as toluene and xylene. Only one type of the solvents listed above may be used, or two or more types may be mixed and used in any combination and ratio.

Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, difunctional glycidyl ethers such as propylene glycol diglycidyl ether, and polyfunctional glycidyl ethers such as trimethylolpropane polyglycidyl ether. Glyceryl ethers, glycidyl esters, and glycidylamines.

Among these solvents or reactive diluents, it is preferable to use 90% by mass or less as a non-volatile component, and the appropriate kind or usage amount is appropriately selected according to the application. For example, in the use of printed wiring boards, polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160° C. or less are preferred, and the amount used is preferably a non-volatile component. It is calculated as 40% by mass to 80% by mass. In addition, for film bonding applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used. The amount used is preferably 30% by mass to 60% by mass in terms of non-volatile components.

The resin composition of the present invention may optionally use a hardening accelerator (except for the hardening accelerator contained in the "hardening agent"). Examples of hardening accelerators include phosphorus compounds such as imidazoles, tertiary amines, and phosphines, metal compounds, Lewis acid, and amine complex salts. These hardening accelerators may be used alone, or two or more of them may be used in combination.

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

In the resin composition of the present invention, for the purpose of improving the flame retardancy of the obtained cured product, various known flame retardants can be used within a range that does not reduce the reliability. Usable flame retardants include, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. Wait. From an environmental point of view, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants can be used alone, or two or more of the same series of flame retardants can be used in combination, and in addition, different series of flame retardants can also be used in combination.

In the resin composition of the present invention, for the purpose of further improving its functionality, components other than the above-listed components (sometimes referred to as "other components" in the present invention) may be included. Examples of the other components include fillers, thermoplastic resins, thermosetting resins, photocurable resins, ultraviolet inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropy imparting agents, smoothing agents, Colorants, pigments, dispersants, emulsifiers, low-elasticity agents, mold release agents, defoamers, ion trapping agents, etc.

As the filler, for example, fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, diaspore (boehmite ), 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, or carbon fiber, Fibrous fillers such as glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, polyaramid fiber, ceramic fiber, etc., or fine particle rubber.

The resin composition of the present invention may also use the conventional thermoplastic resin of the phosphorus-containing phenoxy resin of the present invention in combination. Examples of thermoplastic resins include phosphorus-containing phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, and acrylonitrile butadiene other than those of the present invention. Acrylonitrile Butadiene Styrene (ABS) resin, Acrylonitrile Styrene (AS) resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal Resin, cyclic polyolefin resin, polyimide resin, thermoplastic polyimide resin, polyimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene Ether resin, polyether ether resin, polyether resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc. In terms of compatibility, phosphorus-containing phenoxy resins other than those of the present invention are preferred, and in terms of low dielectric properties, polyphenylene ether resins or modified polyphenylene ether resins are preferred.

Examples of other components include: organic pigments such as quinacridone, azo, and phthalocyanine, or inorganic pigments such as titanium oxide, metal foil-like pigments, and anti-rust pigments, or hindered amine, benzotriazole, etc. , Benzophenone series and other ultraviolet absorbers, or hindered phenol series, phosphorus series, sulfur series, hydrazine series and other antioxidants, or stearic acid, palmitic acid, zinc stearate, calcium stearate and other mold release agents , Leveling agent, rheology control agent, pigment dispersant, anti-sagging agent, defoamer and other additives. The blending amount of these other components is preferably in the range of 0.01% by mass to 20% by mass relative to the total solid content in the resin composition.

The resin composition of the present invention can be obtained by uniformly mixing the respective components. A resin composition prepared with a phosphorus-containing phenoxy resin, a curing agent, and various components as necessary can be easily made into a cured product by the same method as the previously known method. The cured product has an excellent balance of low moisture absorption, dielectric properties, heat resistance, adhesion, etc., and exhibits good cured physical properties. The term "curing" here means that the resin composition is intentionally cured by heat and/or light, and the degree of curing can be controlled according to the required physical properties and applications. The degree of progress may be a fully hardened state or a semi-hardened state, and is not particularly limited, but the reaction rate of the hardening reaction between the epoxy group and the hardening agent is usually 5% to 95%.

