JP2019094415A - Resin composition - Google Patents

Abstract

To provide a resin composition excellent in flame retardancy using a polyphenylene ether resin.SOLUTION: A resin composition contains (A) a polyphenylene ether resin and (E) a phosphorus-containing compound represented by formula (1). In formula (1), m represents an integer of 1 to 10; Rand Reach independently represents an alkyl group, an aryl group or -NRR; Rrepresents a hydrocarbon group that main contain an atom selected from oxygen, sulfur phosphorus and nitrogen; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom or -NR-; Rand Reach independently represent a hydrogen atom, an alkyl group or an aryl group; Reach independently represents a hydrogen atom, an alkyl group or an aryl group. When both Rand Rare -NRR, Rand Rare different groups in some cases.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, and more particularly to a resin composition containing a polyphenylene ether resin and a phosphorus-containing compound.

  In recent years, with the development of information processing and communication, printed wiring boards have been required to have a lower dielectric constant and a lower dielectric loss tangent. The polyphenylene ether resin is expected to be used taking advantage of the property of low dielectric constant, but using it as it is is not sufficient as a material because of problems such as workability and adhesion.

  In order to solve these problems, combinations with epoxy resins which have been widely used for electrical materials such as printed wiring board applications (for example, Patent Document 1) are tried, or cross-linked structures to low molecular weight type polyphenylene ether resins Several methods (for example, patent document 2) which make it have are tried.

  Further, in these applications, flame retardancy is also required. For example, Patent Document 2 describes that a halogen-based flame retardant can be used. However, halogen-based flame retardants are not desired to be used due to environmental impact.

  On the other hand, Patent Document 3, Patent Document 4 and the like propose an epoxy resin composition obtained by combining an epoxy resin and a specific phosphorus-containing compound, but the application of polyphenylene ether resin is completely described. Absent.

Japanese Patent Application Laid-Open No. 6-1823 JP, 2009-29928, A International Publication No. 2016/121750 brochure International Publication No. 2016/152839 brochure

  Therefore, the problem to be solved by the present invention is to use particularly as a laminated board used for a printed wiring board etc. with less environmental load by being excellent in electrical characteristics and excellent in flame retardance even in halogen free. It is to provide a resin composition capable of

Therefore, the present inventors intensively studied and found that by blending a specific phosphorus-containing compound in a polyphenylene ether resin, a cured product excellent in electric properties and excellent in halogen-free flame retardancy can be obtained. The present invention has been reached.
That is, the present invention provides a resin composition comprising (A) a polyphenylene ether resin and (E) a phosphorus-containing compound represented by the following formula (1).

式（１）中、ｍは１〜１０の整数を表し、Ｒ¹及びＲ²はそれぞれ独立して、アルキル基、アリール基、又は−ＮＲ⁴Ｒ⁵を表し、Ｒ³は、酸素、硫黄、リン及び窒素から選ばれる原子を含んでいる場合がある炭化水素基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、酸素原子、硫黄原子、又は−ＮＲ⁶−を表し、Ｒ⁴及びＲ⁵は、それぞれ独立して、水素原子、アルキル基、又はアリール基を表し、Ｒ⁶は、水素原子、アルキル基、又はアリール基を表す。また、Ｒ¹及びＲ²が共に−ＮＲ⁴Ｒ⁵である場合には、Ｒ⁴同士又はＲ⁵同士が異なる基である場合がある。

In formula (1), m represents an integer of 1 to 10, R ¹ and R ² each independently represent an alkyl group, an aryl group, or —NR ⁴ R ⁵ , and R ³ represents oxygen, sulfur, R represents a hydrocarbon group which may contain an atom selected from phosphorus and nitrogen, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or -NR ^6- , R ⁴ and Each R ⁵ independently represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶ represents a hydrogen atom, an alkyl group or an aryl group. Further, when R ¹ and R ² is -NR ⁴ R ⁵ together may R ⁴ together or R ⁵ together are different groups.

  According to the present invention, it is possible to provide a cured product which is excellent in electrical properties, halogen-free, and excellent in flame retardancy. Moreover, the laminated board excellent in the flame retardance can be obtained by using this hardened | cured material.

  The details of the resin composition of the present invention will be described below.

  The use application of the resin composition of the present invention is not particularly limited, and, for example, a laminate used for an electronic circuit board, a sealing agent used for an electronic component, a casting material, a film material, an adhesive, an electrical insulating paint It can be used for composites that require flame retardancy, powder coatings and the like. In the present invention, in particular, it is preferable to use a laminate for use in an electronic circuit substrate, a sealant for use in an electronic component, a casting material, etc., and it is most preferable to use for a laminate. The resin composition of the present invention and the cured product thereof are excellent in electric characteristics and excellent in flame retardancy, and thus can be suitably used as an insulating material such as a printed wiring board.

  The polyphenylene ether resin which is the component (A) used in the present invention is a polymer having a structure represented by the following formula (II).

