WO2002090439A1

WO2002090439A1 - Flame-retardant resin composition

Info

Publication number: WO2002090439A1
Application number: PCT/JP2002/004188
Authority: WO
Inventors: Kazunari Tamura; Katsuichi Otsuki; Hiroshi Tsuji; Takafumi Okawa
Original assignee: Daihachi Chemical Industry Co., Ltd.
Priority date: 2001-05-02
Filing date: 2002-04-25
Publication date: 2002-11-14

Abstract

A flame-retardant resin composition which comprises a thermoplastic resin or thermosetting resin containing no phenylene ether units and added thereto as a flame retardant a naphthyl phosphate compound represented by the general formula (I): (I) wherein n is 1 or 2; R represents C1-4 alkyl; and m is an integer of 0 to 3.

Description

Description Flame-retardant resin composition Technical field

The present invention relates to a flame retardant resin composition to which a naphthyl phosphate compound is added as a flame retardant. More specifically, the present invention imparts excellent flame retardancy and fluidity to a resin by adding a small amount thereof, has excellent hydrolysis resistance, does not reduce the inherent mechanical strength of the resin, and is formed with low volatility. The present invention relates to a flame-retardant resin composition to which a naphthyl phosphate compound, which does not occasionally contaminate a mold and does not impair the appearance of a molded article and is extremely useful as an inexpensive non-halogen flame retardant, is added. Background art

Known flame retardants for resins include inorganic flame retardants, organic halogen flame retardants, and organic phosphorus flame retardants. In order to obtain the desired flame retardancy with an inorganic flame retardant, it is necessary to add a large amount of the flame retardant, and there is a problem that the addition of such a large amount degrades the inherent properties of the resin. In addition, organic halogen-based flame retardants are excellent in flame retardancy, but they are thermally decomposed during resin molding and generate hydrogen halide, which is harmful to the human body when corroding molds or burning due to fire. There is a problem of generating a new gas. For these reasons, attention has been paid to organophosphorus flame retardants.

Japanese Patent Application Laid-Open No. 2001-72852 discloses monomer-type organophosphorus flame retardants such as trifeninolephosphate and tricresinolephosphate as flame retardants for resins. . These organophosphorus flame retardants have the effect of improving the fluidity during resin molding, but because of their low molecular weight, they volatilize during resin molding and contaminate the mold, impairing the appearance of molded products. There is a disadvantage that the work efficiency is lowered. These problems are described in Japanese Unexamined Patent Application Publication No. Hei 2-115262, which is a condensation type polymer (oligomer) such as resorcinobis (diphenolephosphate) and bisphenoleno-Abis (diphenylphosphate). The problem can be solved by using an organic phosphorus-based flame retardant. That is, these compounds can impart to the resin the same flame retardancy as the monomer type, and since they have a high molecular weight, the above-mentioned disadvantages due to volatilization of the monomer can be eliminated. However, these compounds are usually high-viscosity liquids, have low fluidity at the time of resin molding, are difficult to handle, and have the drawback of lowering production efficiency. After reducing the viscosity of the flame retardant using a heating device or a special pump, these compounds can be uniformly added to the resin, but the additional device as described above is required.

In addition, resorcin bis (diphenyl phosphate) has a disadvantage that it has poor hydrolysis resistance and lowers the durability of the resin molded product. In addition, bisphenol A bis (diphenyl phosphate) has a low phosphorus content in the molecule and needs to be added in a large amount in order to exhibit flame retardancy. Working environment for resin molding process (normal temperature) Resorcin bis (di-1,6-xylyl phosphate) has been proposed as an organophosphorus flame retardant that is solid, easy to handle, low volatile, and has excellent hydrolysis resistance. However, it is not suitable for general-purpose products due to its high cost.

Japanese Patent Application Laid-Open Nos. Hei 7-82464 and No. 2001-41072 disclose a method for reducing the contamination of a mold and improving the fluidity of a resin. A technique is described in which a combination of an organic phosphorus-based flame retardant with an oligomer type is used. By using two types of organic phosphorus-based flame retardants in this way, a resin composition having both the fluidity, which is the advantage of the monomer type, and the low volatility, which is the advantage of the oligomer type, can be obtained.

However, even with the above technique, the disadvantages of the two types of organophosphorous flame retardants are not completely eliminated. Japanese Unexamined Patent Publication (Kokai) No. 61-200163 discloses a low volatility as a flame retardant for a polyphenylene ether resin or a resin composition of a polyphenylene ether resin and a polystyrene resin. Naphthyl phosphate compounds have been described.

In general, it is known that polyphenylene ether resin (PPE) itself has considerably high flame retardancy. Such a PPE-based resin is unlikely to cause the adverse effects of adding a large amount of a flame retardant, for example, a problem such as a reduction in the mechanical strength inherent in the resin. Therefore, it is difficult to directly say that a naphthyl phosphate compound can be used as a flame retardant for resins other than PPE.

Japanese Patent Application Laid-Open No. 61-51545 discloses a flame retardant for a resin composition of a polycarbonate (PC) and an ABS resin, which may be an alkyl group which may be halogen-substituted or an aryl group. Phosphates having groups are described. However, the phosphate described in this publication is only described as an additive component, and there is no specific description about the naphthyl phosphate compound.

In Japanese Patent Application Laid-Open No. 52-110750, triaryl phosphate is described as a flame retardant for a resin, and tri (2-naphthyl) phosphate is exemplified. Due to the low rate, there is a problem with flame retardancy. Disclosure of the invention

An object of the present invention is to provide a resin with excellent flame retardancy and fluidity even with a small amount of added syrup, a low volatility and a monomer type non-hagogen-based flame retardant which does not cause mold contamination during molding. To provide a flame-retardant resin composition to which is added.

Thus, according to the present invention, a thermoplastic resin or a thermosetting resin containing no phenylene ether unit can be used as a flame retardant by the general formula (I):

(Wherein n is 1 or 2, R is an alkyl group, m is an integer of 0 to 3), and a flame-retardant resin composition obtained by adding a naphthyl phosphate compound represented by the following formula: Is provided. Embodiment of the Invention

The flame-retardant resin composition of the present invention is obtained by adding a naphthyl phosphate compound represented by the general formula (I) as a flame retardant to a thermoplastic resin or a thermosetting resin containing no phenylene ether unit. .

As the CiCa alkyl group for the substituent R in the general formula (I), a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, iso-propyl, iso-butyl / And branched alkyl groups such as sec-butyl and tert-butyl.

The naphthyl phosphate compound (I) used in the present invention is illustrated below, but the scope of the present invention is not limited by these compounds. 1-naphthinoresiphenyl phosphite,

Di (11-naphtinole) fenii / rephosphate,

2—Naphthinoresphene phosphate,

Di (2-naphthyl) feninole phosphate,

When a mixture of 1-naphthol and 2-naphthol is used as a raw material,

1-naphthinole 2-naphthinolephdinophosphate;

1-naphthynolevis (3-methinorefue phosphate,

1-Naphthino-levis (4-meth / lefeninole) phosphate,

2-naphthyl-bis (3-methynolephene) phosphate, 2-naphthyl-bis (4-methylphenyl) phosphate,

Di (1-naphthyl) -1,3-methylphenyl phosphate,

Di (1-naphthyl) -1-41-methylphenyl phosphate,

Di (2-naphthinole) _3-methylphenyl phosphate,

Di- (2-naphthyl / le) -1-4-methinolephenyl phosphate,

When using a mixture of 1-naphthol and 2-naphthol, or a mixture of 3-methyl / refenol and 4-methylphenol as raw materials,

1-Naphthyl / Lae 2-Naphthyl-1-3-Methynolephenyl Phosphate, 1-Naphthinole 2-Naphthinoleh 4-Methinolephene2-Norphlephosphate, 1-Naphthyl / Lae 3-Methylphenyl-1 4-Methylphenylphosphe 2-naphthinole 3-methynolephene 4-nor-methynolephenylphosphe;

