JP2003213145A - Flame-retardant resin composition and epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition and an epoxy resin composition which not only can eliminate influences on the environment and the human body but also can exhibit excellent fundamental performances such as mechanical properties, heat resistance, and the like, and further can give a cured product excellent in flame-retardancy, and therefore are suitably employable for various applications requiring flame retardancy, and the like. <P>SOLUTION: The flame-retardant resin composition comprises, as essential ingredients, a thermoplastic resin (A), a polyhydric phenol (B) and a crosslinking agent (C) for the polyhydric phenol. The epoxy resin composition comprises, as essential ingredients, an epoxy resin (E), a polyhydric phenol (F) and a thermoplastic resin (G). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition and an epoxy resin composition. More specifically, it relates to a flame-retardant resin composition and an epoxy resin composition that essentially contain polyhydric phenol.

[0002]

2. Description of the Related Art Home appliances, office automation equipment (hereinafter abbreviated as home appliances and OA products), composite materials such as printed wiring boards, semiconductor encapsulation materials, car engine covers and interior materials, fire caused by electrical leakage. High flame retardancy is required to prevent the above. Among them, electrical and electronic equipment,
Regarding printed wiring boards that are widely used in communication equipment, computing equipment, etc., high integration has progressed due to higher wiring density and higher number of layers. Along with this, the heat resistance of wiring laminates has improved. There is an increasing demand for a material, and a material having more excellent electrical characteristics is required in order to cope with broadbandization.

In these applications requiring flame retardancy, a large amount of halogen flame retardants and antimony flame retardants are added to impart flame retardancy. However,
Some halogen-based compounds generate harmful halogen-based gas when burned, and the environmental impact and high impact on human body during incineration of waste and thermal recycling by heat recovery. Has become an issue, and flame retardant technology that can overcome halogen-free is required. There is also concern that antimony compounds also have chronic toxicity.

Therefore, in recent years, substitution with mainly phosphorus compounds such as red phosphorus and phosphoric acid esters has been started. Regarding the recent development trend as a thermoplastic resin composition, JP-A-2000-80253 discloses that a thermoplastic polyester resin (A) and a compound having a phenol skeleton (b1) and a triazine skeleton (b2) ( Regarding the flame-retardant polyester resin composition containing B) as an essential component, it is disclosed that the flame-retardant effect can be improved by using the red phosphorus flame retardant (C) together.
No. 3557 discloses an epoxy resin composition comprising an epoxy resin, a curing agent and a phosphorus-containing compound, which comprises, as a curing agent, a mixture or condensate of a phenol and a compound having a triazine ring and an aldehyde. An epoxy resin composition using a phenol resin composition which does not contain unreacted aldehydes in the condensate and substantially does not contain a methylol group is disclosed.
JP-A-188717 discloses a flame-retardant resin composition containing a thermoplastic resin, a phosphorus compound and a phenol aralkyl resin as essential components. However, phosphorus compounds pose new concerns such as eutrophication of soil and lakes due to phosphorus-containing leaked components from waste waste products, and also deteriorate mechanical properties and moisture resistance of engineering plastic molded products. Therefore, it is possible to satisfy the flame retardancy required for molding materials such as electronic materials, adhesives, paints, etc. without adding such flame retardants so that the basic performance becomes excellent. Coveted.

Regarding the recent development trend of thermosetting resin compositions, JP-A-2000-219716 discloses a method for producing an amino-modified phenol / aralkyl resin by reacting a phenol / aralkyl resin, a triazine derivative and an aldehyde. It is disclosed that a composition used for a molding material or the like having excellent flame retardancy can be prepared by blending the amino-modified phenol / aralkyl resin produced by this production method, and it is disclosed in JP-A-200
No. 0-351822 discloses polyaromatics obtained by reacting phenols (A) and aromatics (B) excluding phenols, and heterocyclic compounds (C) containing nitrogen as a hetero atom. However, regarding a flame-retardant phenolic resin material containing a phenol-based condensate condensed through an aldehyde (D), it is disclosed that it is preferable to use triazines as the heterocyclic compound (C). .
However, in the resin composition according to these techniques, the viscosity of the reaction raw material phenol / aralkyl resin is high, and the viscosity is further increased by reacting this with a triazine derivative and an aldehyde, so that it can be used as a molding material or the like. In order to obtain a thermosetting resin composition that can be obtained, the amount of the triazine derivative introduced is limited, and sufficient flame retardancy cannot be exhibited. Further, since it becomes a cured product having an extremely rigid crosslinked structure, there is a problem of unbalance between crack resistance and mechanical properties. There was room to devise so as to exhibit excellent flame retardancy and to be applicable to applications requiring higher performance.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is capable of eliminating the influence on the environment and the human body and is excellent in basic properties such as mechanical properties and heat resistance. Moreover, it is an object of the present invention to provide a flame-retardant resin composition and an epoxy resin composition which can give a cured product having excellent flame retardancy.

[0007]

[Means for Solving the Problems] The inventors of the present invention have made various studies on flame-retardant resin compositions containing substantially no halogen, and have (1) phenols and (2) a specific triazine ring structure. By reacting a compound and (3) a reaction raw material containing three types of compounds, a hydroxyl group, an alkyl ether group or an alkyl ester group having a specific carbon number at both ends, and a specific aromatic ring. In addition to having basic properties such as physical properties and heat resistance, the resulting polyhydric phenol has a nitrogen atom in addition to having an aromatic ring in the molecule. It has been found that it becomes excellent in flammability and such a polyhydric phenol can be suitably applied as a flame retardant for thermoplastic resins, epoxy resins and the like. In such a polyhydric phenol, the viscosity of each of the three types of compounds (1) to (3) is low, and it is easy to freely adjust the proportion of these compounds. For example, the proportion of the compound (2) is If it is increased, the flame retardancy is further improved. That is, it is possible to exert a synergistic effect of the aromatic ring possessed by the compounds of (1) and (3) and the nitrogen atom possessed by the compound of (2). It can be suitably applied to adhesives, paints and the like. Moreover, in such a polyphenol,
By specifying the compounding molar ratio of the compound of (1) and the compound of (2) or the nitrogen atom content,
It was also found that the action and effect can be exhibited more reliably.

A resin composition containing such a polyhydric phenol and a thermoplastic resin and a crosslinking agent for the polyhydric phenol as essential components exhibits practically flame-retardant properties even without halogen, and has mechanical properties, It was found that the flame-retardant resin composition can form a cured product having excellent moldability and thermal properties. Further, when an epoxy resin, a polyhydric phenol and a thermoplastic resin are essential in the epoxy resin composition, halogen-free is highly flame-retardant and highly compatible, and is toughened without using any elastomer component, and It was found that the resin composition can form a cured product having excellent heat resistance, mechanical properties, and electrical properties. Further, in these flame-retardant resin compositions and epoxy resin compositions, when the thermoplastic resin is an aromatic thermoplastic resin, it is possible to exhibit more excellent flame retardancy, and further, a typical element oxide It has been found that the flame retardancy is further improved by containing the above, and it is conceived that these resin compositions can be suitably applied to various applications in which flame retardancy and the like are required, and thus the present invention has been achieved. is there.