式（II）中、ｓは１〜１００の数を表し、Ｒ²¹〜Ｒ²⁴はそれぞれ独立して水素原子、アルキル基、アルケニル基、アルキニル基、アルキルカルボニル基、又はアルケニルカルボニル基を表す。＊は結合手を表す。

In formula (II), s represents a number of 1 to 100, and R ^{21 to} R ²⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkylcarbonyl group or an alkenylcarbonyl group. * Represents a bond.

As an alkyl group represented by R ^{21 to} R ²⁴ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. Groups are mentioned.
The alkenyl group represented by R ²¹ to R ^24, for example, vinyl group include groups such as allyl groups.
Examples of the alkynyl group represented by R ^{21 to} R ²⁴ include groups such as ethynyl and 2-propynyl.
The alkyl group represented by R ²¹ to R ^24, for example, include groups such as acetyl group.
As an alkenyl carbonyl group represented by R < ²¹ > -R < ²⁴ >, an acryloyl group and a methacryloyl group can be mentioned, for example.
Among the polyphenylene ether resins, it is particularly preferable in the general formula (II) that each of R ^{21 to} R ²⁴ independently is a hydrogen atom or an alkyl group from the viewpoint of cost and easy availability.

  The end of the polyphenylene ether resin as the component (A) used in the present invention may have a hydroxyl group, and the end may be modified by a group having an unsaturated bond or the like.

  In order to improve the heat resistance, chemical resistance, water resistance, etc. of the product obtained from the resin composition of the present invention, the polyphenylene ether resin which is the component (A) contained in the resin composition of the present invention or its cured product is It may be a crosslinked polyphenylene ether resin. For this reason, the resin composition of the present invention may contain a component for crosslinking the polyphenylene ether resin in addition to the resin.

  In the present invention, as a method for crosslinking (A) polyphenylene ether resin, (I) (A) polyphenylene ether resin, (C) a crosslinking type curing agent having two or more ethylenically unsaturated bonding groups in the molecule, D) A method in which a radical initiator is contained in a resin composition, or (II) (A) A polyphenylene ether resin having terminal hydroxyl groups is selected, and (B) epoxy group and / or isocyanate group and ethylenic Examples thereof include a compound having an unsaturated bond group, a crosslinkable curing agent having (C) two or more ethylenically unsaturated bond groups in the molecule, and a (D) radical initiator in the resin composition.

  The polyphenylene ether resin having a hydroxyl group at an end, which is used as the component (A) of the present invention, can be produced by a generally known method. As a polyphenylene ether resin which has a hydroxyl group in the terminal, in the case of cross-linking and using normally, that whose number average molecular weight is 1000-70000 can be used preferably.

  As a commercial item of polyphenylene ether resin which has a hydroxyl group at these terminals, SA-90 (made by Sabic) etc. are mentioned, for example.

  The modified polyphenylene ether resin having an ethylenically unsaturated bond at the end is produced, for example, by reacting a polyphenylene ether resin having a hydroxyl group at the end with a compound having an ethylenically unsaturated bond and a group capable of reacting with the hydroxyl group. can do. As a polyphenylene ether resin having an unsaturated double bond at the end, one having a number average molecular weight of 1,000 to 70,000 can be preferably used in the case of using in general by crosslinking. As an ethylenically unsaturated bond group which comprises the ethylenically unsaturated bond of the terminal of polyphenylene ether resin, an acryloyl group, methacryloyl group, a vinyl group, an allyl group is mentioned, for example. In addition, an ethylenic double bond is mentioned as an ethylenically unsaturated bond, Similarly, an ethylenic double bond group is mentioned as an ethylenically unsaturated bond group.

  As a commercial item of polyphenylene ether resin which has an ethylenically unsaturated bond at these terminal, MX-9000 (made by Sabic) etc. are mentioned, for example.

  In the present invention, when a polyphenylene ether resin having a hydroxyl group at the end is used as the component (A), a compound having an epoxy group and / or an isocyanate group which is the component (B) and an ethylenically unsaturated bond group can be used in combination. Although the structure is not limited as long as it satisfies the requirements, examples thereof include vinyl group-containing epoxides, vinyl group-containing isocyanates, glycidyl methacrylate and the like.

  When a compound which is the component (B) is used in the present invention, the amount of the compound used is the isocyanate group and epoxy group of the component (B) with respect to 1 mole of hydroxyl groups of the polyphenylene ether resin which is the component (A). The total amount is preferably 0.8 to 2.0 moles.

  The crosslinkable curing agent having two or more ethylenic unsaturated bond groups, which is the component (C) which can be used in the present invention, is not limited in its structure, but, for example, divinylbenzene And divinyl naphthalene, divinyl phenyl, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane, 1,7-octadiene, 1,9-decadiene and the like.

  As an ethylenically unsaturated bond group in (B) component and (C) component, what was mentioned above as an ethylenically unsaturated bond group which comprises the ethylenic unsaturated bond of the terminal of polyphenylene ether resin is mentioned.

  In the case of using the crosslinking type curing agent which is the component (C) in the present invention, the amount thereof used is 1 mol of hydroxyl group and / or ethylenically unsaturated bonding group of the polyphenylene ether resin which is the component (A). The amount of the crosslinkable curing agent is preferably 0.5 to 6.0 mol, and more preferably 0.8 to 3.0 mol.