1 naphthysole monobis (2, 6 _ dimethinorefuennole) phosphate,

1-naphthinolevis (2,4-dimethinolepheninole) phosphate, 1-naphthyl-bis (3,5-dimethylphenyl) phosphate,

2-naphthyl / levis (2,6-dimethynolephene / le) phosphate, 2-naphthyl-bis (2,4-dimethylphenyl) phosphate, 2-naphthinolebis (3,5-dimethylphenyl) phosphate, di (1 —Naphthyl ^^) 1,2,6-Dimethynolephenic phosphate, di (1-naphthinole) 1,2,4-dimethylphenylphosphate, di (1-naphthyl) -1,3,5-dimethinolephenyl phosphate, di (2— Naphthyl) 1,2,6-dimethylphenyl phosphate, di (2-naphthyl) 1,2,4-dimethylphenyl phosphate, di (2-naphthyl) 1,3,5-dimethylphenyl phosphate,

When a mixture of two or more selected from a mixture of 1-naphthol and 2-naphthol, 2,6-dimethylphenol, 2,4-dimethinolephenol and 3,5-dimethinophenol as raw materials Is, for example, 1-naphthyl-2-naphthyl-2,6-dimethylphenylphosphate, 2-naphthinole_2,4_dimethinolephenyl 2,6-dimethylphenyl phosphate; etc .;

1-naphthinolene 3-methynolephenynolate 2,6-dimethylphenylenolphosphone 1-naphthyl-4-methylphenyl_2,6-dimethylphenylphosphine ¹ to

1-naphthinole 3-methynolephene 2,2,4-dimethylphenyl phosphate,

1-naphthinole 4-methynorefie / le 2,4—dimethylphene / lephosphate,

1-naphthyl-3-methylphenyl-1,5,5-dimethylphenylphosphate ¹ to

1-naphthyl-1-4-methylphenyl-3,5-dimethylphenylenophosphate,

2-naphthyl-1,3-methylphenyl 2,6-dimethylphenylphosphate,

2-naphthinole 4- 4-methynolephene 2, 2, 6-dimethylpheninolephosphone

2-naphthyl-3-methylphenyl-1,4,4-dimethylphenylphosphate,

2-naphthyl 4-methylphenyl 2,4-dimethylphenylphosphate ¹ to

2-naphthinole-3-methylphenyl-1,3,5-dimethylphenylphosphate,

2-naphthyl-1-41-methylphenyl_3,5-dimethinolephenylphosphate;

1-naphthinolevis (4-ethynolephenyl) phosphate,

2-Naphthyno-levis (4-ethyl / rephenyl) phosphate, Di- (1-naphthyl) -41-ethylphenylphosphate,

Di (2-naphthyl) 1-4-ethylphenyl phosphate,

When a mixture of 11-naphthol and 2-naphthol is used as a raw material,

1-naphthyl _ 2-naphthyl / le 4- 4-ethynolepheninophosphate;

1-Naphtinole 3—Methinolephen 4 1—Ethynolephen 2norephosphenol, 1—Naphtinole 4—Methinolefeninole 1 4—Echinolepheninolephosphene 1 (1) 4-ethynolephen-2-olephosphate, 2-naphthinole-4-methinolefeninole-1, 4-ethynolephenynophenole;

1—Naphtinole 2, 6—Dimethinolephenone 4—Echinolelefeninolephosphate,

1—Naphtinole 2, 4—Dimethinolephenone 4—Echinolenoveninophosphate

1-naphthinole 3-, 5-dimethyl-phenyl-4--4-ethynolephenine-phosphate ^1- ",

2—Naphthyre 2,6_Dimethinolepheninole 1 4-ethynolephenineolephosphate,

2—Naphtinole 2, 4—Dimethinolephenone 4—Echinolelefeninolephosphate,

2-naphthinole-3,5-dimethylphenyl-4-ethylfureninolphosph ¹ to ¹ ;

1-naphthyl / levis (4-n-propyl phenyl) phosphate, 1-naphthino-levis (4-iso-propynolephenyl) phosphate, 2-naphthino-levis (4n-propyl-phenyl) phosphate, 2 _naphthino-levis (4-1-n) iso-propylphenyl phosphate, di (1-naphthyl / re) -141 n-propynolepheninolephosphate, di (1-naphthyl) -1-4-propylpropylphenyl, Di (2-naphthyl) -1-4-n-propynolefeninolephosphate, di. (2-naphthyl) -14-iso-propylphenylphosphate, a mixture of 1-naphthol and 2-naphthol, 4-n When using a mixture of propyl phenol and 4-iso-propyl phenol, for example,

1-naphthinole 21-naphthinole 4 _ n-propyfenolenophosphate, 2-naphthinole 41 η-propynolephate-nore 4-iso-propylephene norephosphate, etc .;

1-Naphthinole 3-Methylphenone 4-n-propynolefeninolephosphate,

1—Naphthinole 3—Methynolepheninole 4—iso—Propinolefeninolephos

1—Naphthinole 4—Methylefeninole 4—n—Propinole feninole phosphate ¹ to

1-naphthyl-1- 4-methylphenyl 4-iso-propylphenyl phosphate,

2-naphthinole 3-methinolephen 4-n-propinolefeninolephosph

2—Naphtinole 3—Methinolefeninole 4—iso—Propinolefeninolephosphate,

2—Naphthinole 4—Met ^ / Feninole 4 1 n—Propiphenylenolephosphate,

2-naphtinole 4-methinolefeninole 4-iso-propinolefeninolephos;

1-naphthyl-1,2,6-dimethylphenyl 4-n-propylphenyl phosphate,

1-naphthyl-1,2,6-dimethylphenyl-4-iso-propylphenolephosphoate, 1-naphthyl-1,2,4-dimethinolephenyl _ 4—n-propylphenyl phosphate,

1-naphthyl-2,4-dimethynolephenine 4—iso propyl phenol

1-naphthyl-3,5-dimethynolephenone 1 4-naphthylphenyl phosphate

1-naphthyl-3,5-dimethylphenol 4-iso-propylphenol phosphate,

2-naphthinole 2,6-dimethynolephenynole 4-n-propylphenyl phosphate,

2-naphthyl-1,2,6-dimethinolefeninoleate 41 iso-propinolefeninolephosphate,

2-naphthyl-1,2,4-dimethinolepheninole 4-n-propylpheninolephosphate,

2-naphthinolate 2, 4-dimethinorefheninole 41 iso-propylefene

2-naphthyl-3,5-dimethynolephen-2-ole_4—n-propylphenynole phosphate

2-Naphthinole 3, 5-Dimethinolefeninole 1 4-iso-propyle-zolephosphate;

1-naphthino-levis (4-n-butylphenyl) phosphate, 1-naphthino-lebis (4-iso-butynolephene) phosphate, 1-naphthyl-bis (4-tert-butylphenyl) phosphate,

2-naphthinolevis (4-n-butynolefetinole) phosphate, 2-naphthinolevis (4-iso-butynolefetinole) phosphate,

2-naphthinolebis (4-tert-butylphenyl) phosphate, di (1-naphthinole) 1-41n-buty ^ / pheninolephosphate, di (1-naphthinole) 141-iso-butynolepheninephosphate, Di (1-naphthinole) -14-tert-butylphenynophosphate, di (2-naphthyl / le) -14-n-petit / lephenylphosphate,

Di (2-naphthine / le) -1- 4-butynolephene / rephosphate, di (2-naphthine) -4-1-tert-butylphenylphosphate,

When a mixture of 1-naphthol and 2-naphthol, 4-n-butynolephenone, 4-iso-butynolephenone and 4-tert-butynenol is used as a raw material, for example, 1-naphthyl-21-naphthyl-4-tert-butylphenylphosphate, 21-naphthyl-4-n-butylphenyl-14-tert-butylphenylphosphate and the like;