The resin composition of the present invention can be cured by the same method as a known epoxy resin composition to obtain a cured product. As a method for obtaining a hardened product, the same method as that of a known epoxy resin composition can be used, and injection molding, injection, potting, dipping, drip coating, transfer molding, and compression can be used as appropriate. Molding or the like, or laminating in the form of a resin sheet, a resin-coated copper foil, a prepreg, etc., and heat and pressure hardening to form a laminated board. The curing temperature at this time is usually in the range of 80°C to 300°C, and the curing time is usually about 10 minutes to 360 minutes. The heating is preferably performed by a two-stage treatment of primary heating at 80°C to 180°C for 10 minutes to 90 minutes and secondary heating at 120°C to 200°C for 60 minutes to 150 minutes. In a formulation system in which the glass transition temperature (Tg) exceeds the temperature of the secondary heating, it is preferable to further perform three heating at 150°C to 280°C for 60 minutes to 120 minutes. By performing such secondary heating and tertiary heating, poor hardening can be reduced. In the production of semi-cured resins such as resin sheets, resin-coated copper foils, and prepregs, the curing reaction of the resin composition is usually carried out by heating or the like so as to maintain the shape. When the resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., and 5 mass% or less of the solvent may remain in the semi-cured resin.

The prepreg obtained using the resin composition of the present invention will be described. As the sheet-like substrate, a woven or non-woven fabric of inorganic fibers such as glass or polyester, polyamine, polyacrylic acid, polyimide, kevlar, cellulose, and other organic fibers can be used, but it is not limited For that. The method for producing a prepreg from the resin composition and the base material of the present invention is not particularly limited. For example, the base material may be impregnated and impregnated with a resin varnish in which the resin composition is adjusted in viscosity with a solvent. It is obtained by performing heat drying to semi-harden the resin component (B-staged), and it can be heated and dried at 100°C to 200°C for 1 minute to 40 minutes, for example. Here, the amount of resin in the prepreg is preferably set to 30% by mass to 80% by mass of the resin component.

The method of manufacturing a laminated board using the prepreg or insulating adhesive sheet of this invention is demonstrated. In the case of using a prepreg to form a laminate, one or more prepreg bulk layers are placed on one side or both sides of the metal foil to form a laminate, and the laminate is heated and pressurized to integrate the laminate . Here, as the metal foil, individual, alloy, or composite metal foils such as copper, aluminum, brass, and nickel can be used. As the conditions for heating and pressing the laminate, as long as the resin composition is hardened, the heating and pressing can be adjusted appropriately. However, when the amount of pressurized pressure is too low, air bubbles remain in the obtained laminate. In the case of the inside, and thus the electrical characteristics are reduced, it is desirable to pressurize under the condition that satisfies the moldability. For example, you can set the temperature to 160°C to 220°C, the pressure to 49.0 N/cm ² to 490.3 N/cm ² (5 kgf/cm ² to 50 kgf/cm ² ), and the heating time to 40 minutes to 240 minutes.

In addition, a single-layer laminated board obtained in this way can be used as an inner layer material to produce a multilayer board. In this case, first, circuit formation is performed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed on one or both sides of the circuit forming surface of the inner layer material by a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer, thereby forming a multilayer board.

When the insulating layer is formed by the insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, the insulating adhesive sheet is arranged between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized and integrally molded, whereby the cured product of the insulating adhesive sheet is formed as an insulating layer, and at the same time, a multilayered inner layer material is formed. Alternatively, the hardened product of the insulating adhesive sheet is used as an insulating layer to form an inner layer material and a metal foil as a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated sheet used as the inner layer material can be used. In addition, heating and pressure forming can be performed under the same conditions as the forming of the inner layer material. When the resin composition is applied to the laminate to form an insulating layer, it is preferable to apply the resin composition to a thickness of 5 μm to 100 μm for the circuit forming surface resin of the outermost layer of the inner layer material, and then Heat and dry at 100°C to 200°C for 1 minute to 90 minutes to form a sheet. It is usually formed by a method called casting method. The thickness after drying is desirably 5 μm to 80 μm. On the surface of the multilayer build-up board formed in this way, a printed wiring board can be formed by further forming a through hole or forming a circuit by an additive method or a subtractive method. In addition, by using the printed wiring board as an inner layer material and repeating the above-mentioned method, a multilayer laminated board can be further formed.