That is, the present invention relates to a thermoplastic resin (A)
And phenols, the following general formula (1);

[0010]

[Chemical 5]

(Wherein R ¹ is the same or different,
It represents an amino group, a methylolamino group or a dimethylolamino group. R ² represents a hydrocarbon group having 1 to 12 carbon atoms. ) And a compound represented by the following general formula (2);

[0012]

[Chemical 6]

(In the formula, R ³ represents a phenylene group, an alkyl-substituted phenylene group, a naphthalene group, an alkyl-substituted naphthalene group, a biphenyl group or an alkyl-substituted biphenyl group. R ⁴ is the same or different and is a hydroxyl group or a carbon group. Alkyl ether group of 1 to 4 or 1 to 4 carbon atoms
4 represents an alkyl ester group. And a polyhydric phenol (B) obtained by reacting a reaction raw material containing a compound represented by the formula (1) as an essential component, and a cross-linking agent (C) for the polyhydric phenol as essential components. The present invention is described in detail below.

The flame-retardant resin composition of the present invention contains a thermoplastic resin (A), a polyhydric phenol (B), and a crosslinking agent (C) for polyhydric phenol as essential components. These may be used alone or in combination of two or more. The blending ratio of the essential components in the flame-retardant resin composition may be appropriately set depending on the performance required for the flame-retardant resin composition, the application, etc., but is, for example, essential with respect to 100% by mass of the flame-retardant resin composition. It is preferable that the total mass of the components is 15% by mass or more. More preferably, it is 30 mass% or more.

As the thermoplastic resin (A), various resins used for molding can be used. For example, olefin resin, acrylic resin, styrene resin, polyamide resin, polyester resin, polycarbonate. -Based resin, polyphenylene oxide-based resin, vinyl-based resin, etc., polyacetal resin, aliphatic polyketone-based resin (ketone resin); polyphenylene sulfide-based resin (for example, polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, polyphenylene sulfide sulfone, etc.) Polysulfone (for example, thermoplastic polysulfone, poly (ether sulfone), poly (4,4'-bisphenol ether sulfone, etc.); polyether ketone; poly (ether ether ketone); polyace Limide; a thermoplastic polyurethane resin (for example, a polymer obtained by reacting a diisocyanate compound such as tolylene diisocyanate with the above glycol and / or the above diamine, a polyurethane which may have a segment such as polytetramethylene glycol) Elastomer, etc.), thermoplastic polyimide, polyoxybenzylene, thermoplastic elastomer, etc. In addition, a preferred form of the thermoplastic resin (A) in the present invention is an aromatic thermoplastic resin, which is flame-retardant. The flame retardancy and electrical characteristics of the resin composition are further improved.Examples of the aromatic thermoplastic resin include polyphenylene ether, aromatic polyester, aromatic polyamide, aromatic polycarbonate, polyphenylene sulfone, polyphenylene sulfide, Polje Teruketon,
Polyimide, polyarylate, and co-condensation type polymers thereof are suitable.

In the flame-retardant resin composition of the present invention, the compounding mass ratio of the thermoplastic resin (A) to the polyhydric phenol (B) is preferably 5/95 or more, and 95 It is preferably / 5 or less. Thermoplastic resin (A) for polyphenol (B)
If the blending mass ratio is less than 5/95, the mechanical properties and the like of the molded product formed from the flame-retardant resin composition may deteriorate, and if it exceeds 95/5, the flame retardancy is insufficient. May be. It is more preferably 10/90 or more, and 90/10 or less.

The polyhydric phenol crosslinking agent (C) may be a compound or polymer having two or more functional groups capable of crosslinking the polyhydric phenol (B), such as epoxy resin and hexa. Examples thereof include methylenetetramine. Among these, epoxy resin is preferable,
An epoxy resin having an aromatic ring in its skeleton is more preferable. Examples thereof include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin and the like.

In the flame-retardant resin composition of the present invention, it is preferable that the compounding mass ratio of the polyhydric phenol crosslinking agent (C) to the polyhydric phenol (B) is 5/100 or more, Further, it is preferable to set it to 150/100 or less. The compounding mass ratio of the crosslinking agent (C) for polyhydric phenol to the polyhydric phenol (B) is 5/1.
If it is less than 00, the mechanical properties and the like of the molded product formed from the flame-retardant resin composition may be deteriorated, and the ratio of 150/1
If it exceeds 00, the flame retardancy may be insufficient.
More preferably 15/100 or more, and 120
/ 100 or less.

The polyhydric phenol (B) is obtained by reacting a reaction raw material containing phenols, a compound represented by the general formula (1) and a compound represented by the general formula (2) as essential components. Let me do it. The reaction raw materials used for producing the polyhydric phenol include phenols that will constitute the product polyhydric phenol, and the general formula (1) above.
A mixture containing, as an essential component, the compound represented by the formula (1) and the compound represented by the general formula (2), containing other compounds used as necessary, and containing a solvent and the like used as necessary for carrying out the reaction. Means The polyhydric phenol in the present invention is produced by using phenols, a compound represented by the above general formula (1) and a compound represented by the above general formula (2) as essential reaction raw materials, and Unlike the polyphenols produced from the compound having the same as the raw material, it is possible to produce the reaction product without having a chlorine-based compound such as hydrogen chloride. The phenols, the compound represented by the general formula (1) and the compound represented by the general formula (2) may be used alone or in combination of two or more kinds. In the present specification, the “polyhydric phenol” means a polymer having a plurality of aromatic rings having a hydroxyl group, which is produced using such a reaction raw material, and the “phenols” is a polyhydric phenol. Means a compound having an aromatic ring having a hydroxyl group, which is one of the raw materials used for producing.

The above-mentioned phenols have 1 in the aromatic ring.
Is not particularly limited as long as it is a compound having one or two or more hydroxyl groups bonded and one or more than one hydroxyl group-containing substituent, and examples of phenols having one hydroxyl group include the following. General formula (3);

[0021]

[Chemical 7]

(In the formula, Rs are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and either one or both of them represents a hydrocarbon group having 1 to 9 carbon atoms. It is preferable to use a compound represented by
Moreover, you may use the phenols and polycyclic phenols which have two or more hydroxyl groups. Examples of the compound represented by the general formula (3) include phenol, o-cresol,
m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, mixed cresol, pn-
Propylphenol, o-isopropylphenol, p
-Isopropylphenol, mixed isopropylphenol, o-sec-butylphenol, m-tert-butylphenol, p-tert-butylphenol, pentylphenol, p-octylphenol, p-nonylphenol, 2,3-dimethylphenol, 2,4-
Dimethylphenol, 2,6-dimethylphenol,
3,4-dimethylphenol, 2,4-di-s-butylphenol, 3,5-dimethylphenol, 2,6-di-s-butylphenol, 2,6-di-t-butylphenol, 3-methyl-4- Isopropylphenol, 3
-Methyl-5-isopropylphenol, 3-methyl-
6-isopropylphenol, 2-t-butyl-4-methylphenol, 3-methyl-6-t-butylphenol, 2-t-butyl-4-ethylphenol and the like can be mentioned. Examples of phenols having two or more hydroxyl groups include catechol, resorcin, biphenol, bisphenol A, bisphenol S, bisphenol F, and the like. Examples of polycyclic phenols include α-naphthol and β- Examples include naphthol.

In the compound represented by the above general formula (1) in the present invention, the hydrocarbon group having 1 to 12 carbon atoms in R ² is, for example, a methyl group, an ethyl group, a propyl group, a butyl group or a vinyl group. , Allyl group, phenyl group and the like. Examples of the compound represented by the general formula (1) include benzoguanamine derivatives such as melamine, benzoguanamine, and acetoguanamine.