1-naphthyl 3- 3-methynolephene / le 4-n-butylphenylphosphite

1—Naphthinole 4—Methynolephenine 4-n—Petit / Refeninolephosphate,

1—Naphthinole 3—Methynolephenone 4—iso—Butylphenylphosphate,

1—Naphtinolé 4—Methinolephene 2 / Leth 4—iso—butinolephenine phosphate

1-naphthyl-3-methylphenyl-4-tert-butylphenylphosphate,

1—Naphthinole 4—Methynolephenone 4—tert—Petit / Refeninolephosphate,

2-naphthinol 3- 3-methynolephenyl 4-n-butylphenylphosphate,

2-naphthinol 4- 4-methynolephene 2-z-n-butylphenylphosphate,

2-Naphthinole 3—Methynolephenone 4 4-iso-Butylphenylphosphate, 2-naphthinol 4- 4-methynolefenorin 41 iso-butynolefeninolephosphate,

2-Nafuchinore one 3-Mechinorefueniru one 4-tert- butyl Roh reflex Eni Norre phosphine E ¹ - "door,

2-naphthinole 4-methinolephenyl 4-tert-butylphenylenophosphate;

1—Naphtinolé 2, 6—Dimethynolephene 2 / Let 4—n—Buchinolefeninolefo,

1-naphtinole 2, 4-dimethinolefe / le 4-n-butynolefenislephate,

1—Naphtinole 3, 5—Dimethinolephen 2 _ 4—n—Buchinorefeni / Lejo sulfate,

1-naphthyl 1,2,6-dimethylphenyl 4-iso-butylphenyl phosphite,

1-naphthyl-2,4-dimethylphenylenolate 41 iso-butylphenyl phosphate,

1-naphthinole 3,5-dimethylphenyl 4-iso-butylphenyl phosphate,

1-naphthinole-1,6-dimethynolepheninoleate 4-tert-butynolepheninole phosphate,

1-naphthynole-1,4-dimethylphenyl-4-tert-butynolephenyl phosphite,

1-naphthinole 3,5-dimethylphenyl 4-tert-butynolephenyl phosphite,

2-naphthyl-1,2,6-dimethylphenylenol 4-n-butynolephenyl phosphate,

2-naphthyl 1, 2,4-dimethynolephen-4 1-n-butylphenylenophosphate, 2-naphthyl ^ / — 3, 5-dimethinorefhenol 4-n-butynolefeninolephate,

2-naphthyl-1,2,6-dimethylphenylenol 4-iso-butynolephenyl phosphite ¹ to

2 Nafuchiru 2, 4 Jimechirufue two / Leh 4-an iso-Buchirufue two Honoré Sufue ¹ bets,

2-naphthinole 3,5-dimethylphenyl 4-iso-butylphenyl phosphate,

21-naphthyl-2,6-dimethylphenyl / le-41-tert-butylphenylethanol phosphate,

2-naphthyl-1,2,4-dimethylphenyl 4-tert-butylphenyl phosphite,

2-naphthyl-3,5-dimethylphenyl-1-tert-butylphenyl phosphite

When these naphthyl phosphate compounds (I) are used as flame retardants for resins, they can be used alone or as a mixture of two or more. Such a mixture may be a mixture obtained by mixing high-purity compounds or a mixture obtained by synthesis. Examples of the naphthyl phosphate compound (I) include, for example, 2-naphthyl diphenyl phosphate, 1-naphthyl diphen-nore phosphate, di (2-naphthinole) pheninole phosphate, and 2-naphthinoresphene phosphate as described in Examples below. And di (2-naphthinole) phenyl phosphate, a mixture of 2-naphthyl dicresyl phosphate and di (2-naphthyl) cresyl phosphate, and a mixture of 2-naphthyl-bis (2,6-dimethylphenyl) phosphate And a mixture of di (2-naphthyl) -1,2,6-dimethylphenylphosphate.

Among the naphthyl phosphate compounds (I) of the present invention, the compound (mononaphthyl dicresyl phosphate) wherein n = l, scale = methyl group, m == l For example, the target compound can be obtained with high purity by the following method.

(1) Method of reacting 1 mol of naphthol with 1 mol of dicresyl phosphorochloridate

(2) Method of reacting 1 to 2 mol of phosphorus oxychloride with 1 mol of naphthol, removing unreacted oxysalt, and then reacting with 2 mol of cresol

In the naphthyl phosphate compound (I), the compound (dinaphthyl monocresyl phosphate) with n = 2, R = methyl group, and m = l is, for example, the target compound if produced by the following method. It can be obtained with high purity.

(3) Method of reacting 1 mol of monocresyl phosphorodichloridate with 2 mol of naphthol

(4) A method of reacting 1 to 2 mol of phosphorus oxychloride with 1 mol of cresol, removing unreacted oxychlorinated ichlin and then reacting with 2 mol of naphthol

The naphthyl phosphate compound (I) obtained by the above method is generally a compound of the general formula (I) containing one of the compounds represented by n = 1 or n = 2 as a main component and the compound of n = l In the general formula (I), the compound of n = 0 (triphenyl phosphate and / or tri (alkyl-substituted phenyl) phosphate), the compound of n = 2 and the compound of η = 3 (trinaphthyl phosphate) ) May be contained as an impurity. In the case of the compound of η = 2, compounds of η = 0, η = 1 and η = 3 in the general formula (I) may be contained as impurities. The content ratio of impurities in these compounds of η = 1 or η = 2 is not particularly limited as long as the desired resin composition performance is maintained.

In the mixed phosphoric acid ester containing the above impurities, the triphenylphosphorus represented by η = 0 and / or If the content of (phenyl) phosphate is large, the boiling point will be low and the volatility will be high, so that it will volatilize during resin molding and contaminate the mold, leading to a reduction in the working efficiency of the molding process.

Further, when the content of trinaphthyl phosphate represented by n = 3 is large, the volatility is reduced, but the phosphorus content is reduced, and the flame retardancy is reduced. As a result, the amount of the flame retardant must be increased, and the inherent mechanical strength (eg, impact resistance) of the resin is reduced.

On the other hand, in the production of the naphthyl phosphate compound (I) of the present invention, particularly in industrial production, n == 0 and n = 3 in addition to the compound of n = l or n = 2 in the general formula (I). As a by-product, a mixed phosphate ester is obtained.

Therefore, the smaller the amount of the above-mentioned by-products contained in the naphthyl phosphate compound (I) of the present invention, the better, but it is contained within a range that does not impair the physical properties of the flame-retardant resin composition of the present invention. You may.

In the present invention, “containing no phenylene ether unit” means that a thermoplastic resin such as polyphenylene ether is not contained. Examples of the thermoplastic resin used in the present invention include polyethylene, polypropylene, polystyrene, impact-resistant polystyrene (high impact polystyrene: HIPS), ACS resin, AS resin, ABS resin (ABS), polycarbonate (PC), Polyamide, polyimide, polymethyl methacrylate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polyarylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal, polyether ketones, Examples include polyether nitrile, polythioether sulfone, polybenzimidazole, polycalimide, liquid crystal polymers, and polymer blends and alloys of these. .

Unmodified styrenic polymer in the present invention, Styrene, alpha-Mechiresuchiren, consisting C ₁ ~C ₄ 7 ₁ or more kinds of Honoré kill styrene and aromatic Bulle monomer component selected from halogenated styrenes (a) (co) polymers, and

One or more of component (a) and acrylonitrile, methacrylonitrile, C ₁ -C ₈ alkyl acrylate, C i C g alkyl methacrylate, maleic anhydride, dialkyl maleate, and N-substituted and non-substituted It means a copolymer selected from substituted male midokas with one or more kinds of the vinyl monomer component (b) copolymerizable with the component (a).