In addition, when the insulating layer is formed by the prepreg, one or more prepreg bulk layers are arranged on the circuit forming surface of the inner layer material, and a metal foil is arranged on the outer side to form a laminate. Then, the laminate is integrally molded by heating and pressing to form the hardened product of the prepreg as an insulating layer, and at the same time, the metal foil on the outer side thereof is formed as a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated sheet used as the inner layer material can also be used. In addition, heating and pressure forming can be performed under the same conditions as the forming of the inner layer material. Furthermore, the printed wiring board can be molded by forming a through hole or forming a circuit on the surface of the multilayer laminate formed in this manner by an additive method or a subtractive method. In addition, by using the printed wiring board as an inner layer material and repeating the above-mentioned method, a multi-layer multilayer board can be further formed.

The cured product obtained from the resin composition of the present invention and the laminated board for electric and electronic circuits have excellent flame retardancy and strength. [Example]

Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, parts means parts by mass, and% means mass%. The analysis method and measurement method are as follows. In addition, the units of various equivalents are g/eq.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn): Determined by GPC measurement. Specifically, it is used on the main body HLC8320GPC (manufactured by Tosoh Co., Ltd.) including columns (TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H, the above are manufactured by Tosoh Co., Ltd.) , And set the column temperature to 40°C. In addition, DMF (containing 20 mM lithium bromide) was used as the eluent, the flow rate was set to 0.3 mL/min, and the differential refractive index detector was used as the detector. A sample obtained by dissolving 0.1 g of a measurement sample in terms of solid content in 10 mL of DMF and filtering it with a 0.45 μm micro filter was used in 20 μL. Based on the calibration curve obtained from standard polyethylene oxide (manufactured by Tosoh Co., Ltd., SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150) Perform conversion to find Mw. In addition, the data processing used GPC8020 model II version 6.00 manufactured by Tosoh Corporation.

(2) Epoxy equivalent: The measurement is carried out in accordance with the Japanese industrial standard (JIS) K 7236 standard. Specifically, a potentiometric titration device is used, cyclohexanone is used as a solvent, a tetraethylammonium bromide acetic acid solution is added, and a 0.1 mol/L perchloric acid-acetic acid solution is used. In addition, the solvent-diluted product (resin varnish) is a value calculated from the non-volatile content as a solid content conversion value.

(3) Phosphorus content rate: Sulfuric acid, hydrochloric acid, and perchloric acid are added to the phosphorus-containing phenoxy resin, and heated for wet ashing, so that all phosphorus atoms become orthophosphoric acid. The metavanadate and molybdate are reacted in a sulfuric acid acid solution, and the absorbance at 420 nm of the formed phosphovanadomolybdic acid complex is measured, and the phosphorus content calculated by the calibration curve prepared in advance is expressed in% (P/resin). In addition, the solvent-diluted product (resin varnish) is calculated from the non-volatile content as a solid content conversion value.

(4) Non-volatile ingredients: Measured in accordance with JIS K 7235 standard. The drying temperature is 200°C, and the drying time is 60 minutes.

(5) Glass transition temperature (Tg): Measured according to the Institute of printed circuits (IPC)-TM-650 2.4.25.c standard. Specifically, using a differential scanning calorimetry device EXSTAR6000 DSC6200 (manufactured by SII nanotechnology Co., Ltd.), under a temperature increase of 10°C/min, in the range of 20°C to 280°C, the thickness is 4 The sample with a diameter of 3 mm and a diameter of 3 mm was measured in two cycles, which is represented by the glass transition temperature (Tmg) at the middle point in the second scan measurement chart obtained.