  Examples of the radical initiator which is the component (D) that can be used in the present invention include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-1-methyl-1-propan-1-one, 2-hydroxy -1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2- (dimethylamino) -2-one (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) A mixture of phenyl phosphine oxide, phenylglyoxylic acid methyl ester, oxyphenylacetic acid-2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid-2- (2-hydroxyethoxy) ethyl ester, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), α, α'-di (tert-butylpero) Di) diisopropylbenzene, benzoin, benzoin methyl, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, thioxanthone, 2,4-diethylthioxanthone, 4,4'-diazide chalcone, 2,6-bis (4'-) (Azidobenzal) cyclohexanone, 4,4'-diazide benzophenone, azobisisobutylonitrile, 2,2'-azobispropane, m, m'-azoxystyrene, hydrazone, 2,5-dimethyl-2,5-di ( Tert-Butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoctyl) hexyne-3, dicumyl peroxide, isobutyl peroxide, α, α'-bis (neodecanoylper) Oxy) diisopropylbenzene, cumylperoxy neodecanoate, di-n Propyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, diisopropyl peroxycarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2-ethoxy Ethylperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, tertiary hexylperoxyneodecanoate, dimethoxybutylperoxydecanoate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, Tributyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, 1,1,3,5-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-di (2-ethylhexano Ruperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxybutyrate, tert-butyltrimethylsilylperoxide, etc. It can be mentioned.

In addition, the crosslinking of the components (A), (B) and (C) of the present invention can also be carried out by a cationic reaction using a cationic initiator instead of the radical reaction using a (D) radical initiator . Examples of the cationic initiator include diallyliodonium salts, triallyl phosphonium salts, aliphatic sulfonium salts, etc. in which BF ₄ , PF ₆ , AsF ₆ and SbF ₆ are counter anions.

  In the case of using the radical initiator which is the component (D) in the present invention, the amount thereof used is relative to the total amount of the ethylenically unsaturated bonding groups of the components (A), (B) and (C). Preferably, it is 0.01 to 20 equivalents.

  Next, the phosphorus-containing compound represented by the following formula (1) which is the component (E) of the present invention will be described.

式（１）中、ｍは１〜１０の整数を表し、Ｒ¹及びＲ²はそれぞれ独立して、アルキル基、アリール基、又は−ＮＲ⁴Ｒ⁵を表し、Ｒ³は、酸素、硫黄、リン及び窒素から選ばれる原子を含んでいる場合がある炭化水素基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、酸素原子、硫黄原子、又は−ＮＲ⁶−を表し、Ｒ⁴及びＲ⁵は、それぞれ独立して、水素原子、アルキル基、又はアリール基を表し、Ｒ⁶は、水素原子、アルキル基、又はアリール基を表す。また、Ｒ¹及びＲ²が共に−ＮＲ⁴Ｒ⁵であった場合には、Ｒ⁴同士又はＲ⁵同士が異なる基である場合がある。

In formula (1), m represents an integer of 1 to 10, R ¹ and R ² each independently represent an alkyl group, an aryl group, or —NR ⁴ R ⁵ , and R ³ represents oxygen, sulfur, R represents a hydrocarbon group which may contain an atom selected from phosphorus and nitrogen, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or -NR ^6- , R ⁴ and Each R ⁵ independently represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶ represents a hydrogen atom, an alkyl group or an aryl group. Further, when R ¹ and R ² were -NR ⁴ R ⁵ together may R ⁴ together or R ⁵ together are different groups.

  In formula (1), m is preferably 1 to 7, and more preferably 2 to 5. When m is a number larger than 10, it is not preferable because the viscosity becomes high and the production becomes difficult when producing the phosphorus-containing compound. Moreover, when m is 2 or more, since it is easy to prevent the bleed-out after hardening, it is preferable.

In formula (1), R ¹ and R ² are those which are alkyl or aryl group, or both are preferably used because those are -NR ⁴ R ⁵ can be easily manufactured.

Examples of the alkyl group represented by R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ in the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropyl group, a butyl group, an isobutyl group, and Examples thereof include a tributyl group, an amyl group, an isoamyl group, a tertiary amyl group, a hexyl group, an isohexyl group, an octyl group, a 2-ethylhexyl group, a tertiary octyl group, a nonyl group and a decyl group. Among these alkyl groups, those having 1 to 6 carbon atoms are preferable, and those having 1 to 2 carbon atoms are more preferable. The aryl group represented by R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ is preferably an aryl group having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group Can be mentioned.