In the compound represented by the general formula (2) in the present invention, the phenylene group, the naphthalene group and the biphenyl group in R ³ are represented by the following chemical structural formula (4).
It is represented by (6). Further, the position at which two substituents represented by R ⁴ —CH ₂ — are bonded is, in the phenylene group, an ortho position, a meta (meta) position or a para (pa) position.
When the carbon atom is numbered as in the chemical structure formula below, the naphthalene group is 1,3-, 1,4-,
1,5-, 1,6-, 1,7-, 1,8-, 2,4-,
2,5-, 2,6-, 2,7- or 2,8-position, and in the biphenyl group, 2,2'-, 2,3'-, 2,
The positions are 4'-, 3,3'-, 3,4'- or 4,4'-. These phenylene group, naphthalene group and biphenyl group may be an alkyl-substituted group, in which case it is preferably a group substituted with an alkyl group having 1 to 9 carbon atoms.

[0025]

[Chemical 8]

The hydrocarbon group constituting the alkyl ether group having 1 to 4 carbon atoms and the alkyl ester group having 1 to 4 carbon atoms in R ⁴ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group or a vinyl group. Group, an allyl group, etc., and a substituent (R ⁴ — having such a hydrocarbon group
As CH ₂ —, a methoxymethyl group (me
thoxymethyl), ethoxymethyl group (eth
oxymethyl), propoxymethyl group (prop
oxymethyl), butoxymethyl group (butho
xymethyl), pentoxymethyl group (pento
xymethyl), vinyloxymethyl group (vinyl)
an alkyl ether group such as oxymethyl); an acetyloxymethyl group,
Propanoyloxymethyl group (propanoyloxy)
methyl), butanoyloxymethyl group (butan)
oyloxymethyl), pentanoyloxymethyl group, (meth) acryloyloxymethyl group ((meth) acry)
(loyloxymethyl), (meth) allyloyloxymethyl group ((meth) allyloxyloxyme)
Examples thereof include alkyl ester groups such as thyl), and more preferably alkyl ester groups.

Examples of the compound represented by the above general formula (2) include o-diacetyloxymethylbenzene and m-
Diacetyloxymethylbenzene, p-diacetyloxymethylbenzene, o-dipropanoyloxymethylbenzene, m-dipropanoyloxymethylbenzene, p-dipropanoyloxymethylbenzene, o-dibutanoyloxymethylbenzene, m -Dibutanoyloxymethylbenzene, p-dibutanoyloxymethylbenzene, o-dipentanoyloxymethylbenzene, m-dipentanoyloxymethylbenzene, p-dipentanoyloxymethylbenzene, o-di (meth) acryloyl Roxymethylbenzene,
m-di (meth) acryloyloxymethylbenzene, p-
Di (meth) acryloyloxymethylbenzene, o-di (meth) allyloyloxymethylbenzene, m-di (meth) allyloyloxymethylbenzene, p-di (meth) allyloyloxymethylbenzene, 1,3- Diacetyloxymethylnaphthalene, 1,4-diacetyloxymethylnaphthalene, 1,5-diacetyloxymethylnaphthalene,
1,6-Diacetyloxymethylnaphthalene, 1,7-Diacetyloxymethylnaphthalene, 1,8-Diacetyloxymethylnaphthalene, 2,4-Diacetyloxymethylnaphthalene, 2,5-Diacetyloxymethylnaphthalene,
2,6-Diacetyloxymethylnaphthalene, 2,7-Diacetyloxymethylnaphthalene, 2,8-Diacetyloxymethylnaphthalene, 1,3-Dipropanoyloxymethylnaphthalene, 1,4-Dipropanoyloxymethyl Naphthalene, 1,5-dipropanoyloxymethylnaphthalene, 1,6-dipropanoyloxymethylnaphthalene,
1,7-dipropanoyloxymethylnaphthalene, 1,8
-Dipropanoyloxymethylnaphthalene, 2,4-dipropanoyloxymethylnaphthalene, 2,5-dipropanoyloxymethylnaphthalene, 2,6-dipropanoyloxymethylnaphthalene, 2,7-dipropanoyloxymethyl Naphthalene, 2,8-dipropanoyloxymethylnaphthalene.

1,3-dibutanoyloxymethylnaphthalene, 1,4-dibutanoyloxymethylnaphthalene, 1,
5-dibutanoyloxymethylnaphthalene, 1,6-dibutanoyloxymethylnaphthalene, 1,7-dibutanoyloxymethylnaphthalene, 1,8-dibutanoyloxymethylnaphthalene, 2,4-dibutanoyloxymethylnaphthalene, 2, 5-dibutanoyloxymethylnaphthalene,
2,6-dibutanoyloxymethylnaphthalene, 2,7-
Dibutanoyloxymethylnaphthalene, 2,8-dibutanoyloxymethylnaphthalene, 1,3-dipentanoyloxymethylnaphthalene, 1,4-dipentanoyloxymethylnaphthalene, 1,5-dipentanoyloxymethylnaphthalene, 1 , 6-dipentanoyloxymethylnaphthalene, 1,7-dipentanoyloxymethylnaphthalene,
1,8-dipentanoyloxymethylnaphthalene, 2,4
-Dipentanoyloxymethylnaphthalene, 2,5-dipentanoyloxymethylnaphthalene, 2,6-dipentanoyloxymethylnaphthalene, 2,7-dipentanoyloxymethylnaphthalene, 2,8-dipentanoyloxymethyl Naphthalene, 1,3-di (meth) acryloyloxymethylnaphthalene, 1,4-di (meth) acryloyloxymethylnaphthalene, 1,5-di (meth) acryloyloxymethylnaphthalene, 1,6-di ( (Meth) acryloyloxymethylnaphthalene, 1,7-di (meth) acryloyloxymethylnaphthalene, 1,8-di (meth) acrylonyloxymethylnaphthalene, 2,4-di (meth) acryloyloxymethylnaphthalene 2,5-di (meth) acryloyloxymethylnaphthalene, 2,6-di (meth)
Acryloyloxymethylnaphthalene, 2,7-di (meth) acryloyloxymethylnaphthalene, 2,8-di (meth) acryloyloxymethylnaphthalene.