Examples of the aromatic vinyl monomer components (a), styrene; o-methylstyrene Ren, m- methylstyrene, p- methyl styrene, and α- methylate ^ / C i~C ₄ alkyl styrene such as styrene Ren, and chlorostyrene And halogenated styrenes such as

Further, the vinyl monomer component (b) copolymerizable with the component (a) includes acrylonitrile;

Methacrylonitrile;

Methyl Atari rate, Echiruatari rate, n- Buchiruatari rate, iso- Buchiruakuri rate, tert- Buchiruaku Li rate and C ₁ -C ₈ 7 such as 2 _ Kishiruakuri rate to E Ji Le Norekiruakuri rate; Mechirumetakuri rate Echirumetatari rate, n C ₁ -C ₈ alkyl ^^ methacrylates such as -butyl methacrylate, iso-butynole methacrylate, tert-butynole methacrylate and 2-ethynolehexyl methacrylate;

maleic anhydride;

Maleic acid di-n-amyl ester, maleic acid di-isobutyl ester, maleic acid dimethinoleester, maleic acid di-n-propyl / ester, maleic acid octyl ester, maleic acid dinonyl ester and anhydrous Maleic acid dialkyl esters such as maleic acid; N-substituted or unsubstituted maleimides, such as maleimide, N-methinolemalide, N-echi / lemaleimide, N-feelmaleimide and N-cyclohexylmaleimide

Is mentioned.

Examples of the unmodified styrene-based polymer as described above include polystyrene and AS resin.

The rubber-modified styrenic polymer in the present invention,

In the presence of a rubber-modified component comprising diene-based polymer (c), styrene, alpha-methyl styrene, C i~C ₄ alkylstyrene Contact Yopi aromatic vinyl monomer component selected from halogen Kas styrene ( and one or more a), acrylonitrile, methacrylonitrile, C ₁ -C ₈ Arukirua chestnut rate, c ₁ to c ₈ alkyl methacrylates rate, maleic anhydride, Ma maleic acid dialkyl ester and N- substituted and unsubstituted A graft polymer selected from male midoka, which is obtained by copolymerizing component (a) with one or more copolymerizable bull monomer components (b)

Means

Examples of the rubber-modified component (c) composed of a diene polymer include butadiene, dicyclopentadiene, isoprene, cloprene, phenylpropadiene, cyclopentadiene, 1,5-nonolevonadiene, 1,3-cyclohexadiene, Examples thereof include 1,4-cyclohexadiene, 1,5-cyclohexadiene, and 1,3-cyclooctadiene.

The rubber-modified styrenic polymer as described above includes, for example, ABS resin.

The aromatic polycarbonate is specifically obtained by a reaction between a divalent or higher-valent phenol compound and a carbonic acid diester compound such as phosgene or diphenyl carbonate.

The divalent phenol compound is not particularly limited. However, in view of the balance between the flame retardancy and other physical properties of the obtained resin composition, 2,2— Bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) is preferred.

In addition, the divalent phenol compounds other than bisphenol A include bis (4-hydroxyphene / methane), bis (4-hydroxyphene) phenolemethane, and bis (4-hydroxyphene) naphthymethane Bis (4-hydroxyphenyl) methane, bis (3,5-dimethinolate 4-hydroxyphenyl) / methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) ethane, 1, -phenyl_1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane , 2-Methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-14-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4-methyl-1,2,2-bis ( 4-Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) Dihydroxydiarylalkanes such as nonane and 1,10-bis (4-hydroxyphenyl) decane;

1,1-bis (4-hydroxyphenyl) -3,3,5-trimethinolecyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Dihydroxydiarylcycloalkanes such as cyclodecane;

Bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethinolate 4-hydroxyphenyl) sulfone, etc. Phones;

Dihydroxydiaryl ethers such as bis (4-hydroxyphenyl) ether and bis (.3,5-dimethyl-4-hydroxyphenyl) ether;

4,4'-dihydroxybenzophenone, 3,3 ', 5,5,1-tetramethynolele 4,4'-dihydroxydarylic ketones such as dihydroxybenzobenzophenone;

Bis (4-hydroxydroxyphenyl) snorefide, bis (3-methynole-1-41-hydroxylphenyl) snorefide, bis (3,5-dimethynole-l 4-hydroxyhydroxyphenyl) sulfide and other dihydroxydiaryl sulfides ;

Dihydroxydiarylsulfoxides such as bis (4-hydroxyphenyl) snorreoxide;

Dihydroxybiphenyls such as 4,4 'dihydroxybiphenyl; dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene

And the like.

In place of the above divalent phenol compound, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene are used. It can also be used.

These divalent phenol compounds and compounds replacing them can be used alone or in combination of two or more.

Examples of the carbonic acid diester compound to be reacted with the divalent phenol compound include diaryl carbonates such as diphenyl carbonate; dialkyl carbonates such as dimethyl carbonate and getyl carbonate.

Examples of thermosetting resins include polyurethane, phenolic resin, Examples thereof include a lamin resin, a urea resin, an epoxy resin, an unsaturated polyester, a diaryl phthalate resin, and polymer blends and alloys thereof. Among them, the naphthyl phosphate compound (I)

) Is particularly suitable for phenolic resins Z or epoxy resins. In addition, the thermoplastic resin used in the present invention preferably contains the above-mentioned unmodified styrene-based polymer and / or rubber-modified styrene-based polymer, and preferably contains the above-mentioned aromatic polycarbonate. That is, as the thermoplastic resin, polymer blends and polymer alloys of the above resins are preferable. Specifically, PCZABS polymer alloy is preferred in view of the balance between flame retardancy and other physical properties of the obtained resin composition.

Naphthyl phosphate compound (I) in the flame-retardant resin composition of the present invention

) The amount of the flame retardant to be added is appropriately determined according to the type of the resin to be provided with flame retardancy and the required degree of flame retardancy.

When the resin is a thermoplastic resin containing no phenylene ether unit, the amount of the flame retardant comprising the naphthyl phosphate compound (I) is usually 1 to 4 parts by weight based on 100 parts by weight of the resin. The range of 0 parts by weight is preferable, the range of 5 to 40 parts by weight is more preferable, and the range of 10 to 30 parts by weight is further preferable.

When the amount of the naphthyl phosphate compound (I) is less than 1 part by weight, a sufficient flame retarding effect cannot be obtained, which is not preferable. On the other hand, if the addition amount exceeds 40 parts by weight, there is a possibility that adverse effects such as a decrease in mechanical strength of a molded article of the obtained resin composition and acceleration of resin decomposition may occur, which is not preferable. .

When the resin is a thermosetting resin, the amount of the flame retardant comprising the naphthyl phosphate compound (I) is usually in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the resin. Preferably, the range is 5 to 50 parts by weight, and more preferably, the range is 10 to 30 parts by weight. If the amount of the naphthyl phosphate compound (I) is less than 1 part by weight, a sufficient flame retarding effect cannot be obtained. On the other hand, if the amount exceeds 100 parts by weight, it is not preferable because adverse effects such as a decrease in mechanical strength of a molded article of the obtained resin composition and acceleration of decomposition of the resin may occur. .

In the flame-retardant resin composition of the present invention, various additives generally added to the resin composition may be added as needed, if necessary, as long as the physical properties are not impaired. These additives may be used alone or in combination of two or more. Such additives include, for example, other flame retardants other than the naphthyl phosphate compound (I), flame retardant aids, anti-dripping agents, fillers

, Antioxidants (stabilizers), antistatic agents, lubricants (softeners), pigments, ultraviolet absorbers (light stabilizers), reinforcing materials, and the like.

Other flame retardants include trifenyl phosphate, tricresyl phosphate, cresinorespheninolephosphate, trixylyl phosphate, dicresyl-1,2,6-dimethylphenyl phosphate, tris (2,6-dimethylphenyl) phosphate and the like. Monomer type organophosphorus flame retardant, resorcin bis (diphenyl phosphate), bisphenol monophosphate A bis (diphenyl phosphate), rezonolecin bis [(bis-1,2,6-dimethylphenyl) phosphate], hydroquinone bis [( Organophosphorus flame retardants of the oligomer type, such as bis-2,6-dimethinolephenophosphate), 4,4'-biphenorenorbis [(bis-1,2,6-dimethylpheninole) phosphate], magnesium hydroxide, water Aluminum oxide Stabilized red phosphorus such as melamine phosphate, melamine cyanurate, polyammonium phosphate, melamine, red phosphorus coated with thermosetting resin, red phosphorus coated with olefin, red phosphorus coated with titanium oxide and red phosphorus coated with titanium aluminum condensate Red phosphorus powders such as powders; silicone-based flame retardants such as silicone resin, silicone starch, silicone rubber, and silicone oil. Examples of the flame retardant aid include graphite, activated carbon, borates, low-melting glass, and carbon powders such as carbon black produced by an oil furnace method, a gas furnace method, a channel method, or an acetylene method. .