As a hydrocarbon group represented by R ³ in the formula (1), for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, amyl group, isoamyl group, tertiary Alkyl groups such as amyl group, hexyl group, isohexyl group, octyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, decyl group; aryl groups such as phenyl group and naphthyl group; methylene group, ethylene group, propylene Groups, alkanediyl groups such as ethanediyl group and octanediyl group; alkanetriyl groups such as methanetriyl and 1,1,2-ethanetriyl group; alkanetetrayl groups such as 1,1,2,2-ethanetetrayl; hydroquinone Residues of mononuclear polyhydric phenol compounds such as resorcin, pyrocatechol, phloroglucinol etc .; Roxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (ortho cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene (ortho cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxy) (Cumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane , Thio bisphenol, sulfonyl bisphenol, oxy bisphenol, phenol novolak, ortho cresol novolak, ethyl phenol novolak, butyl phenol novolak, octyl phenol novolak, resor The residue which remove | eliminated the hydroxyl group from polynuclear polyhydric phenol compounds, such as a cinnovolak and a terpene phenol, is mentioned. The hydrocarbon group represented by R ³ may contain an atom selected from oxygen, sulfur, phosphorus and nitrogen, in which case, for example, oxygen, sulfur, phosphorus and Preferably, an atom selected from nitrogen is included.

  In the phosphorus-containing compound which is the component (E) used in the present invention, in the above formula (1), X is an oxygen atom, and Y is a group from the viewpoint that raw materials for production are easily available. It is preferably an oxygen atom.

The phosphorus-containing compound which is the component (E) to be used in the present invention has both R ¹ and R ^{2 in} the above formula (1) from the viewpoint that the phosphorus content in the component (E) can be mentioned. Preferred are those which are alkyl groups, or those in which R ¹ and R ² are both —NR ⁴ R ⁵ , R ⁴ is a hydrogen atom, and R ⁵ is an alkyl group. In particular, those in which R ¹ and R ² are both —NR ⁴ R ⁵ , R ⁴ is a hydrogen atom, and R ⁵ is an alkyl group are preferable.

From the viewpoint of physical properties of a cured product obtained by curing the flame retardant resin composition of the present invention, the phosphorus-containing compound of the component (E) used in the present invention is a compound containing at least one aromatic ring in its skeleton Preferably, in the above formula (1), R ³ is selected from the following general formulas (2-1), (2-2), (2-4), (2-5), and (2-6) The compound which is a group which has any structure is mentioned as a preferable compound.

式（２−１）中、ｐは０〜３の整数を表し、Ｒ⁷は、水素原子又は炭素数が１〜４のアルキル基を表し、Ｒ⁸は単結合、メチレン基、又は−Ｃ（ＣＨ₃）₂−を表し、Ｒ⁹及びＲ¹⁰は、独立して、水素原子、又は炭素数が１〜６のアルキル基を表し、＊は結合手を表す。

In formula (2-1), p represents an integer of 0 to 3, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a single bond, a methylene group or -C ( CH _{3) 2} - represents, R ⁹ and R ¹⁰ are independently hydrogen atom, or a carbon number represents 1-6 alkyl group, * represents a bond.

式（２−２）中、ｎは０〜３の整数を表し、ｏは０〜５０の整数を表し、Ｒ¹¹は、水素原子、又は炭素数が１〜４のアルキル基を表し、Ｒ¹²は酸素及び硫黄から選ばれる原子を含んでいる場合がある炭化水素基を表し、Ｚは水酸基、又は下記一般式（２−３）で表される官能基であり、＊は結合手を表す。

In formula (2-2), n represents an integer of 0 to 3, o represents an integer of 0 to 50, R ¹¹ represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, R ¹² Represents a hydrocarbon group which may contain an atom selected from oxygen and sulfur, Z represents a hydroxyl group, or a functional group represented by the following general formula (2-3), and * represents a bond.

式（２−３）中、Ｒ¹及びＲ²は、上記式（１）のそれと同様の基を表す。＊は結合手を表す。

In formula (2-3), R ¹ and R ² each represent the same group as that of the above formula (1). * Represents a bond.

式（２−４）中、＊は結合手を表す。

In Formula (2-4), * represents a bond.

式（２−５）中、＊は結合手を表す。

In Formula (2-5), * represents a bond.

式（２−６）中、＊は結合手を表す。

In Formula (2-6), * represents a bond.

In the formula, the alkyl group having 1 to 6 carbon atoms represented by R ⁹ and R ¹⁰ and the alkyl group having 1 to 4 carbon atoms represented by R ⁷ and R ¹¹ include the above-mentioned R ¹ and R ¹ Among the groups exemplified as the alkyl group represented by ² , R ⁴ , R ⁵ and R ⁶ , those having a predetermined carbon number can be mentioned.
As a hydrocarbon group which may contain an atom selected from oxygen and sulfur represented by R ¹² , in addition to an alkylene group having 1 to 6 carbon atoms, -S-, -SO-, -SO _2- It can be mentioned.

Among these preferably mentioned compounds, those in which R ³ is a group represented by the formula (2-1) or (2-2) are preferable, and in particular, R ³ is represented by the formula (2-1) Preferred are those in which R ⁷ is a hydrogen atom.