(6) Flame retardancy: It is evaluated by UL94V (Underwriters Laboratories Inc.) V test. The test piece was prepared in accordance with UL94-V by the method described below. Test 5 test pieces, and determine the same standard based on the total time of flame burning after the first and second exposure to flame (5 exposures to the flame 2 times each, totaling 10 times) Standard V-0, V-1, and V-2 are used for judgment. The flame retardancy is V-0 the most excellent, and it deteriorates in the order of V-1 and V-2. However, the person who burns completely is denoted as X. In addition, in the case of a resin film, it is evaluated by the vertical method in accordance with UL94VTM. Evaluation is based on VTM-0, VTM-1, and VTM-2. Regarding flame retardancy, VTM-0 is the most excellent, and it deteriorates in the order of VTM-1 and VTM-2. However, the person who burns completely is denoted as X.

(7) Solubility: Use cyclohexanone to make phosphorus-containing phenoxy resin into a resin varnish with 30% resin content, and add the same amount of bisphenol A epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-128), shake with an oscillator for 1 hour, and visually confirm the state after being allowed to stand in a thermostat at 25°C for 24 hours. The evaluation is as follows. ○: uniform and showing transparency, ×: turbid or separated

(8) Strength: According to the JIK K 7110 standard, it is evaluated by a test piece that has not been cut. When the strength is less than 100 kJ/m ² , the strength is insufficient, and 100 kJ/m ² or more is considered acceptable.

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

A1: Bisphenol A epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-128, epoxy equivalent 186, m≒0.09) A2: 3,3',5,5',-tetramethyl-4,4'-bisphenol epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent 196, m≒0.11)

B1: 10-(2,5-Diacetoxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (active equivalent 204) B2: 10-(2,7-Diethoxynaphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (active equivalent 229) B3: 2,2-bis(4-acetoxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd., active equivalent 156)

[Phenolic compound] C1: 10-(2,5-Dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanguang Chemical Co., Ltd., HCA-HQ, hydroxyl Equivalent 162) C2: 10-(2,7-dihydroxynaphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanguang Chemical Co., Ltd., HCA=NQ, hydroxyl Equivalent 187)

[catalyst] D1: N,N'-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) D2: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2E4MZ)

[Solvent, solvent] S1: Cyclohexanone

[Acid anhydride] E1: Acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) E2: Benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[hardener] H1: Dicyandiamide (manufactured by Carbide Industry Co., Ltd., product name: DIHARD, active hydrogen equivalent 21)

Synthesis example 1 Put 100 parts of C1, 315 parts of E1, 0.05 parts of dibutyltin maleate, and 186 parts of acetic acid into a glass reaction vessel including a stirring device, a thermometer, a nitrogen introduction device, a cooling tube, and a dripping device at room temperature. The nitrogen gas was allowed to flow and the temperature was raised to 110°C while stirring, and the reaction was carried out for 2 hours. Thereafter, it was dried under reduced pressure under conditions of 130° C. and 1.3 kPa (10 torr) for 3 hours to obtain 98 parts of B1.

Synthesis Example 2 Put 100 parts of C2, 272 parts of E1, 0.04 parts of dibutyl tin maleate, and 160 parts of acetic acid into the glass reaction vessel at room temperature, flow nitrogen gas, and heat to 110°C while stirring, proceed 2 Hour response. Thereafter, it was dried under reduced pressure under conditions of 130°C and 10 torr for 3 hours to obtain 98 parts of B2.

Example 1 Put 100 parts of A1, 104 parts of B1, and 88 parts of S1 into a glass reaction vessel including a stirring device, a thermometer, a nitrogen introduction device, a cooling tube, and a dripping device at room temperature, and let the nitrogen flow while stirring. The temperature was raised to 130°C, 0.2 part of C1 was added, and then the temperature was raised to 145°C, and the reaction was performed at this temperature for 7 hours. 389 parts of S1 as a dilution solvent were used for dilution and mixing to obtain a phosphorus-containing phenoxy resin varnish (R1) of 30% non-volatile content.