As the anti-dripping agent, a known fluorine resin is preferably used. Examples of the fluorine-based resin include polytetrafluoroethylene (PTFE), polytetrafluoroethylene-polyhexafluoropropylene copolymer, polytetrafluoroethylene-polyfluoroalkyl vinyl ether copolymer, Examples thereof include polytetrafluoroethylene-ethylene copolymer, and polytrifluoromonoethylene. The form may be any form such as emulsion form, suspension form, microfibril form, powder form, and granular form. These can be used alone or in combination of two or more.

Examples of fillers include powdered, granular, and plate-like inorganic fillers such as glass fiber, carbon fiber, metal fiber, ceramic fiber, my strength, silica, talc, calcium carbonate, alumina, glass beads, glass balloons, and glass flakes. Fillers and organic fillers such as wood flour. These can be used alone or in combination of two or more.

Other additives include phosphorus-based compounds such as pentaerythritol diphosphate derivative, phenol-based compounds such as hindered phenol derivatives, amine-based and sulfur-based antioxidants (stabilizers); cationic activators; Antistatic agents such as nonionic activators; lubricants (softening agents) such as fatty acid derivatives and high-melting-point resins; pigments such as titanium oxide and phthalocyanine; benzophenone, salicylate, benzotriazole and acrylonitrile UV absorbers (light stabilizers); reinforcing materials such as glass fibers, metal fibers and whiskers.

In producing the flame-retardant resin composition of the present invention, the order of mixing the components and the method of mixing are not particularly limited. For example, the naphthyl phosphate compound of the present invention It is obtained by mixing the product (I), the thermoplastic resin or the thermosetting resin, and, if necessary, the various additives described above by a known method, and melt-kneading the mixture. For mixing and melt kneading, general-purpose devices such as single-screw extruders, twin-screw extruders such as twin-screw extruders with vents, Henschel mixers, Banbury mixers, kneaders, mixers, and knurls can be used alone or separately. Can be used in combination.

The obtained resin composition is further subjected to known methods such as injection molding and extrusion molding for thermoplastic resins, and casting, compression molding, transfer molding and lamination molding for thermosetting resins. By molding, it is possible to obtain a desired shape, for example, a plate-like, sheet-like or film-like molded product. Example

The present invention will be described more specifically with reference to the following synthesis examples, examples and comparative examples, but the scope of the present invention is not limited by these examples.

The flame retardants obtained in the synthesis examples and the components used in the examples and comparative examples are described below.

(1) Resin component

PC / AB S: PC / AB S polymer alloy

(Manufactured by Daicel Chemical Industries, Ltd., product name: Novalloy S 1500) A B S: A B S resin

(Manufactured by Daicel Chemical Industries, Ltd., trade name: SEVIAN V 500 S F) Epoxy: bisphenol A type epoxy resin

(Made by Yuka Shell Epoxy Co., Ltd., product name: Epicoat 828) Phenols: Novolac phenol resin

(Arakawa Chemical Industries, Ltd., product name: Tamanor 759)

(2) Flame retardant component Flame retardant 1: 2-naphthyl diphenyl phosphate (Synthesis example 1) Flame retardant 2: 1-naphthyl diphenyl phosphate (Synthesis example 2) Flame retardant 3: di (2-naphthyl) phenyl phosphate (Synthesis example 3) Difficult Flame retardant 4: 2-naphthyl phosphate mixture A (Synthesis example 4) Flame retardant 5: tri (2-naphthyl) phosphate (Synthesis example 5) Flame retardant 6: 2-naphthyl phosphate mixture B (Synthesis example 6) Flame retardant 7: 2 —Naphthyl phosphate mixture C (Synthesis example 7) Flame retardant 8: 2-naphthyl phosphate mixture D (Synthesis example 8) Flame retardant 9: 2-naphthyl dicresyl phosphate (Synthesis example 9) Flame retardant 10: 2-naphthyl dixylyl phosphate (Synthesis example 10) Flame retardant 11 1: Trifenyl phosphate (the following formula)

Melting point: 49 ° C

(Daichi Chemical Industry Co., Ltd., product name: TPP)

Flame retardant 1 2: Resorcin bis (diphenyl phosphate) (following formula) Viscosity (20 ° C): 0.97 Pa · s

(Product name: CR-733 S, manufactured by Daihachi Chemical Industry Co., Ltd.)

Flame retardant 13: bisphenol A bis (diphenyl phosphate) (formula below)

Viscosity (20 ° C): 42 Pa · s

(Daichi Chemical Industry Co., Ltd., product name: CR-741)

Flame retardant 14: Tris (2,6-dimethylphenyl) phosphate (Formula below)

(Daichi Chemical Industry Co., Ltd., product name: PX_130)

(3) Other ingredients

Anti-dripping agent: Polytetrafluoroethylene (PTFE)

(Mitsui DuPont Fluorochemical Co., Ltd., trade name: PTFE 6—J

)

Curing catalyst: imidazole curing catalyst

(Product name: Epicure EM124, manufactured by Yuka Shell Epoxy Co., Ltd.) The composition of the product obtained in the following synthesis example was analyzed by liquid chromatography. The measurement was performed under the following conditions.

Measurement conditions Column: Tosoh Corporation, ODS-8 OTM

Eluent: 90 vol% methanol-10 vol% water

(Synthesis example:! ~ 9)

Asetonitorinore 80 vol ^_0/0 - Water 20 volume ^_0/0 (Synthesis Example 10)

Detector wavelength: 254 nm Synthesis Example 1 (Synthesis of flame retardant 1: 2-naphthyldiphenylphosphate) In a 2 liter four-necked flask equipped with a stirrer, a reflux tube and a thermometer, 2_naphthone 432.5 g (3 monoles), 805.8 g (3 mol) of diphenyl phosphorochloridate, 1.5 g of anhydrous magnesium chloride and 30 g of toluene were charged, and the mixed solution was stirred under a nitrogen atmosphere. The mixture was heated to 150 ° C over 2 hours and refluxed under reduced pressure (about 27 kPa) at the same temperature (150 ° C) for 3 hours. After reflux, the reaction mixture was cooled to 80 ° C, brought to normal pressure with nitrogen, washed successively with 3.5% hydrochloric acid and 1% aqueous sodium hydroxide at the same temperature (80 ° C), and finally washed. Was washed with water. Furthermore, steam distillation was performed under reduced pressure of 150 ° C (about 2.7 kPa) to remove low boiling components from the reaction product, to obtain 1105.9 g of a light brown solid. The crude yield was 98%, assuming that all of the solid was the target compound.

The composition of the product obtained was determined by liquid chromatography. Composition: 2-Naphthyl diphenyl phosphate 98.8% Trifenyl phosphate (TPP) 0.7% Di (2-naphthyl) phenyl phosphate 0.5% Also measure the melting point and phosphorus content of the obtained product did.

Melting point: 63 ° C

Phosphorus content: 8.2% Synthesis Example 2 (flame retardant 2: synthesis of .1-naphthyldiphenyl phosphate) 1055.2 g of a slightly brown solid was obtained in the same manner as in Synthesis Example 1 except that 1-naphthol was used instead of 2-naphthol. . The crude yield was 93% assuming that all of the solid was the target compound.

The composition, melting point and phosphorus content of the obtained product were measured in the same manner as in Synthesis Example 1.

Composition: 1-Naphthyl diphenyl phosphate 98.8% Trifenyl phosphate (TPP) 0.7% Di (1-naphthyl) phenyl phosphate 0.5% Melting point: 52 ° C

Phosphorus content: 8.2% Synthesis Example 3 (Flame retardant 3: Synthesis of di (2-naphthyl) fuel phosphate)

Synthesized except using 70.8 g (5 mol) of 2-naphthol, 527.5 g (2.5 mol) of monophenyl phosphorodichloridate, 1.2 g of anhydrous magnesium chloride and 30 g of toluene as starting materials In the same manner as in Example 1, 1043.8 g of a slightly brown solid was obtained. The crude yield was 98%, assuming that all of the solid was the target compound.