1,3-di (meth) allyloyloxymethylnaphthalene, 1,4-di (meth) allyloyloxymethylnaphthalene, 1,5-di (meth) allyloyloxymethylnaphthalene, 1,6-di (Meth) allyloyloxymethylnaphthalene, 1,7-di (meth) allyloyloxymethylnaphthalene, 1,8-di (meth) allylonyloxymethylnaphthalene, 2,4-di (meth) allyloyloxymethyl Naphthalene, 2,5-di (meth) allyloyloxymethylnaphthalene, 2,6-di (meth) allyloyloxymethylnaphthalene, 2,7-di (meth) allyloyloxymethylnaphthalene, 2,8-di ( (Meth) allyloyloxymethylnaphthalene, 2,2'-diacetyloxymethylbiphenyl, 2,3'-diacetyloxymethylbiphenyl,
2,4'-Diacetyloxymethylbiphenyl, 3,3 '
-Diaceteroxymethylbiphenyl, 3,4'-diacetyloxymethylbiphenyl, 4,4'-diacetyloxymethylbiphenyl, 2,2'-dipropanoyloxymethylbiphenyl, 2,3'-dipropanoyloxy Methylbiphenyl, 2,4'-dipropanoyloxymethylbiphenyl, 3,3'-dipropanoyloxymethylbiphenyl, 3,4'-dipropanoyloxymethylbiphenyl,
4,4'-dipropanoyloxymethylbiphenyl, 2,
2'-dibutanoyloxymethylbiphenyl, 2,3'-
Dibutanoyloxymethylbiphenyl, 2,4'-dibutanoyloxymethylbiphenyl, 3,3'-dibutanoyloxymethylbiphenyl, 3,4'-dibutanoyloxymethylbiphenyl, 4,4'-dibutanoyloxymethylbiphenyl, 2,2'-dipentanoyloxymethylbiphenyl, 2,3'-dipentanoyloxymethylbiphenyl, 2,4'-dipentanoyloxymethylbiphenyl,
3,3'-dipentanoyloxymethylbiphenyl, 3,
4'-dipentanoyloxymethylbiphenyl, 4,4 '
-Dipentanoyloxymethylbiphenyl, 2,2'-di (meth) acryloyloxymethylbiphenyl, 2,3 '
-Di (meth) acryloyloxymethyl biphenyl, 2,
4'-di (meth) acryloyloxymethylbiphenyl,
3,3'-di (meth) acryloyloxymethylbiphenyl, 3,4'-di (meth) acryloyloxymethylbiphenyl, 4,4'-di (meth) acryloyloxymethylbiphenyl, 2,2'- Di (meth) allyloyloxymethylbiphenyl, 2,3'-di (meth) allyloyloxymethylbiphenyl, 2,4'-di (meth) allyloyloxymethylbiphenyl, 3,3'-di (meth) ari Examples thereof include, but are not limited to, leuroxymethylbiphenyl, 3,4′-di (meth) allyloyloxymethylbiphenyl, and 4,4′-di (meth) allyloyloxymethylbiphenyl. The compound preferably used in the present invention is a diacetyloxymethylated product.

As the reaction sequence of the above-mentioned reaction raw materials, phenols and the compound represented by the general formula (1) before the reaction start,
And a compound represented by the general formula (2) in advance, and before the reaction between the phenol and the compound represented by the general formula (2) is completed, the compound represented by the general formula (1) is added. It is preferable to react, for example, phenols and a compound represented by the general formula (1) and a compound represented by the general formula (2) are reacted at the same time, or at the first stage, phenols and the above general formula After reacting with the compound represented by the formula (1), it is preferable to further react with the compound represented by the general formula (2) in the second step. This allows
The flame retardancy can be more reliably improved, and the composition can be suitably applied to molding materials such as electronic materials, adhesives, paints, and the like. More preferably, the phenols and the compound represented by the general formula (1) are reacted in the first step, and then the compound represented by the general formula (2) is further reacted in the second step. The polyhydric phenol thus produced is one of the preferred forms of the present invention.

The compounding molar ratio of the compound represented by the above general formula (1) and the compound represented by the above general formula (2) used in the production of the polyhydric phenol in the present invention is as follows: The ratio of the compound represented by the general formula (1) to the compound represented by 2) (the compound represented by the general formula (1) / the compound represented by the general formula (2)) is, for example, 10 / It is preferably 90 or more, and 9
It is preferably 0/10 or less. When the amount of the compound represented by the general formula (1) is less than 10/90, it is considered that the molding material such as an electronic material, the adhesive, the paint and the like have sufficient basic performance such as physical properties and heat resistance and flame retardancy. May not occur. When the amount of the compound represented by the general formula (1) is more than 90/10, physical properties and flame retardancy may not be sufficiently compatible with each other. More preferably, 30 /
It is 70 or more and 70/30 or less.

The compounding molar ratio of the phenols used in the production of the polyhydric phenol of the present invention and the compound represented by the general formula (1) is as follows. The ratio (phenols / compound represented by the general formula (1)) is, for example, preferably 1/1 or more, and more preferably 10/1 or less. If the amount of phenols is less than 1/1, gelation may occur during the production of polyhydric phenols.
If the amount of phenols is more than 1/1, the polyhydric phenol may be hard to cure. More preferably, since the polyhydric phenol can exhibit high strength at high temperature, it is 1.3 / 1 or more, further preferably 2
/ 1 or more. Further, it is more preferably 8/1 or less, and further preferably 5/1 or less.

The polyhydric phenol in the present invention preferably has a nitrogen atom content of 1% by mass or more.
It is preferably 50% by mass or less. If it is less than 1% by mass, flame retardancy may not be sufficient in molding materials such as electronic materials, adhesives, paints, etc.
When the content is more than mass%, the physical properties and the flame retardancy may not be sufficiently compatible with each other. It is more preferably 3% by mass or more and 30% by mass or less, further preferably 5% by mass or more and 20% by mass or less. The nitrogen atom content is the mass ratio of nitrogen atoms constituting the polyhydric phenol when the polyhydric phenol is 100% by mass.

The polyhydric phenol in the present invention is preferably obtained by reacting the above reaction raw materials in the presence of a catalyst. The catalyst that can be used for producing the polyhydric phenol is not particularly limited as long as it can react the above-mentioned reaction raw materials, and for example, it is preferable to use an ion exchange resin.

The ion exchange resin is not particularly limited, but is preferably a strongly acidic cation exchange resin. The strongly acidic cation exchange resin means an acidic cation exchange resin having a stronger acidity than the carboxylic acid type ion exchange resin, and examples thereof include sulfonic acid type ion exchange resin and perfluoroalkanesulfonic acid type ion exchange resin. Can be mentioned. These may be used alone or in combination of two or more. The amount of the ion exchange resin used when producing the polyhydric phenol in the present invention is not particularly limited, and is represented by, for example, phenols, compounds represented by the general formula (1) and general formula (2). When the total mass of the compound and the ion exchange resin is 100% by mass, it is preferably 0.01% by mass or more and 10% by mass or less. The content is more preferably 0.01% by mass or more, and further preferably 1% by mass or more.
Further, it is 8% by mass or less, and more preferably 5% by mass.
It is the following.

The above-mentioned polyhydric phenol includes the aromatic ring in phenols, the substituent represented by R ¹ in the compound represented by the general formula (1) and R ⁴ -in the compound represented by the general formula (2). It is obtained by condensation with a substituent represented by CH ₂ — (R ⁴ is the same as above), and at this time, a polycarboxylic acid, a carboxylic acid represented by R ⁴ H, an alcohol, and water. Will be a by-product. Thus by-produced carboxylic acid and alcohol, water is distilled off under reduced pressure during the reaction or after the reaction, or by performing an operation such as azeotroping with a solvent without requiring a complicated step. A polyhydric phenol that can be easily removed from the reaction product and is produced by removing by-produced carboxylic acid and the like from the reaction product is one of the preferred embodiments of the present invention. Incidentally, the reaction product means a mixture containing all those obtained by reacting as described above, for example, in addition to polyhydric phenol and by-produced carboxylic acid and alcohol, water, if necessary. It will include the catalyst used and the solvent described below.