  Although the compounding quantity of the said (E) phosphorus-containing compound in the resin composition of this invention is not specifically limited, (A) component of a resin composition, and (B) component added as needed It is preferable that the blending amount of (E) component is 0.5 to 50% by mass with respect to the total mass of (C) component, (D) component, and (F) component described later, and 5 to 25 mass More preferably, the amount is%. By making the compounding quantity of (E) component 1 mass% or more, it is easy to prevent the fall of the flame retardance of a resin composition. On the other hand, when the compounding quantity of (E) component shall be 100 mass% or less, it will be easy to prevent the fall of the water resistance of a resin composition. Moreover, 1-100 mass parts is preferable with respect to 100 mass parts of (A) component of a resin composition from the same viewpoint to the compounding quantity of said (E) phosphorus compound, and 10-50 mass parts is more preferable.

  In the resin composition of the present invention, a flame retardant other than the phosphorus-containing compound which is the component (E) [component (F)] can be used. For example, a phosphorus-containing compound other than the component (E), a nitrogen-containing compound And boron-containing compounds, halogen compounds, silicon compounds, inorganic compounds and the like. In particular, when environmental load is considered, phosphorus-containing compounds other than the component (E) having a phosphorus atom in the molecular skeleton are suitably used.

  Examples of phosphorus-containing compounds other than the above component (E) include aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, etc .; triphenyl phosphate, cresyl diphenyl phosphate, dicrete Dylphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis (isopropylphenyl) phenyl phosphate, tris (trimethylphenyl) phosphate, tris (t -Butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate Aromatic phosphoric acid esters such as sulfate; resorcinol polyphenyl phosphate, 1,3-phenylene bis (2,6-dimethylphenyl phosphate), resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, Hydroquinone poly (2,6-xylyl) phosphates and condensed phosphate esters such as condensates thereof; phosphates such as ammonium phosphate and melamine phosphate; condensed phosphates such as ammonium polyphosphate and melamine polyphosphate; tris (Diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, zinc bis (diethylphosphinic acid), zinc bis (methylethylphosphinic acid), zinc bis (diphenylphosphinate), zinc triphosphinate, bis Diethyl phosphinic acid) Metal salts of phosphinic acids such as titanyl tetrakis (diethyl phosphinic acid) titanium, bis (methyl ethyl phosphinic acid) titanyl, titanium tetrakis (diphenyl phosphinic acid), titanyl tetra phosphinate, etc .; Methyl, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO), 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa Phosphate ester such as -10-phosphaphenanthrene-10-oxide; Addition reaction product of DOPO and acrylic ester, addition reaction product of DOPO and epoxy resin, addition reaction product of HCA and hydroquinone, etc. Compounds; Phosphine oxide compounds such as diphenylvinyl phosphine oxide, triphenyl phosphine oxide, trialkyl phosphine oxide, tris (hydroxyalkyl) phosphine oxide; Phosphazen derivatives such as hexacyclotriphosphazene, hexaphenylcyclotriphosphazene; Red phosphorus Etc.

  Among the phosphorus-containing compounds other than the component (E), for example, ammonium polyphosphate, melamine polyphosphate, aluminum tris (diethylphosphinate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide (HCA), 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (HCA-HQ manufactured by Sanko Co., Ltd.), hexaphenylcyclo It is still more preferable that it is a triphosphazene or the flame retardant represented by either of following formula (6-1)-(6-11).

式（６−２）中、２つのＸは、両方が下記式（6−2−1）で表される基であるか、或いは、一方が下記式（6−2−1）で表される基であり且つ他方が下記式（6−2−2）で表される基である。

In formula (6-2), two X's are both a group represented by the following formula (6-2-1), or one is represented by the following formula (6-2-1) And the other is a group represented by the following formula (6-2-2).

（式中Ｐｈはフェニル基を表す）

(Wherein Ph represents a phenyl group)

F in the formula (6-1) is an integer of 1 to 50; g in the formula (6-2) represents an integer of 1 to 20;
A, b and c in formulas (6-3) to (6-5) each independently represent an integer of 1 to 5;
D and e in the formulas (6-6) and (6-7) each independently represent an integer of 1 to 10;
H in formula (6-8) represents an integer of 1 to 50, A in formula (6-11) represents a hydrogen atom, or -OR ¹⁷ and R ¹⁷ represents an alkyl group having 1 to 6 carbon atoms .

The alkyl group having 1 to 6 carbon atoms represented by R ¹⁷ in A in Formula (6-11), exemplified as the alkyl group represented by R ¹ to R ⁴ and R ⁶ in the formula (1) Among those mentioned above, those having 1 to 6 carbon atoms can be mentioned.

  Among the above-mentioned phosphorus-containing compounds, tris (diethylphosphinic acid) aluminum and 10- (2,5-phosphophenanthrene-10-oxide are particularly preferable in that the flame retardancy effect is very excellent.

  Examples of the nitrogen-containing compound include silicon nitride, aluminum nitride, and compounds which form a triazine compound and a salt of cyanuric acid or isocyanuric acid. A salt of a triazine compound and cyanuric acid or isocyanuric acid is an adduct of a triazine compound and cyanuric acid or isocyanuric acid, and is usually 1 to 1 (molar ratio), and sometimes 2 to 1 (molar ratio). Adduct having the composition of Among triazine compounds, compounds which do not form a salt with cyanuric acid or isocyanuric acid are excluded.