Composition: di (2-naphthyl) phenyl phosphate 98 7% trifenyl phosphate (TPP) 0 3% 2-naphthyl diphenyl phosphate 0 1% tri (2-naphthyl) phosphate 0 9% Melting point: 63 ° C

Phosphorus content: 7.2% Synthesis Example 4 (Synthesis of Flame Retardant 4: 2-Naphthyl Phosphate Mixture A) In a 3-liter four-necked flask equipped with a stirrer, a reflux tube and a thermometer, 432.5 g (3 mol) of 2-naphthol, oxychloride 506.1 g (3.3 mol) of phosphorus and 1.5 g of anhydrous magnesium chloride were charged, and the mixed solution was heated to 120 ° C for 2 hours while stirring under a nitrogen atmosphere, and heated at the same temperature ( (120 ° C) for 1 hour. Thereafter, pressure reduction was started at the same temperature (120 ° C.), and excess oxychloride was recovered until the pressure reached about 1.3 kPa. The reaction mixture was cooled to room temperature, and 564.0 g (6 mol) of phenol and 30 g of toluene were added. The mixture was heated to 150 ° C over 2 hours while stirring under a nitrogen atmosphere. The mixture was refluxed under the reduced pressure of C) (about 27 kPa) for 2 hours. After the reflux, the same post-treatment as in Synthesis Example 1 was performed to obtain 1021.7 g of a slightly brown solid.

With respect to the obtained product, the composition and the melting point and the phosphorus content were measured in the same manner as in Synthesis Example 1.

Composition: 2-Naphthyl diphenyl phosphate 81.2% Di (2-naphthyl) phenyl phosphate 18.1% Tri (2-naphthyl) phosphate 0.2% Trifenyl phosphate (TPP) 0.5% Melting point: 59 ° C

Phosphorus content: 8.0% Synthesis Example 5 (Synthesis of Flame Retardant 5: Tri (2-naphthyl) phosphate) 2-Naphthol 1081 in a 3 liter four-necked flask equipped with a stirrer, a reflux tube and a thermometer. 2 g (7.5 mol), 1.3 g of anhydrous magnesium chloride and 1000 g of o-dichlorobenzene were charged, and the mixture was heated to 120 ° C while stirring under a nitrogen atmosphere. 383.4 g (2.5 mol) of phosphorus oxychloride at 120 ° C for 1 hour Added. Next, the reaction solution was heated to 150 ° C. over 2 hours, and refluxed at the same temperature (150 ° C.) under reduced pressure (about 27 kPa) for 3 hours. After the reflux, the reaction mixture was cooled to room temperature, brought to normal pressure using nitrogen, 1000 g of ethanol was further added, and the mixture was allowed to stand at room temperature to precipitate crystals. The precipitated crystals were separated by filtration and dried under reduced pressure at 100 ° C. to obtain 1071.6 g of white crystals. The crude yield was 91%, assuming that all of the solids were the target compound.

Composition: tri (2-naphthyl) phosphate 99% or more Melting point: 111 ° C

Phosphorus content: 6.5% Synthesis Example 6 (Synthesis of Flame Retardant 6: 2-Naphthyl Phosphate Mixture B) 2-Naphthol 432.5 in a 2-liter four-necked flask equipped with a stirrer, a reflux tube and a thermometer. g (3 moles), 414.0 g (2.7 moles) of oxychloride phosphorus and 1.5 g of anhydrous magnesium chloride, and the mixed solution was stirred under a nitrogen atmosphere until 120 ° C. The mixture was heated and heated over a period of time, and stirred at the same temperature (120 ° C) for 1 hour. Then, pressure reduction was started at the same temperature (120 ° C), and hydrogen chloride gas generated by the reaction was removed until the pressure reached approximately 2.7 kPa. The reaction mixture was cooled to room temperature, and further added 480.0 g (5.1 mol) of phenol and 30 g of toluene. The mixture was heated to 150 ° C over 2 hours while stirring under a nitrogen atmosphere. Dehydrochlorination was performed under reduced pressure (about 20 kPa) at a temperature (150 ° C) for 2 hours. After dehydrochlorination, the reaction mixture was cooled to 80 ° C, brought to normal pressure with nitrogen, washed successively with the same temperature (80 ° C) with 3.5% hydrochloric acid and 1% sodium hydroxide aqueous solution, and finally washed. Washing was performed. Further, steam distillation was performed at 150 ° C under reduced pressure (about 2.7 kPa) to remove low-boiling components from the reaction product. 972.0 g of a light brown liquid were obtained.

The composition and phosphorus content of the obtained product were measured in the same manner as in Synthesis Example 1.

Ito Katsunori: 2-Naphthyl diphenyl / rephosphate 68.8% Di (2-naphthyl) phenyl phosphate 29.5% Trifenyl phosphate (TPP) 1.3% Tri (2-naphthyl) phosphate 0.4% Phosphorus Content: 8.2% Synthesis Example 7 (Synthesis of Flame Retardant 7: 2-Naphthyl Phosphate Mixture C) As starting materials, 345.0 g (2.25 mol) of oxychloride phosphorus, 352.8 g of phenol In the same manner as in Synthesis Example 6 except that (3.75 mol) was used, 849.0 g of a slightly brown liquid was obtained.

Composition: 2-Naphthyl diphenyl phosphate 49.2% Di (2-naphthyl) phenyl phosphate 48.9% Trifenyl phosphate (TPP) 0.3% Tri (2-naphthyl) phosphate 1.6% Phosphorus content: 8.0% Synthesis Example 8 (Synthesis of Flame Retardant 8: 2-Naphthyl Phosphate Mixture D) As starting materials, 20.1 g (1.5 mol) of oxychloride phosphorus, 141.3 g of phenol (1. (5 mol) in the same manner as in Synthesis Example 6 to obtain 621. Og of a slightly brown liquid.

Composition: 2-naphthyldiphenyl phosphate 5.8% Di (2-naphthinole) phenylephosphate 74.8% Trifenyl phosphate (TPP) 0.2% Tri (2-naphthyl) phosphate 19.1% Phosphorus content: 7.2% Synthesis example 9 (flame retardant 9 : Synthesis of 2_ naphthyl dicresyl phosphate) In a 2 liter four-necked flask equipped with a stirrer, a reflux tube and a thermometer, 432.5 g (3 mol) of 2-naphthol, 920.0 g of phosphorus oxychloride (6 Mol) and 1.5 g of anhydrous magnesium chloride, and the mixture was heated to 120 ° C over 2 hours while stirring under a nitrogen atmosphere, and stirred at the same temperature (120 ° C) for 1 hour. did. Thereafter, decompression was started at the same temperature (120 ° C), and excess oxychlorine was recovered until the pressure reached about 2.7 kPa. The reaction mixture is cooled to room temperature, and a mixture of 3-methylphenol and 4-methinophenol (648.0 g, 6 mol) is added. The mixture is stirred at 150 ° C for 2 hours under a nitrogen atmosphere. The temperature was raised to C, and dehydrochlorination was performed for 2 hours under reduced pressure (about 4.0 kPa) at the same temperature (150 ° C). After the completion of dehydrochlorination, the reaction mixture is cooled to 80 ° C, brought to normal pressure using nitrogen, and washed successively with the same temperature (80 ° C) with 3.5% hydrochloric acid and 1.7% aqueous sodium carbonate solution. Was washed with water. Further, steam distillation was performed at 150 ° C under reduced pressure (about 2.7 kPa) to remove low-boiling components from the reaction product to obtain 1138.4 g of a slightly brown liquid. The crude yield was 94%, assuming that all of the liquid was the target compound. The composition and phosphorus content of the obtained product were measured in the same manner as in Synthesis Example 1.