Example 2 to Example 7, Comparative Example 1 to Comparative Example 2 According to the input amount (part) of each raw material shown in Table 1-Table 2, the same operation as Example 1 was performed, and the phosphorus containing phenoxy resin varnish was obtained. In addition, the molar ratio in the table represents the molar ratio of the difunctional epoxy resin to the diester compound and the bifunctional phenol compound, and the varnish represents the phosphorus-containing phenoxy resin varnish.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 A1 100 100 100 100 A2 100 B1 104 99 104 52 B2 117 C1 41 D1 0.2 0.2 0.2 0.2 D2 0.2 Molby 1.05 1.05 1.05 1.05 1.05 Response time (Hr) 7 7 7 7 9 Reaction temperature (℃) 145 145 145 145 145 (Reaction solvent) S1 88 93 85 88 83 (Dilution solvent) S1 389 414 379 389 369 Varnish R1 R2 R3 R4 R5

[Table 2] Example 6 Example 7 Comparative example 1 Comparative example 2 A1 100 100 100 100 B1 115 100 B3 80 C1 83 D1 0.2 0.2 0.2 0.2 Molby 0.95 1.10 1.05 1.05 Response time (Hr) 7 7 7 7 Reaction temperature (℃) 145 145 145 145 (Reaction solvent) S1 92 86 77 78 (Dilution solvent) S1 410 380 343 348 Varnish R6 R7 RH1 RH2

Example 8 100 parts of the phosphorus-containing phenoxy resin varnish (RH2) obtained in Comparative Example 2 (40 parts in terms of solid content) and 600 parts of S1 were prepared, and after the temperature was raised to 100°C, 6 parts of E1 were added, and the reaction was carried out for 4 hours. The obtained resin varnish was added to methanol, the precipitated insoluble components were filtered, and the filtrate was dried with a vacuum dryer at 150° C. and 0.4 kPa (3 torr) for 1 hour to obtain a phosphorus-containing phenoxy resin. To the obtained phosphorus-containing phenoxy resin, 99 parts of S1 was added to uniformly dissolve the phosphorus-containing phenoxy resin varnish (R8) with 30% non-volatile content.

Example 9 Except that E1 was 14 parts and S1 of the dilution solvent was 105 parts, the same operation as Example 8 was performed, and the phosphorus containing phenoxy resin varnish (R9) was obtained.

Example 10 Except that instead of E1, E2 was 33 parts, and S1 of the dilution solvent was 120 parts, the same operation as Example 8 was performed, and the phosphorus containing phenoxy resin varnish (R10) was obtained.

Vacuum the phosphorus-containing phenoxy resin varnish R1 to resin varnish R10 obtained in Example 1 to Example 10 and the phosphorus-containing phenoxy resin varnish RH1 to resin varnish RH2 obtained in Comparative Example 1 to Comparative Example 2 The dryer was dried under the conditions of 200°C and 0.4 kPa (3 torr) for 1 hour, and then subjected to vacuum pressing of 2 MPa at 230°C for 1 hour to obtain a resin film. The epoxy equivalent, phosphorus content, Mw, and solubility are measured using a phosphorus-containing phenoxy resin varnish, and Tg and flame retardancy are measured using a resin film. The results are shown in Table 3. In addition, the "dialysis rate" in the table represents the content rate (mol %) of the diaphanous group in all Z in the formula (1).

[table 3] Varnish Epoxy equivalent Mw Phosphorus content rate (%) Fusion rate Tg (℃) Flame retardant Solubility R1 9000 32000 4.0 98 133 VTM-0 ○ R2 8700 27000 3.7 98 142 VTM-0 ○ R3 9300 31000 3.9 97 141 VTM-0 ○ R4 6500 23000 4.0 98 133 VTM-0 ○ R5 7400 25000 4.2 42 138 VTM-0 ○ R6 7800 29000 4.0 98 131 VTM-0 ○ R7 5200 15000 4.0 98 133 VTM-0 ○ R8 8500 25000 4.3 50 136 VTM-0 ○ R9 9000 25000 4.1 100 130 VTM-0 ○ R10 8800 24000 3.6 100 139 VTM-0 ○ RH1 8100 26000 0 98 80 X ○ RH2 8900 24000 4.5 0 140 VTM-0 X