  Examples of the triazine compounds are melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3. And 5-triazine and the like.

  Examples of the boron compound include boric acid (such as orthoboric acid and metaboric acid), borate (such as an alkali metal borate such as sodium tetraborate, an alkaline earth metal salt such as barium metaborate, and zinc borate And the like, the condensed boric acid (salt) (pyroboric acid, tetraboric acid, pentaboric acid, octaboric acid or metal salts thereof), boron nitride and the like. These boron-containing compounds may be hydrates (for example, borax, which is hydrous sodium tetraborate). These boron-containing compounds may be used alone or in combination of two or more.

  As the above-mentioned halogen compounds, for example, tetrabromobisphenol A, carbonate oligomers of tetrame bisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), Tetrabromobisphenol A derivatives such as tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct; decabromodiphenyl ether, octabromodiphenyl ether, ethylenebistetrabromophthalimide, hexabromocyclododecane, 1,2-bis (pentabromophenyl) Ethane, 2,3-dibromopropyl pentabromophenyl ether, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-to Brominated aromatic compounds such as (2,4,6-tribromophenoxy) -1,3,5-triazine, brominated polystyrene, polybrominated styrene, pentabromobenzyl acrylate (monomer), etc .; chlorinated paraffin; chlorine Naphthalene; tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (bromochloropropyl) phosphate, tris (2,3-dibromopyrrolyl) phosphate, tris (bromochlorophenyl) phosphate, 2,3 Halogen-containing phosphoric acid esters such as dibromopropyl-2,3-dichloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate and the like .

  Examples of the inorganic compound include antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, boehmite, graphite and the like.

  Moreover, as a flame retardant marketed as (F) component, phosphate ester (For example, PN-600 made from ADEKA, and PFR), phosphorus containing phenoxy resin (for example, Nippon Nippon Steel Chemical Co., Ltd.) Fenotote ERF-001M30 and TX-0924K30 etc.), hydroxyl group-containing phosphate esters (eg DAIGUARD-580 produced by Daihachi Chemical Industry Co., Ltd., and DAIGUARD-610 etc.), HCA derivatives (eg HCA-HQ, M-Ester, and ME-P8, etc.), Intomescent flame retardants that are composite flame retardants (eg, FP-2100 JC, FP-2200 S, FP-C manufactured by ADEKA Co., Ltd.) 2500S) and the like.

  In the present invention, the amount of the component (F) to be used is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the phosphorus compound which is the component (E), in the case of using this; It is more preferable that it is a mass part, and it is still more preferable that it is 30-300 mass parts. In particular, in consideration of the load on the environment, even when it is necessary to use a halogen compound etc., it is preferable to keep the amount as small as possible, and 100 parts by mass of the phosphorus compound which is the component (E) On the other hand, the amount of the halogen compound is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less.

  As the usage-amount of (F) component in case the phosphorus atom contains in the flame retardant which is (F) component, (A) component of a resin composition, (E) component, and it is added as needed It is preferable that the phosphorus content derived from the (F) component is 0.1 to 5% by mass in the total mass of the (B) component, the (C) component, the (D) component, and the (F) component. More preferably, the amount is 0.5 to 3% by mass. By making phosphorus content into 0.1 mass% or more, it is easy to prevent that the flame retardance of a resin composition falls. On the other hand, by setting the phosphorus content to 5% by mass or less, the water resistance of the resin composition can be prevented from being significantly reduced.

  Other resins can be used together with the polyphenylene ether resin in the resin composition of the present invention. As other resin, an epoxy resin, a phenol resin, a melamine resin, a urea resin, unsaturated polyester resin, an alkyd resin, a polyurethane resin, thermosetting imide resin, cyanate resin etc. are mentioned, for example. Among these, epoxy resins can be mentioned as preferable resins. The resin composition of the present invention preferably contains 10 parts by mass or more, more preferably 20 parts by mass, and particularly preferably 50 parts by mass or more based on 100 parts by mass of the total resin amount. .

  The epoxy resin is not particularly limited in molecular structure, molecular weight, etc., as long as it has at least two epoxy groups in the molecule, and can be appropriately selected from known epoxy resins, but it is used properly depending on the application to be used Is preferred.

  Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcine, pyrocatechol, phloroglucinol, etc .; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (ortho cresol), ethylidene Bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (ortho cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene) 1,1,3-Tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxy Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol Polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide addition Polyglycidyl of polyhydric alcohol compounds such as Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Glycidyl ester compounds of aliphatic, aromatic or alicyclic polybasic acids such as acid, pyromellitic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid and homopolymers or copolymers of glycidyl methacrylate; N, N-di- Glycidyl aniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl ortho toluidine, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-Methylaniline, N, N-bis (2,3-epoxypropyl) -4 Epoxy compounds having a glycidyl amino group such as-(2,3-epoxypropoxy) aniline, N, N, N ', N'-tetra (2,3-epoxypropyl) -4,4-diaminodiphenylmethane; vinyl cyclohexene di- Epoxide, cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4- Epoxides of cyclic olefin compounds such as epoxy-6-methylcyclohexylmethyl) adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer; Heterocyclic rings such as triglycidyl isocyanurate Compounds, and the like. In addition, these epoxy resins are those which are internally crosslinked by a prepolymer of terminal isocyanate, or those which are polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) May be.