In the reaction for producing the polyhydric phenol, the reaction conditions are not particularly limited, and for example, the reaction temperature is preferably a temperature at which the by-produced carboxylic acid and the like are volatilized and distilled off. For example, 100 to 2
The temperature is preferably 40 ° C. More preferably 110
To 180 ° C, and more preferably 130 to 160 ° C.
Is. As described above, in the production of the polyhydric phenol in the present invention, the carboxylic acid represented by R ⁴ H and the like are by-produced, but it can be easily removed from the reaction product. The reaction time depends on the raw materials used, the type and amount of the catalyst, the reaction temperature, and the like, but the reaction time includes phenols, a compound represented by the general formula (1) and a compound represented by the general formula (2). The reaction is preferably completed until the reaction is completed, that is, carboxylic acid, alcohol or water is not generated, and for example, 30 minutes to 24 hours is preferable. More preferably, it is 1 to 12 hours.

As a reaction method for producing the above-mentioned polyhydric phenol, for example, the reaction can be carried out without a solvent, but the reaction may be carried out using a solvent. In this case, as the solvent to be used, it is preferable to use an organic solvent inert to the reaction between the phenol and the compound represented by the general formula (1) and the compound represented by the general formula (2). Toluene, xylene, monochlorobenzene, dichlorobenzene and the like can be used. By using the solvent, the raw materials can be dissolved in the solvent to be homogenized, and as described later, the ion exchange resin and the like can be easily removed from the reaction product by filtration.

When the carboxylic acid or solvent is removed from the reaction product in the production of the above-mentioned polyphenol, for example,
It is preferable to distill off by distilling at the above temperature under a reduced pressure of 0.1 to 10 kPa. At this time, since unreacted phenols may be distilled off, it is preferable to carry out the reaction after the reaction is substantially completed.

When the ion exchange resin is used in the production, the polyhydric phenol is preferably produced by collecting the ion exchange resin from the reaction product by filtration. In the production of polyhydric phenol, it is preferable to use an ion exchange resin as a catalyst, but since the ion exchange resin is a solid catalyst,
The reaction product can be easily removed from the reaction product by filtering. That is, since the ion exchange resin is generally a granular copolymer of 10 to 100 mesh having a fine three-dimensional cross-linking structure and is insoluble in a solvent, it can be easily obtained by going through a filtration process using a filter having a pore size smaller than the particle size. Can be collected. As described above, when the ion exchange resin is used in the production of polyhydric phenol, the catalyst can be removed from the reaction product without performing industrially complicated steps such as a water washing step and a vacuum drying step. Also,
The ion exchange resin can collect ions in any solution regardless of the polarity of the solvent and can selectively remove various ion components eluted in the reaction system. Therefore, the ion-exchange resin, which is a catalyst, can be removed from the reaction product to produce an impurity-free polyhydric phenol. Furthermore, since the ion-exchange resin that is the catalyst is regenerable, it can be used multiple times in the production by recovering and regenerating the catalyst after the reaction. Therefore, it is also possible to recycle it after use and recovery and use it for manufacturing a plurality of times.

In the polyphenol, the compound represented by the general formula (2) used as a raw material is oxygen, palladium, ultrafine gold particles, and Periodic Table IIA.
Of a benzyl compound and a carboxylic acid in the presence of an oxidation reaction catalyst containing at least one element selected from the group consisting of group IIIA, group VIA, group VIA, group IIB, group VB, group VIII, and an alkali metal It is preferably a compound produced by the reaction. This gives the general formula (2)
The compound represented by can be industrially, efficiently and inexpensively produced, and the process in producing the polyhydric phenol can be a more industrially efficient process. A method for preparing the oxidation reaction catalyst,
The reaction method of the above-mentioned oxidation reaction is not particularly limited, and for example, it can be carried out in the same manner as the method described in JP-A-2000-70718. Further, the catalyst component for oxidation reaction is preferably supported on a carrier. This makes it possible to suppress the elution of the metal component, which is the catalyst component, into the reaction product, and to use the compound in which the content of impurities is suppressed for the production of polyhydric phenol.

Specific examples of the benzyl compound include alkylbenzene such as toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, sec-butylbenzene and trimethylbenzene; xylene and ethyltoluene. , N
-Propyltoluene, isopropyltoluene, n-butyltoluene, sec-butyltoluene, o-, m
-, P-dialkylbenzene; aryl-substituted alkylbenzene such as 4,4'-dimethylbiphenyl; o-, m-, p-hydroxy-substituted alkylbenzene such as cresol; o-, m-, p-halogen such as chlorotoluene Substituted alkylbenzene; Nitro group-substituted alkylbenzene such as o-, m-, p-nitrotoluene; O-, m-, p-amino group-substituted alkylbenzene such as methylaniline;
O-, m-, p-amide group-substituted alkylbenzenes such as methylbenzamide; o-, m such as methylanisole
-, P-alkyloxy-substituted alkylbenzene; o-, m-, p-aryloxy-substituted alkylbenzene such as phenoxytoluene; o-, m such as tolyl acetate, tolyl propionate, tolyl butanoate, tolyl benzoate, etc.
-, P-carboxy substituted alkylbenzene (carboxylic acid tolyl ester); o-, m-, p-carbonyl substituted alkylbenzene such as methylacetophenone and methylbenzophenone; o-, such as methylbenzyl acetate
m-, p-carboxyalkyl-substituted alkylbenzene;
Etc. Of the above-exemplified benzyl compounds, alkylbenzene, dialkylbenzene, and carboxyalkyl-substituted alkylbenzene are more preferable, and o
-, M-, p-xylene and o-, m-, p-methylbenzyl acetate are particularly preferred.

The above-mentioned carboxylic acid is a compound having a carboxyl group. More specifically, as the carboxylic acid, a monocarboxylic acid is preferable, and specifically, for example, acetic acid, propionic acid, butanoic acid, etc. Examples thereof include aliphatic carboxylic acids; aromatic carboxylic acids such as benzoic acid; however, they are not particularly limited. Among the carboxylic acids exemplified above,
Acetic acid and propionic acid are more preferable, and acetic acid is particularly preferable.

The flame-retardant resin composition of the present invention preferably further comprises a typical element oxide (D). As a result, flame retardancy is further improved. As the typical element oxide, for example, silica, tin oxide and the like are preferably used, and one kind or two or more kinds can be used.

Since the flame-retardant resin composition of the present invention contains the above-mentioned polyhydric phenol (B), it has excellent flame-retardant properties without using a compound having a halogen atom, a phosphorus compound or an antimony compound as a flame retardant. However, known flame retardants that are commonly used can be appropriately used in combination. Such a flame retardant is not particularly limited as long as it exhibits a flame retardant effect, for example, a phosphorus-containing compound,
Fluorine compounds, silicon compounds, antimony compounds, nitrogen compounds, sulfur compounds, boron compounds, thermally expansive graphite, metal oxides other than the typical element oxide (D), metal hydroxides, alkali (earth) metal salts, poly Examples include nucleus-substituted hydroxystyrene and alcohol compounds. These may be used alone or in combination of two or more. Among these, it is preferable to use one that does not contain a halogen atom because a gas harmful to the environment may be generated during combustion.

In the flame-retardant resin composition of the present invention, if necessary, a filler, a fiber reinforcing material, a solvent, a pigment, a colorant, a flameproofing agent, an antifoaming agent, a wetting agent, a dispersing agent, a rust preventive agent. , Antistatic agents, surface treatment agents, release agents, elastomers, lubricants, plasticizers, UV absorbers, light stabilizers, antioxidants, heat stabilizers, anti-aging agents, anti-drip agents, etc. it can. Further, an impact strength improver, a compatibilizing component, etc. for improving the properties of the flame-retardant resin composition can be blended. The amount of these additives is not particularly limited and may be appropriately set according to the intended use, desired performance, etc., but the total amount of these additives added should be 100 parts by weight of the thermoplastic resin (A). For example, it is preferably 0.01 part by weight or more, and preferably 50 parts by weight or less. The amount is more preferably 0.1 part by weight or more, and further preferably 0.5 part by weight or more. Also, more preferably,
It is 30 parts by weight or less, and more preferably 20 parts by weight or less.