Example 11 to Example 13 and Comparative Example 3, Comparative Example 4 100 parts (40 parts in terms of solid content) of the phosphorus-containing phenoxy resin varnish (R1, R2, R6, RH1) obtained in Example 1, Example 2, Example 6 and Comparative Example 1 to Comparative Example 2 were formulated , RH2), 50 parts of A5 as an epoxy resin, 2.8 parts of H1 as a hardening agent, and 0.6 parts of D2 as a hardening accelerator using a 20% MEK solution to obtain a resin composition. The obtained resin composition was impregnated in glass cloth (WEA7628XS13, manufactured by Nitto Textile Co., Ltd., 0.18 mm thick), and dried in a hot air circulation oven at 150° C. for 8 minutes to obtain a prepreg in a B-stage state. The obtained prepreg was laminated with 8 sheets and 50 sheets, and then copper foil (manufactured by Mitsui Metal Mining Co., Ltd., 3EC, thickness 35 μm) was superimposed on the upper and lower layers of the prepreg. Carrying out 2 MPa pressure and curing under vacuum pressing to obtain 1.6 mm and 10.0 mm thick laminates. Both sides of the obtained laminated board were etched to obtain test pieces for flame retardancy evaluation and impact strength evaluation.

[Table 4] Example 11 Example 12 Example 13 Comparative example 3 Comparative example 4 Varnish R1 R2 R6 RH1 RH2 Tg (℃) 150 158 149 101 156 Flame retardant V-1 V-1 V-1 X V-1 Strength (kJ/m ² ) 112 123 106 145 85

As can be seen from Table 3, the phosphorus-containing phenoxy resin of the present invention is excellent in flame retardancy and solubility. In addition, as can be seen from Table 4, the cured product containing the phosphorus-containing phenoxy resin composition of the present invention is also excellent in flame retardancy and strength. [Industrial availability]

The phosphorus-containing phenoxy resin and resin composition of the present invention can be applied to various fields such as adhesives, paints, civil construction materials, and insulating materials for electrical and electronic parts, especially as insulating injection molding and laminates in the electrical and electronic fields. Materials, sealing materials, etc. are useful. The phosphorus-containing phenoxy resin of the present invention and the resin composition containing the phosphorus-containing phenoxy resin can be suitably used for multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, film adhesives, and liquid adhesives. Adhesives, semiconductor sealing materials, primer materials, three-dimensional large-scale integration (3D-LSI) inter-chip filling (Inter Chip Fill) materials, insulating sheets, prepregs, Radiating substrate, etc.

none

none.

Claims (11)

A phosphorus-containing phenoxy resin represented by the following formula (1), with a weight average molecular weight of 10,000 to 200,000, and a phosphorus content of 1 mass% to 6 mass%,

In the formula, X is independently a divalent group containing a dioxy group represented by the following formula (2), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, or a glycidyl group, Z is an acyl group or a hydrogen atom having a hydrocarbon group with 1 to 20 carbons, and 5 mol% or more is the acyl group, n is the average value of the number of repetitions, and is 15 or more and 500 or less,