  The above epoxy resins may be used alone or in combination of two or more. When the flame retardant epoxy resin composition is for a laminate, it is preferable to use a polyglycidyl ether compound of a polynuclear polyhydric phenol compound as the epoxy resin, and among them, novolac epoxy resin and / or bisphenol epoxy resin Use of a resin is more preferable in terms of inexpensiveness and availability.

  Moreover, when using an epoxy resin for the resin composition of this invention, the curing agent for epoxy resins can be used, As a curing agent for epoxy resins, phenolic resins, aliphatic amines, aromatic amine , Latent hardeners, and acid anhydrides. In the present invention, it is preferable to use these curing agents properly depending on the application. In particular, when the present invention is used for laminate applications, the use of phenolic resins or latent hardeners is preferred.

The amount of the curing agent used can be changed as needed. For example, when a phenolic resin is selected as the curing agent, it is preferable to blend 0.3 to 1.5 hydroxyl groups in the phenolic resin with respect to one epoxy group of the epoxy resin, It is more preferable to mix | blend so that it may become 0.8-1.2 pieces.
When a latent curing agent is selected as the curing agent, it is 0.1 to 80% by mass, preferably 0.5 to 60% by mass, and more preferably to the total amount of the epoxy resin and the latent curing agent. It is 1-40 mass%.

  The resin composition of the present invention may, if necessary, contain an organic solvent as a viscosity modifier. Examples of the organic solvent in this case include amides such as N, N-dimethylformamide; ethers such as ethylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; and aroma such as benzene and toluene Group hydrocarbons and the like. In the present invention, at least one solvent selected from these solvents is added to components (A), (B), (C), (D), and (D) of the present invention, and a reaction optionally used. It can be mix | blended in the quantity which will be 1 to 90 mass%, for example with respect to the total mass of the sex diluent.

  The resin composition of the present invention may optionally contain an inorganic filler. As such an inorganic filler, for example, silica such as fused silica and crystalline silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium carbonate, calcium silicate, potassium titanate, beryllia, zirconia And zircon, forsterite, steatite, spinel, mullite, powders such as titania, or beads obtained by spheronizing them, glass fibers, and the like. These inorganic fillers may be used alone or in combination of two or more.

  In the present invention, it is preferable to properly use the above-mentioned inorganic filler depending on the application to be used. With respect to the use of the laminate, it is preferable to use fused silica, aluminum hydroxide or the like. With respect to the use of the sealant, it is preferable to use fused silica, crystalline silica or the like, and it is particularly preferable to use fused silica. With respect to the use of the casting material, it is preferable to use fused silica, crystalline silica, aluminum hydroxide or the like, and it is particularly preferable to use fused silica.

  Moreover, in the resin composition of this invention, additives other than the said inorganic filler may be contained as needed. As the above additives, non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar; fibrous fillers such as glass fibers, pulp fibers, synthetic fibers, ceramic fibers, etc .; , Aramid cloth, reinforcing material such as carbon fiber; pigment; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N'- β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyl Triethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ- Silane coupling agents such as aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc .; candelilla wax, carnauba wax, wax wax, ivota wax, Lubricants such as beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, aromatic ether, etc .; thickeners; thixotropic agents; antioxidants; Stabilizers; UV absorbers; antifoaming agents; rust inhibitors; and conventional additives such as colloidal silica and colloidal alumina. In the present invention, tacky resins such as xylene resin and petroleum resin can also be used in combination.

  The resin composition of the present invention is a laminate used for an electronic circuit board, a sealing material used for an electronic component, a casting material, a film material, an adhesive, an electrical insulating paint, a composite material requiring flame retardancy, a powder paint It can be used as a floor material, an anticorrosion paint, a concrete repair material, etc., and is particularly suitable for use as a laminate, a semiconductor sealing material, an interlayer insulating film, a resin-coated copper foil.

EXAMPLES The present invention will next be described in more detail by way of Examples and Comparative Examples, which should not be construed as limiting the invention thereto.
In the following examples and the like,% is by mass unless otherwise specified.

  The item evaluated in the examples is flame retardancy.

  The cured product of the resin composition obtained in the following Examples and Comparative Examples was crushed to about 5 mm square and ignited using a lighter in a state of being held by tweezers. Those showing self-extinguishing were marked ○, those not showing self-extinguishing and those with drip were marked ×. The evaluation results are shown in [Table 1].