The method for producing the flame-retardant resin composition of the present invention is not particularly limited, and the essential components are thermoplastic resin (A), polyhydric phenols (B) and polyhydric phenol crosslinking agent (C). ) And other components added as necessary can be performed. The mixing method is not particularly limited as long as it can uniformly mix these, and for example, mixing by a mixing machine such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, a heating roll, kneading, etc. are applied. be able to.

The flame-retardant resin composition of the present invention may also be a powder mixture or a melt mixture. The method for forming a molded article using the flame-retardant resin composition of the present invention is not particularly limited, and for example, (1) each component is mixed and kneaded and extruded with a uniaxial or biaxial extruder to form pellets. And (2) once preparing pellets (masterbatch) having different compositions, mixing (diluting) the pellets in a predetermined amount, and subjecting to molding to obtain a molded article having a predetermined composition. (3) A method of directly charging one or two or more of each component into a molding machine can be applied. Further, in the preparation of the composition used for the molded product, when a part or all of the thermoplastic resin powder and other components (flame retardant, etc.) are mixed and melt-kneaded, the dispersibility of the other components is improved. It is advantageous to improve.

The molding conditions for the flame-retardant resin composition of the present invention are not particularly limited. For example, the molding temperature is preferably 80 ° C. or higher, and preferably 300 ° C. or lower. More preferably, it is 120 ° C. or higher and 250 ° C. or lower.

The flame-retardant resin composition of the present invention is capable of eliminating the influence on the environment and the human body, and is excellent in mechanical properties, moldability and thermal characteristics, and is also a cured product excellent in flame retardancy. And can be suitably used, for example, as a molding material for home appliances, casings of IT equipment, car engine covers, interior materials, and the like.

The present invention also comprises reacting an epoxy resin (E) with a phenol, a compound represented by the general formula (1) and a reaction raw material containing the compound represented by the general formula (2) as an essential component. It is also an epoxy resin composition containing the polyphenol (F) thus obtained and a thermoplastic resin (G) as essential components.

The epoxy resin composition of the present invention contains the epoxy resin (E), phenols, the compound represented by the general formula (1) and the compound represented by the general formula (2) as essential components. The polyhydric phenol (F) obtained by reacting the reaction raw materials and the thermoplastic resin (G) are essential components. These may be used alone or in combination of two or more. The blending ratio of the essential components in the epoxy resin composition may be appropriately set depending on the performance required for the epoxy resin composition, the use, etc., but for example, the total mass of the essential components with respect to 100% by mass of the epoxy resin composition is 20. It is preferable that the content be at least mass%. More preferably, it is 35 mass% or more.

The above-mentioned epoxy resin (E) is not particularly limited as long as it is a compound having at least one epoxy group, and for example, bisphenols such as bisphenol A, bisphenol F and bisphenol S and epihalohydrin. Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of: phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, naphthol, hydroquinone and other phenols and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde Polyphenols obtained by condensation reaction of benzene, dicyclopentadiene, terpenes, coumarin, paraxylylene dimethyl ether, dichloroparaxylene, etc. , A novolak aralkyl type glycidyl ether type epoxy resin obtained by further condensation reaction with epihalohydrin; glycidyl ether type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; hydrogenation Examples thereof include a glycidyl ether type epoxy resin obtained by a condensation reaction of bisphenol or glycols with epihalohydrin; and an amine-containing glycidyl ether type epoxy resin obtained by a condensation reaction of hindertoin or cyanuric acid with epihalohydrin.
Further, it may be a compound having an epoxy group in the molecule by an addition reaction of these epoxy resins with polybasic acids and / or bisphenols.

In the epoxy resin composition of the present invention,
The compounding mass ratio of the epoxy resin (E) to the polyhydric phenol (F) is preferably 30/70 or more, and more preferably 70/30 or less. When the compounding mass ratio of the epoxy resin (E) to the polyhydric phenol (F) is less than 30/70, the mechanical properties of the cured product formed from the epoxy resin composition may be deteriorated, and the ratio of 70/30 is If it exceeds, flame retardancy may be insufficient. It is more preferably 40/60 or more, and 60/40 or less.

The polyhydric phenol (F) used in the present invention is the same as the polyhydric phenol (B), and the thermoplastic resin (G) is the same as the thermoplastic resin (A). A preferred form of the thermoplastic resin (G) in the present invention is an aromatic thermoplastic resin, which further improves the flame retardancy and electrical characteristics of the epoxy resin composition. The aromatic thermoplastic resin is the same as the above thermoplastic resin (A).

In the epoxy resin composition of the present invention,
The blending mass ratio of the thermoplastic resin (G) to the polyhydric phenol (F) is preferably 5/95 or more, and preferably 95/5 or less. If the blending mass ratio of the thermoplastic resin (G) to the polyhydric phenol (F) is less than 5/95, the mechanical properties and the like of the molded product formed from the resin composition may be deteriorated. If it exceeds, flame retardancy may be insufficient. It is more preferably 10/90 or more, and 90/10 or less.

The epoxy resin composition of the present invention preferably further contains a typical element oxide (H). As a result, flame retardancy is further improved. The typical element oxide is the same as the typical element oxide (D) described above.

The epoxy resin composition of the present invention also preferably contains a curing accelerator for epoxy resin in order to smoothly carry out the curing reaction. As the curing accelerator for epoxy resin, any publicly known and commonly used epoxy resin can be used, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like. Imidazoles; benzyldimethylamine; 2,4,6-tris (dimethylaminomethyl)
Phenol; 1,4-diazabicyclo [2.2.2. ]
Octane; 1,8-diazabicyclo [5.4.0. ]-
Examples include tertiary amines such as 7-undecene; phosphines such as triphenylphosphine; quaternary ammonium salts such as tetrabutylammonium bromide and benzyltriethylammonium bromide; and phosphonium salts such as tetraphenylammonium bromide. The mixing amount of the curing accelerator for the epoxy resin is preferably 0.01% by mass or more and is preferably 10.00% by mass or less based on the total mass of the polyhydric phenol and the epoxy resin. . If it is out of this range, there is a possibility that a good curing acceleration effect cannot be obtained. More preferably,
It is 0.1% by mass or more and 5% by mass or less.

The epoxy resin composition of the present invention may contain other components such as known flame retardants, if necessary, as long as the effects of the present invention are exhibited. As the other component, one kind or two or more kinds such as those described above can be used.

The method for producing the epoxy resin composition of the present invention is not particularly limited, and the epoxy resin (E), the polyhydric phenol (F) and the thermoplastic resin (G), which are essential components, and if necessary, It can be performed by mixing with other components to be added. The mixing method is not particularly limited as long as it can uniformly mix these,
For example, the same method as that for the flame-retardant resin composition described above can be applied.

The epoxy resin composition of the present invention may also be a powder mixture or a melt mixture. The method for forming a molded article using the epoxy resin composition of the present invention is not particularly limited, and, for example, the same method as for the flame-retardant resin composition can be applied. Further, a method of mixing a fiber reinforcing material or the like with an epoxy resin composition to form a paste-like composition, forming a predetermined shape or pattern from this composition, and heating and curing, and impregnating the fiber reinforcing material with the epoxy resin composition. A method of heating and pressing into a prepreg can also be suitably applied.