Composition: 2-Naphthyl dicresyl phosphate * 92. 73% Di (2-naphthyl) cresyl phosphate ** 6.82% Tricresyl phosphate 0.45%

*: Mixture of the following compounds 2-Naphth-bis (3-methinorefue Λ ^) phosphate

2-Naphtinolevis. (4-methinorefue Λ ^) phosphate

2—Naphthinole 3—Methinolephenone 4—Methinolefeninolephosphate

**: Mixture of the following compounds

Di (2-naphthyl) -1,3-methylphenyl phosphate

Di- (2-naphthinole) 1-4-methinolephene phosphate

Phosphorus content: 7.6% Synthesis Example 10 (flame retardant 10: synthesis of 2-naphthyl dixylyl phosphate)

In the same manner as in Synthesis Example 9 except that 732.0 g (6 mol) of 2,6-dimethinolephenol was used instead of the mixture of 68.0 g (6 monoles) of a mixture of 3-methylphenol and 4-methylphenol. 1047.7 g of a slightly brown solid were obtained. The crude yield was 81% assuming that all of the solid was the target compound.

Composition: 2-naphthyl dixylyl phosphate * 91.89% di (2-naphthyl) xylinole phosphate ** 8.05% trixylinole phosphate *** 0.03% tri (2-naphthyl) phosphate 0.04%

*: 2-Naphthinolevis (2,6-dimethynolephene) phosphate * *: Di (2-naphthyl) -1,2,6-dimethylphenyl phosphate * * *: Tris (2,6-dimethylphenyl) phosphate containing phosphorus Rate '. Ί. 1%

Melting point: 53 ° C The physical properties of the resin compositions obtained in the following Examples and Comparative Examples were measured based on the following test methods. The vertical flammability test was also used to determine the amount of flame retardant added.

(1) Vertical flammability (UL) test

Test method: Based on UL 94 (average quenching time of 5 samples)

Test piece: thickness 1.6 mm

3.2 mm thick (Example 6 only)

Rating: Ranks V-0, V-1 and V-2 according to regulations

(2) Izod impact value (Examples 1-4 and Comparative Examples 1-4)

Test method: Conforms to JISK-7110

Specimen: thickness 3.2mm, notch

Single iL: kgf · cva./cm

(3) Loss on heating (Examples 1 to 5 and 7 to 16 and Comparative Examples 1 to 9) Resin pellets (diameter: about 2 mm, length: approx. 3mm, about 1 Omg) was heated to a predetermined temperature * at a heating rate of 20 ° C / min, and the weight loss rate (% by weight) was measured.

*: 250 ° C (Example:! ~ 5 and Comparative Example:! ~ 5)

300 ° C (Examples 7 to: 16 and Comparative Examples 6 to 9)

(4) Hydrolysis resistance (durability) test (Examples 1-4 and Comparative Examples 1-4)

The resin composition was exposed to specific conditions, dried, and the MFR (melt mass flow rate, gZlO content) was measured. The MFR before exposure was measured in advance, and it was determined that the larger the change in MFR before and after exposure, the lower the hydrolysis resistance (durability).

Specimen: Resin pellet (diameter: approx. 2 mm, length: approx. 3 mm) Exposure conditions: 1 2 atmospheres saturated steam at 20 ° C, 12 hours

Drying conditions: 95 ° C, 3 hours

Measurement method: Conforms to JIS K-7210 Measurement conditions: 230 ° C, load 5. O kg

+ Unit: g / l 0 minutes

(5) Flexural strength (Examples 1-4 and Comparative Examples 1-4)

Test method: Conforms to JISK-7171

Specimen: thickness 6.4mm

Single 1 ^: kgf / cm ²

(6) Flexural modulus (Examples 1-4 and Comparative Examples 1-4)

Test method: Conforms to JIS K-7171

Specimen: thickness 6.4mm

Unit: kgf Zc m ²

(7) Deflection temperature under load (Examples 1-4 and Comparative Examples 1-4)

Test method: According to JISK-7191

Test piece: thickness 12.8mm

Condition: Bending stress measured at 18.5 kgf / cm ²

Unit: ° C

(8) Fluidity test (Examples 7 to 16 and Comparative Examples 6 to 9)

The resin composition was dried under specified conditions, and the MFR was measured.

Sample: Resin pellet (diameter: about 2mm, length: about 3mm) Drying condition: 95 ° C, 3 hours

Measurement method: According to JISK-7210

Measurement conditions: 230 ° C, load 5. O kg

(Examples 7 to 11 and Comparative Examples 6 to 7) 200 ° C, load 5.O kg

(Examples 12 to: I6 and Comparative Examples 8 to 9)

(9) Smoke emission test (Examples 7 to 16 and Comparative Examples 6 to 9)

The state of generation of smoke during the molding of the resin composition was visually observed. The case where no smoke was observed was indicated by “〇”, and the case where smoke was observed was indicated by “X”. Examples 1-4 and Comparative Examples 1-4

To 100 parts by weight of PCZAB S polymer alloy, 0.4 parts by weight of the flame retardant and anti-dripping agent shown in Table 1 or Table 2 were mixed with a Henschel mixer and melt-kneaded with a vented twin-screw extruder. Thus, a pellet of the resin composition was obtained. The obtained pellets were molded by an injection molding machine, and test pieces for flame retardancy (vertical burning) test and test pieces for measuring mechanical properties were prepared, and the physical properties were measured based on the above test methods. The results obtained are shown in Tables 1 and 2 together with the components of the resin composition and the proportions thereof.

The amount of the flame retardant was determined so that the evaluation of the resin composition in the vertical flammability (UL) test achieved V-0.

Example Example Example Example Example

1 2 3 4

(1) Resin component PC / AB S 100 100 100 100 pairs

Composition Flame retardant 1 14

Flame retardant 2 14

(2) Flame retardant component

Flame retardant 3 16 parts

Flame retardant 4 16

(3) Other components Anti-drip agent 0.4 0.4 0.4 0.4 Izod impact strength kgf -cm / cm 66 64 54 56 Material Heat loss 1.3 1.4 0.4 0.6 Property Hydrolysis resistance g / 10min 14.9 16.5 17.0 20.0

(FR) After g / 10min 94.9 76.7 114.1 149.4

Table 2

From the results in Tables 1 and 2, the resin composition of Example 14 showed excellent flame retardancy with a small amount of added flame retardant, low volatility (less heat loss), and hydrolysis resistance It is clear that the resin has excellent strength (durability), has a small decrease in the mechanical strength inherent in the resin, and has sufficient strength for practical use. Thus, the naphthyl phosphate compound (I) of the present invention imparts excellent flame retardancy to a resin, is low in volatility, has excellent hydrolysis resistance, and does not lower the inherent mechanical strength of the resin. It turns out that it is a very useful non-halogen flame retardant.

On the other hand, the resin composition of Comparative Example 14 in which a known flame retardant was added instead of the naphthyl phosphate compound (I) of the present invention was inferior in any respects.

Specifically, the resin composition of Comparative Example 1 has a low Izod impact strength and a low hydrolysis resistance because a large amount of a flame retardant is added to achieve the flame retardancy rank V-0. Is also inferior.

The resin composition of Comparative Example 2 has a large loss on heating, and may cause mold contamination during molding. The resin composition of Comparative Example 3 has extremely poor hydrolysis resistance and poor durability.

The resin composition of Comparative Example 4 has no particular problem in various physical properties, but is inferior in handling because the flame retardant itself is a very high viscosity liquid material.

For the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4, the flexural strength, flexural modulus and deflection temperature under load were measured based on the above test method.i Significant difference between the Example and Comparative Example However, all were practically usable for the resin composition.

The numerical range of the obtained measurement results is shown below.