Example 1
60 parts by mass of NORYL SA-90 (manufactured by SABIC; low molecular weight polyphenylene ether resin), 40 parts by mass of triallyl isocyanurate (TAIC), perbutyl P (Nippon Yushi Co., Ltd. Made of a radical generator) 1.0 part by mass of the radical generating agent and 29 parts by mass of the following phosphorus-containing compound P-1 are put into toluene and stirred at 90 ° C. until completely dissolved to prepare a resin composition in the form of a resin solution did.
Next, the obtained resin composition was heated and dried at 130 ° C. for 2 hours, and then heated at 220 ° C. for 4 hours to prepare a cured product of the resin composition.

（式中、ｐは０〜３である。その平均値は０．１である。）

(In the formula, p is 0 to 3. The average value is 0.1.)

Example 2
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 24 parts by mass of the following phosphorus-containing compound P-2, and the same evaluation as in Example 1 was performed. .

[Example 3]
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 28 parts by mass of the following phosphorus-containing compound P-3, and the same evaluation as in Example 1 was performed. .

（式中、ｐは０〜３である。その平均値は０．１である。）

(In the formula, p is 0 to 3. The average value is 0.1.)

Example 4
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 27 parts by mass of the following phosphorus-containing compound P-4, and the same evaluation as in Example 1 was performed. .

[Example 5]
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 25 parts by mass of the following phosphorus-containing compound P-5, and the same evaluation as in Example 1 was performed. .

[Example 6]
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 25 parts by mass of the following phosphorus-containing compound P-6, and the same evaluation as in Example 1 was performed. .

（式中、ｏは０〜１０である。その平均値は３．２である。）

(In the formula, o is 0 to 10. The average value is 3.2.)

Comparative Example 1
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was not used, and the same evaluation as in Example 1 was performed.

Comparative Example 2
A resin composition and a cured product thereof were produced in the same manner as in Example 1 except that the phosphorus-containing compound P-1 was changed to 42 parts by mass of the following phosphorus-containing compound HP-1 and evaluated in the same manner as in Example 1. .

（表中、数字は質量部である）

(In the table, numbers are parts by mass)

  As shown by the above-mentioned examples, the resin composition of the present invention is mainly used for polyphenylene ether resin excellent in electric characteristics, and is suitably used particularly for electronic material applications since it is excellent in flame retardancy. Can.

Claims (12)

A resin composition containing (A) a polyphenylene ether resin and (E) a phosphorus-containing compound represented by the following formula (1).

In formula (1), m represents an integer of 1 to 10, R ¹ and R ² each independently represent an alkyl group, an aryl group, or —NR ⁴ R ⁵ , and R ³ represents oxygen, sulfur, R represents a hydrocarbon group which may contain an atom selected from phosphorus and nitrogen, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or -NR ^6- , R ⁴ and Each R ⁵ independently represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶ represents a hydrogen atom, an alkyl group or an aryl group. Further, when R ¹ and R ² were -NR ⁴ R ⁵ together may R ⁴ together or R ⁵ together are different groups. The resin composition according to claim 1, wherein in formula (1), R ¹ and R ² are each independently an alkyl group or an aryl group. The resin composition according to claim 1, wherein in the formula (1), R ¹ and R ² are both -NR ⁴ R ⁵ .   The resin composition according to any one of claims 1 to 3, wherein in the formula (1), both X and Y are oxygen atoms. The resin composition according to any one of claims 1 to 4, wherein in formula (1), R ³ is a hydrocarbon group having at least one aromatic ring. In formula (1), any one of R ³ is selected from the following general formulas (2-1), (2-2), (2-4), (2-5), and (2-6) The resin composition according to claim 5, which is a group having a structure.

In formula (2-1), p represents an integer of 0 to 3, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a single bond, a methylene group or -C ( CH _{3) 2} - represents, R ⁹ and R ¹⁰ are independently hydrogen atom, or a carbon number represents 1-6 alkyl group, * represents a bond.

In formula (2-2), n represents an integer of 0 to 3, o represents an integer of 0 to 50, R ¹¹ represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, R ¹² Represents a hydrocarbon group which may contain an atom selected from oxygen and sulfur, Z represents a hydroxyl group, or a functional group represented by the following general formula (2-3), and * represents a bond.

In formula (2-3), R ¹ and R ² each represent the same group as that of the above formula (1). * Represents a bond.

In Formula (2-4), * represents a bond.

In Formula (2-5), * represents a bond.

In Formula (2-6), * represents a bond.   The resin composition according to any one of claims 1 to 6, wherein the polyphenylene ether resin as the component (A) is a polyphenylene ether resin having a hydroxyl group at an end.   The resin composition according to any one of claims 1 to 6, wherein the polyphenylene ether resin as the component (A) is a modified polyphenylene ether resin having an ethylenic double bond at an end.   The resin composition according to any one of claims 1 to 8, which contains (B) a compound having an epoxy group and / or an isocyanate group and an ethylenic double bond group.   The resin composition according to any one of claims 1 to 9, which contains (C) a crosslinkable curing agent having two or more ethylenic double bond groups in the molecule.   The resin composition according to any one of claims 1 to 10, which contains (D) a radical initiator.   The laminated board which has a hardened | cured material of the resin composition in any one of Claims 1-11.