The molding conditions for the epoxy resin composition of the present invention are not particularly limited. For example, the molding temperature is preferably 80 ° C. or higher, and preferably 300 ° C. or lower. More preferably, it is 120 ° C. or higher,
Moreover, it is 250 degrees C or less.

The epoxy resin composition of the present invention is capable of eliminating the effects on the environment and the human body, has high flame retardancy and high compatibility, and does not use an elastomer component at all. It can be toughened and has excellent heat resistance, mechanical properties, and electrical characteristics. For example, it can be suitably used as an electric insulating material for forming a printed wiring board or the like. . A printed wiring board using the epoxy resin composition of the present invention is one of the preferred embodiments of the present invention.

[0064]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is
It means "parts by weight".

Synthesis Example 1 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Benzoguanamine 65.52 g 37% Formaldehyde 56.81 g Phenol 329.39 g Methanol 25 ml p-Diacetyloxymethylbenzene 77.78 g After adjusting the pH of the mixture in the system to 5 or less with oxalic acid, under nitrogen gas flow. The temperature was raised to 120 ° C. with stirring. Over a period of 3 hours, 12.6 ml of produced water and methanol were collected by the Dean Stark trap. Further, 7.3 g of a strongly acidic ion exchange resin Amberlyst15 Dry (trade name, manufactured by Room & Haas) was charged into the system, and the temperature was raised to 150 ° C. while stirring under a nitrogen gas flow, and 9 g of acetic acid produced over 6 hours. Was captured by the Dean Stark Trap. After cooling to room temperature, the ion-exchange resin was removed from the mixture in the reactor by filtration, and phenol was removed from the product using an evaporator. 21
0 g of reddish brown solid polyhydric phenol A was obtained at room temperature. The heat softening temperature was 62 ° C. and the number average molecular weight was 330.

Synthesis Example 2 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Melamine 15.76 g 37% Formaldehyde 20.29 g Phenol 47.1 g Methanol 33 ml 1,4-Dihydroxymethylbenzene 17.27 g After adjusting the pH of the mixture in the system to 8 or more with triethylamine, under nitrogen gas flow The temperature was raised to 80 ° C. with stirring. Strongly acidic ion exchange resin Amber
2.3 g of lyst15 Dry (trade name, manufactured by Room & Haas) was charged into the system, and 150 under nitrogen gas flow.
The temperature was raised to 0 ° C. with stirring, and 20 g of water was collected by a Dean Stark trap over 8 hours. After cooling to room temperature, the ion-exchange resin was removed from the mixture in the reactor by filtration, and phenol was removed from the product using an evaporator. 65 g of reddish brown solid polyphenol B was obtained at room temperature. The heat softening temperature was 121 ° C. and the number average molecular weight was 540.

Synthesis Example 3 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Benzoguanamine 14.04 g 37% Formaldehyde 12.17 g Phenol 28.23 g Methanol 25 ml 1,1'-Diacetyloxymethylbiphenyl 22.3
The pH of the mixture in the system was adjusted to 7 or higher with 7 g of triethylamine, and then the temperature was raised to 120 ° C. with stirring under a nitrogen gas flow. Produced water 10.4 over 3 hours
ml and methanol were collected with a Dean Stark trap. Strongly acidic ion exchange resin Amberlyst 15
Dry (product name, Room & Haas) 1.5g
Was charged into the system, the temperature was raised to 150 ° C. under nitrogen gas flow with stirring, and 9 g of acetic acid produced was collected by a Dean-Stark trap over 6 hours. After cooling to room temperature, the ion-exchange resin was removed from the mixture in the reactor by filtration, and phenol was removed from the product using an evaporator. 50 g of reddish brown polyphenol C which is solid at room temperature
was gotten. Thermal softening temperature is 125 ° C, number average molecular weight is 7
It was 20.

Synthesis Example 4 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Benzoguanamine 14.04 g 37% Formaldehyde 12.17 g Phenol 28.23 g Methanol 25 ml 2,6-Diacetyloxymethylnaphthalene 20.42
g The pH of the mixture in the system was adjusted to 8 or higher with triethylamine, and then the temperature was raised to 120 ° C. with stirring under a nitrogen gas flow. 10.4 ml of produced water over 3 hours
And methanol were collected in the Dean Stark trap.
Strongly acidic ion exchange resin Amberlyst 15 D
1.5 g of ry (trade name, manufactured by Room & Haas) was charged into the system, the temperature was raised to 150 ° C. with stirring under a nitrogen gas flow, and 9 g of acetic acid produced was collected by a Dean Stark trap over 6 hours. did. After cooling to room temperature, the ion exchange resin was removed from the mixture in the reactor by filtration,
Phenol was removed from the product using an evaporator. 50 g of reddish brown solid polyphenol D was obtained at room temperature. Thermal softening temperature is 130 ° C, number average molecular weight is 68
It was 0.

Synthesis Example 5 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Phenol 47.06 g p-Diacetyloxymethylbenzene 55.56 g Strongly acidic ion exchange resin Amberlyst15 Dry
(Trade name, manufactured by Room & Haas) 2.2 g While stirring, the temperature was raised to 150 ° C. under a nitrogen gas flow, and 6
Over a period of time, 30 g of the produced acetic acid was collected by the Dean Stark trap. After cooling to room temperature, the ion-exchange resin was removed from the mixture in the reactor by filtration, and phenol was removed from the product using an evaporator. 65 g of red-brown solid polyphenol P at room temperature was obtained. The heat softening temperature was 72 ° C. and the number average molecular weight was 515.

Synthesis Example 6 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Ethylene glycol 35.64 g Tris (hydroxyethyl) isocyanurate 86.
86 g terephthalic acid 53.99 g 4,4'-oxydianiline 65.07 g trimellitic anhydride 124.89 g The temperature was raised to 100 ° C. under nitrogen gas flow, and stirring was started when the raw material became fluid. The temperature was raised to 230 ° C., and 35 g of the produced water was collected by the Dean Stark trap over 24 hours. A polyesterimide resin (thermoplastic resin A) was obtained by washing the product with a mixed solution of methanol / hexane. The yield was 300 g, and the intrinsic viscosity of the thermoplastic resin A was 1.88 g / dL (in DMSO,
At a concentration of 0.2 g / dL), the glass transition temperature was 143 ° C.

Synthesis Example 7 The following compounds were placed in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Dimethyl terephthalate 194.2 g 1,4-butanediol 180.3 g Dibutyltin oxide 0.12 g The temperature was raised to 200 ° C. with stirring under normal pressure and nitrogen gas flow. 60 g of methanol was collected in a Dean-Stark trap over 6 hours. Further, the Dean-Stark trap was replaced with a cold trap, and the temperature was raised to 260 ° C. under reduced pressure of 150 Pa while stirring. 85 g of 1,4-butanediol was collected in a cold trap over 4 hours. A polybutylene terephthalate resin (thermoplastic resin B) was obtained by washing the product with a mixed solution of methanol / hexane. The yield is 230 g, the thermoplastic resin B has an intrinsic viscosity of 0.53 g / dL (concentration 0.2 g / dL in DMSO), a melting point of 225 ° C., and an HDT of 65 ° C.
was.