Flexural strength: 736-900 kgf / cm ²

Flexural modulus: 23300 to 25500 kg f cm

Deflection temperature under load: 76 to 86 ° C Example 5 and Comparative Example 5

Example 1 was repeated except that the amount of the flame retardant added was determined so that the evaluation of the vertical flammability (UL) test of the resin composition achieved V-2 using the ABS resin composition described in Table 3. Test pieces were prepared in the same manner as in Nos. 1 to 4, and the flame retardancy (UL-94) and loss on heating were measured. The results obtained are shown in Table 3 together with the components of the resin composition and their proportions. Table 3

Example 5 Comparative Example 5

(1) Resin component AB S 100 100 Composition

Flame retardant 1 20

(Parts by weight) (2) Flame retardant component

Flame retardant 11 20

UL-94 Rank V- 2 V- 2 Physical properties

Heat loss 1.1 4.2 Example 6

A test piece was prepared in the same manner as in Examples 1 to 4 except that the test piece was molded by casting using the epoxy resin composition shown in Table 4, and the flame retardancy (UL-94) was determined. It was measured. The results obtained are shown in Table 4 together with the components of the resin composition and their proportions. Table 4

From the results in Tables 3 and 4, it can be seen that similar effects can be obtained with other resins than the PCZABS polymer alloy. Examples 7 to 11 and Comparative Examples 6 to 7

To 100 parts by weight of the P CZA BS polymer alloy, 0.4 parts by weight of the flame retardant and the anti-dripping agent shown in Table 5 or Table 6 were mixed with a Henschel mixer, and the mixture was extruded with a vented twin-screw extruder. The mixture was melt-kneaded to obtain a pellet of the resin composition. The obtained pellets were molded by an injection molding machine to prepare test pieces for evaluating flame retardancy (vertical combustibility), and the physical properties were measured based on the above test methods. The results obtained are shown in Tables 5 and 6, together with the components and proportions of the resin composition.

The amount of the flame retardant was determined so that the evaluation of the resin composition in the vertical flammability (UL) test achieved V-0. Table 5

Composition (parts by weight) Table 6

Composition (parts by weight) From the results in Table 5, the resin compositions of Examples 7 to 11 show excellent flame retardancy and fluidity even when a small amount of flame retardant is added, and have low volatility and low heat loss. Slightly), it can be seen that no smoke is observed during molding. Therefore, the naphthyl phosphate compound (I) of the present invention has excellent flame retardancy and fluidity. It is found that this is a very useful monomer-type non-halogen flame retardant that is low in volatility and does not cause mold contamination during molding.

On the other hand, from the results in Table 6, the resin compositions of Comparative Examples 6 and 7 in which a known flame retardant was added instead of the naphthyl phosphate compound (I) of the present invention were inferior in the following points. That is, since these resin compositions have a large loss on heating, they may contaminate the mold during molding, and smoke may be observed, which may deteriorate the working environment. Also, the fluidity is equivalent to or slightly inferior to Examples 7 and 8. Example 12: L6 and Comparative Examples 8 to 9

Except for using the ABS resin compositions shown in Tables 7 and 8 (the amount of the flame retardant added was fixed at 20 parts and the anti-dripping agent was not added), the same procedures as in Examples 7 to 11 were carried out. Test pieces were prepared, and various physical properties were measured in the same manner as in Examples 7 to 11. The obtained results are shown in Tables 7 and 8 together with the components of the resin composition and their ratios. The evaluation of the vertical flammability (UL) test for all the resin compositions was V-2.

Table 7

Composition (parts by weight) Table 8

Composition (parts by weight) From the results in Table 7, it can be seen that the same results as those of the PC / ABS polymer alloy can be obtained with the ABS resin.

On the other hand, from the results in Table 8, the resin compositions of Comparative Examples 8 and 9 in which a known flame retardant was added instead of the naphthyl phosphate compound (I) of the present invention were inferior in the following points. Specifically, the resin composition of Comparative Example 8 has the same fluidity as those of Examples 12 to 16, but has a large loss on heating, and may contaminate the mold during molding. Smoke emission may deteriorate the working environment.

In addition, the resin composition of Comparative Example 9 is significantly inferior to Examples 12 to 16 in all physical properties. According to the present invention, a monomer-type non-halogen flame retardant that imparts excellent flame retardancy and fluidity to a resin with a small amount of added sardine and does not cause mold contamination during molding is added. Thus, a flame-retardant resin composition can be provided.

In addition, this non-halogen flame retardant has excellent hydrolysis resistance, does not decrease the mechanical strength inherent in the resin, does not impair the appearance of the molded product, and is also inexpensive.

As described above, the naphthyl phosphate compound (I) of the present invention has the characteristics of a monomer-type organophosphorus flame retardant that improves fluidity during resin molding, hardly lowers the inherent mechanical strength of the resin, and is inexpensive. It also has the characteristics of a polymer-type condensed organic phosphorus-based flame retardant, which is difficult to volatilize during resin molding.

Claims

The scope of the claims

1. Thermoplastic or thermosetting resin not containing phenylene ether units, as flame retardant, general formula (I):

Wherein n is 1 or 2, R is a C i C alkyl group, and m is an integer of 0 to 3. A flame-retardant resin composition comprising a naphthyl phosphate compound represented by the following formula:

2. The naphthyl phosphate compound is 2-naphthinoresiphenyl phosphate, 1-naphthyl dipheninolephosphate, di (2-naphthyl) phenylinolephosphate, 2-naphthinoresiphenyl phosphate and di (2-naphthyl) phenyl phosphate A mixture with enyl phosphate, a mixture with 2-naphthyl dicresyl phosphate and di (2-naphthyl) cresyl phosphate, or a mixture with 2-naphthyl-bis (2,6_dimethinorefuennole) phosphate and di (2-naphthyl) 1 2 2. The flame-retardant resin composition according to claim 1, which is a mixture with 6,6-dimethylphenyl phosphate.

3. The flame-retardant resin composition according to claim 1 or 2, wherein the thermoplastic resin contains an unmodified styrenic polymer and a _ or rubber-modifying styrenic polymer.

Styrene, α-methynolestyrene, C _1- . ₍₄ ) A (co) polymer comprising one or more aromatic vinyl monomer components ( _a ) selected from benzoquinone styrene and halogenated styrene, or

One or more of the above components (a), acrylonitrile, methacrylonitrile, and C. 8 alkyl atarilate, C i C g alkyl meta Tallylate, maleic anhydride, dialkyl maleate and

The copolymer according to claim 3, which is a copolymer selected from N-substituted and unsubstituted male midokas with one or more vinyl monomer components (b) copolymerizable with the component (a). The flame-retardant resin composition according to the above.

5. The flame-retardant resin composition according to claim 4, wherein the unmodified styrene-based polymer is polystyrene or an AS resin.

6. When the rubber-modified styrenic polymer is

In the presence of a rubber-modified component comprising diene-based polymer (c), styrene, _alpha - methyl styrene, C i~C ₄ alkylstyrene and aromatic Biel monomer component selected from halogen Kas styrene (a) and one or more, acrylonitrile, methacrylonitrile Tali acrylonitrile, C ₁ -C ₈ Arukirua chestnut rate, Ci～C ₈ alkyl methacrylates rate, maleic anhydride, Ma maleic acid dialkyl ester and N- substituted and unsubstituted maleimide The flame retardant according to claim 3, which is a graft polymer selected from Doka, which is obtained by copolymerizing the component (a) with one or more kinds of a copolymerizable bule-based monomer component (b). Resin composition.

7. The flame-retardant resin composition according to claim 6, wherein the rubber-modified styrenic polymer is an ABS resin.

8. The flame-retardant resin composition according to any one of claims 1 to 7, wherein the thermoplastic resin contains an aromatic polycarbonate.

9. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is PCZAB S polymer alloy.

10. The flame-retardant resin composition according to any one of claims 1 to 9, wherein a flame retardant is added in a ratio of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin.

11. The flame-retardant resin composition according to claim 10, wherein a flame retardant is added in a ratio of 5 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin.

12. Thermosetting resin is phenolic resin and / or epoxy resin 3. The flame-retardant resin composition according to claim 1 or 2.

13. The flame retardant according to any one of claims 1, 2 and 12, wherein the flame retardant is added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the thermosetting resin. Flammable resin composition.

14. The flame-retardant resin composition according to claim 13, wherein the flame-retardant is added in an amount of 5 to 50 parts by weight based on 100 parts by weight of the thermosetting resin.