In the formula, A is a trivalent aromatic hydrocarbon group having 6 to 20 carbons, W is a phosphorus-containing group represented by the formula (3), and R ¹ and R ² are each independently a carbon number of 1 to 20 that may contain a hetero element The hydrocarbon group of may be linear, branched or cyclic, and R ¹ and R ² may be bonded to form a cyclic structure, and k1 and k2 are independently 0 or 1, respectively. The phosphorus-containing phenoxy resin according to claim 1 has an epoxy equivalent of 2000 g/eq. to 50000 g/eq. A resin composition comprising the phosphorus-containing phenoxy resin according to claim 1 and a hardener. The resin composition according to claim 3, wherein the curing agent is contained in a solid content of 0.1 to 100 parts by mass relative to 100 parts by mass of the solid content of the phosphorus-containing phenoxy resin. The resin composition according to claim 3, which contains the phosphorus-containing phenoxy resin, epoxy resin, and hardener according to claim 1 or 2, and the phosphorus-containing phenoxy resin and epoxy The mass ratio of the solid content of the resin is 99/1 to 1/99. The resin composition according to claim 5, wherein the resin composition contains a solid content of 0.1 to 100 parts by mass relative to 100 parts by mass of the total solid content of the phosphorus-containing phenoxy resin and epoxy resin. Agent. The resin composition according to claim 3, wherein the hardener is selected from the group consisting of acrylate resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, and cationic polymerization initiators. At least one of the group consisting of an agent, an organic phosphine, a polyisocyanate compound, a blocked isocyanate compound, and an active ester curing agent. A hardened product obtained by hardening the resin composition according to any one of Claims 3 to 7. A laminated board for electrical and electronic circuits, which is obtained by using the resin composition described in any one of Claims 3 to 7. A method for producing a phosphorus-containing phenoxy resin, characterized by reacting a difunctional epoxy resin represented by the following formula (4) with a compound represented by the following formula (5) to obtain a weight average molecular weight of 10,000 Phosphorus-containing phenoxy resin represented by the following formula (1) with a phosphorus content of 1% to 6% by mass and a phosphorus content of ~200,000,

Wherein, X ¹ independently an dioxo (2) X represents two groups as a divalent radical of formula (4) and (5) in ^an integral formula (2) represented by the following formula Group, Z ¹ is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbons, and 5 mol% or more is the acyl group. Here, the compound represented by formula (5) may be two groups ^{selected from Z 1} A mixture of two or more of a compound having an acyl group, a compound having an acyl group, and a compound having both hydrogen atoms, m is the average of the number of repetitions, and is 0 or more and 6 or less,

In the formula, A is a trivalent aromatic hydrocarbon group having 6 to 20 carbons, W is a phosphorus-containing group represented by the formula (3), and R ¹ and R ² are each independently a carbon number of 1 to 20 that may contain a hetero element The hydrocarbon group of can be linear, branched, or cyclic, and R ¹ and R ² can be bonded to form a cyclic structure, and k1 and k2 are independently 0 or 1, respectively,

In the formula, X is independently a divalent group containing the dioxy group represented by the formula (2), and Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbon atoms, or a glycidyl group, Z is an acyl group or a hydrogen atom having a hydrocarbon group having 1 to 20 carbon atoms, and 5 mol% or more is the acyl group, and n is the average value of the number of repetitions, which is 15 or more and 500 or less. A method for producing a phosphorus-containing phenoxy resin, characterized in that the alcoholic hydroxyl equivalent of the phosphorus-containing phenoxy resin (a) represented by the following formula (6) is 1 mol of an acylating agent, The reaction is carried out at 0.05 mol or more and 2.0 mol or less to obtain a phosphorus-containing phenoxy group represented by the following formula (1) with a weight average molecular weight of 10,000 to 200,000 and a phosphorus content of 1 mass% to 6 mass% Resin,

In the formula, X ^{2 is} independently a divalent group containing a dioxy group represented by the following formula (2), Y ^{2 is} independently a hydrogen atom or a glycidyl group, and n is the average of the number of repetitions, which is 15 Above and below 500,

In the formula, A is a trivalent aromatic hydrocarbon group having 6 to 20 carbons, W is a phosphorus-containing group represented by the formula (3), and R ¹ and R ² are each independently a carbon number of 1 to 20 that may contain a hetero element The hydrocarbon group of can be linear, branched, or cyclic, and R ¹ and R ² can be bonded to form a cyclic structure, and k1 and k2 are independently 0 or 1, respectively,

In the formula, X and n respectively have the ^{same meaning as X 2} and n in formula (6), Y is each independently a hydrogen atom, an acyl group having a hydrocarbon group with 1 to 20 carbons, or a glycidyl group, and Z is a carbon The number of the acyl group or the hydrogen atom of the hydrocarbon group of 1 to 20, and 5 mol% or more is the acyl group.