Synthesis Example 8 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. Bisphenol A 228.3 g Triphosgene 98.9 g Methylene chloride 500 mL While stirring at 40 ° C. under normal pressure and nitrogen gas flow, 40.0 g of sodium hydroxide was added in 12 portions over 6 hours. After 4 hours, the mixture was cooled to room temperature, the solid content was removed by suction filtration, and further washed with water. The obtained purified liquid was dropped into hexane and collected by filtration to obtain a polycarbonate resin (thermoplastic resin C). The yield is 242 g, and the intrinsic viscosity of the thermoplastic resin C is 0.68 g / dL (DMSO
Medium, concentration 0.2g / dL), glass transition point 147 ℃
was.

Synthesis Example 9 The following compounds were charged in a four-necked flask equipped with a gas inlet, a Dean-Stark trap, a thermometer and a stirrer. 2,6-xylenol 244.3 g Copper (I) chloride 0.27 g N, N, N ', N'-tetramethylethylenediamine
0.45 g Toluene 500 mL At normal pressure, the temperature was raised to 65 ° C. with stirring, and then 50 ml /
Oxygen gas bubbling was started at a rate of minutes. After 12 hours, the purified solution obtained was dropped into hexane and collected by filtration to obtain a polyphenylene ether resin (thermoplastic resin D). Yield 220g, thermoplastic resin D
Has an intrinsic viscosity of 2.51 g / dL (in DMSO, a concentration of 0.
The glass transition point was 210 ° C. at 2 g / dL).

As the thermoplastic resin E and the epoxy resins A to C, those described below were used. Thermoplastic resin E: ABS resin "GR-GT-14" (manufactured by Denki Kagaku Kogyo Co., Ltd.) Epoxy resin A: Bisphenol F type epoxy resin "Epototo YDF-170" (manufactured by Toto Kasei Co.) Epoxy resin B: Cresol novolac type epoxy Resin "Sumiepoxy ESCN195X" (Sumitomo Chemical Co., Ltd.) Epoxy resin C: Biphenyl type epoxy resin "Epicoat YX-4000" (Japan Epoxy Resin Co., Ltd.)

In Examples 1 to 14 and Comparative Examples 1 to 6, polyphenols A to E, thermoplastic resins A to E, and epoxy resins A to C were added at the respective compounding ratios shown in Tables 1 and 2 to Henschel. After mixing with mixer, 15mmφ, L / D = 4
0 twin screw extruder (KZW15-40M manufactured by Techno Bell Co.)
G) was used, melt-kneaded and extruded at 220 to 270 ° C., and pelletized by a pelletizer. Further, a test piece was produced using an injection molding machine.

For Examples 15 to 23 and Comparative Examples 7 to 8, polyhydric phenols A to E, thermoplastics A to E and epoxy resins A to C were mixed at the compounding ratios shown in Table 3, and then the mixture 100 was added. After adding 2 parts of triphenylphosphine to 1 part, kneading at 110 ° C. using a three-roll mill, 9.8 ×
Press molding was performed at 10 ² kPa and 180 ° C. for 1 hour.

The flame retardancy is determined by the method according to UL-94.
Oxygen index is an oxygen index measurement tester (manufactured by Toyo Seiki Seisakusho)
Respectively investigated by. Further, for Examples 15 to 23 and Comparative Examples 7 to 8, fracture toughness values were determined by the following method. The results are shown in Tables 1 to 3.

[Fracture Toughness Value] A sample of a cured product having a size shown in FIG. 1 was prepared, and a starter crack was formed by a razor at the tip of the central notch. The cutout length is 2m
m, the width is 1 mm, the length of the starter crack is 2 mm, so that a is 4 mm. For this sample,
Load (Load) when a downward load (Load P) is applied to the center of the sample at a speed of 10 mm / min-
The time (Time) curve (FIG. 2) was obtained, and the fracture toughness value (MPa · m ^1/2 ) was calculated from the load (Pc) at the time of fracture, the crack length (a), etc. by the following formula.

[0079]

[Formula 1]

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

Tables 1 to 3 will be described. HDT is a heat distortion temperature measured according to JIS K7207. Kic is the fracture toughness value (unit: MPa · m
^1/2 ).

[0084]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention, having the above-mentioned constitution, is capable of eliminating the influence on the environment and the human body and is excellent in mechanical properties, moldability and thermal characteristics. Moreover, it is possible to give a cured product having excellent flame retardancy, and it can be suitably used as a molding material for home appliances, IT equipment casings, car engine covers, interior materials and the like. Further, the epoxy resin composition of the present invention,
Because of the above-mentioned constitution, it is possible to eliminate the influence on the environment and the human body, and at the same time, it has high compatibility, and is toughened without using any elastomer component, and has heat resistance,
Since a cured product having excellent mechanical properties, moldability, and electrical properties can be provided, it can be suitably used as an electrical insulating material for forming a printed wiring board or the like.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a cured test piece for measuring a fracture toughness value.

FIG. 2 is a load-time curve when a fracture toughness value is measured.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 C H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4J002 BB01W BC03W BG03W CB00W CC03X CC18X CD04Y CD05Y CD06Y CF03W CG01W CH07W CH09W CJ00W CK02W CL00W CM04W CN01W CN03W DE096 DJ016 FD12X FD136 GJ01 GQ00 GQ01 JAQ06 JA08060813 FB05 FA03 FB05 FA03 A08 AJ AB06 A11 A01 A01 AB01 JA15 4M109 AA01 CA21 EA12 EB07

Claims (6)

[Claims] 1. A thermoplastic resin (A), a phenol,
The following general formula (1): (In the formula, R ¹ is the same or different and represents an amino group, a methylolamino group or a dimethylolamino group.
² represents a hydrocarbon group having 1 to 12 carbon atoms. ) And a compound represented by the following general formula (2); (In the formula, R ³ represents a phenylene group, an alkyl-substituted phenylene group, a naphthalene group, an alkyl-substituted naphthalene group, a biphenyl group or an alkyl-substituted biphenyl group.
⁴ are the same or different and represent a hydroxyl group, an alkyl ether group having 1 to 4 carbon atoms or an alkyl ester group having 1 to 4 carbon atoms. ) A polyhydric phenol (B) obtained by reacting a reaction raw material containing a compound represented by
And a cross-linking agent for polyhydric phenol (C) as essential components, a flame-retardant resin composition. 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is an aromatic thermoplastic resin. 3. The flame-retardant resin composition according to claim 1, further comprising a typical element oxide (D). 4. An epoxy resin (E) and phenols,
The following general formula (1); (In the formula, R ¹ is the same or different and represents an amino group, a methylolamino group or a dimethylolamino group.
² represents a hydrocarbon group having 1 to 12 carbon atoms. ) And a compound represented by the following general formula (2); (In the formula, R ³ represents a phenylene group, an alkyl-substituted phenylene group, a naphthalene group, an alkyl-substituted naphthalene group, a biphenyl group or an alkyl-substituted biphenyl group.
⁴ are the same or different and represent a hydroxyl group, an alkyl ether group having 1 to 4 carbon atoms or an alkyl ester group having 1 to 4 carbon atoms. ) A polyhydric phenol (F) obtained by reacting a reaction raw material containing a compound represented by
And a thermoplastic resin (G) as essential components. 5. The epoxy resin composition according to claim 4, wherein the thermoplastic resin (G) is an aromatic thermoplastic resin. 6. The epoxy resin composition according to claim 4, further comprising a typical element oxide (H).