JPH0987466A - Flame-resistant thermoplastic resin composition excellent in thermal stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-resistant thermoplastic resin composition prevented in the thermal deterioration of the resin in a kneading process and in a molding process and excellent in the mechanical strength and the recycling property. SOLUTION: This resin composition comprises (A) 5-98 pts.wt. of a polycarbonate resin, (B) 2-95 pts.wt. of a rubber-reinforced thermoplastic resin composition containing a grafted polymer produced by graft-polymerizing one or more kinds of vinylic compounds capable of being graft-copolymerized to a rubbery polymer to the rubbery polymer, wherein at least one kind of emulsifier used for the emulsion graft-polymerization is an emulsifier having a radical-polymerizable double bond in the molecule, and (C) a flame-retardant in an amount of 0.1-30 pts.wt. per 100 pts.wt. of the total amount of the components (A) and (B). The objective flame-retardant thermoplastic resin composition excellent in thermal stability, impact resistance, rigidity and recycling property is thus obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-reinforced thermoplastic resin in which free residual emulsifiers are extremely unlikely to diffuse into a polycarbonate-based resin blended therein, and the polycarbonate-based resin composition is unlikely to undergo thermal decomposition, resulting in kneading. The present invention relates to a flame-retardant thermoplastic resin composition that suppresses thermal deterioration of a resin during molding and processing, is less susceptible to burning, and has excellent mechanical strength and recyclability.

[0002]

2. Description of the Related Art Conventionally, ABS resins and the like, which are representative of rubber-reinforced thermoplastic resins, have been represented by vinyl cyanide monomers represented by acrylonitrile and styrene by the presence of a conjugated diene rubber latex represented by polybutadiene. Emulsion graft polymerization of aromatic vinyl monomer by batch polymerization, semi-batch polymerization or continuous polymerization, and then coagulation,
It is often made through dehydration, drying and extrusion processes. In this emulsion graft polymerization, in order to increase the stability of the latex and suppress the generation of coagulation, a method of adding an emulsifier consisting of a non-polymerizable carboxylic acid metal salt, a sulfate metal salt or the like in the emulsion graft polymerization step. Has been taken.
However, the use of a non-polymerizable emulsifier causes foaming in the residual monomer recovery step, necessitating the use of an antifoaming agent,
Further, it is not preferable because it causes a decrease in impact resistance and rigidity when a resin molded product is formed, and causes mold contamination during molding.

Further, when processing a composition of a rubber-reinforced thermoplastic resin and another thermoplastic resin, residual emulsifiers and defoamers diffuse into the thermoplastic resin to lower the heat resistance of the molded product,
It is not preferable because the phenomena of lower gloss and lower recyclability become remarkable. In JP-A-3-2204, a specific emulsifier is used for preventing them, but the effect is not sufficient.

Further, a method has been used in which various antioxidants are added at the time of extrusion or molding to suppress coloration and deterioration of impact resistance due to heat deterioration, but the impact resistance and fluidity at high temperature are not always required. It is impossible to suppress the decrease in the impact strength and the impact strength during retention.

As described above, according to the conventional technique, the emulsifier and the defoaming agent remain in the rubber-reinforced resin and diffuse into other thermoplastic resins when formed into a composition with the polycarbonate resin. As a result, it was difficult to obtain a thermoplastic resin composition having excellent heat resistance and mechanical strength.

[0006]

In contrast to the present situation, the present invention has extremely little free residual emulsifier and defoaming agent at the time of emulsion graft polymerization, and has thermal stability, mechanical strength and recyclability of the thermoplastic resin composition. It relates to a flame-retardant thermoplastic resin composition having excellent properties.

[0007]

That is, the present invention is
(A) Polycarbonate resin 5 to 98 parts by weight, (B)
In the process of producing a graft polymer obtained by graft-polymerizing one or more vinyl compounds graft-copolymerizable with the rubber-like polymer, at least one kind of emulsifier used for emulsion graft polymerization is a molecule. 2 to 95 parts by weight of a rubber-reinforced thermoplastic resin composition containing a graft polymer, which is an emulsifier having a radically polymerizable double bond,
For the total of 100 parts by weight of the components (A) and (B),
(C) A flame-retardant thermoplastic resin composition containing 0.1 to 30 parts by weight of a flame retardant.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polycarbonate resin (A) used in the present invention is produced by reacting a dihydric phenol with phosgene or a carbonic acid diester. As the dihydric phenol, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is particularly preferable. Further, part or all of bisphenol A may be substituted with another dihydric phenol compound. The dihydric phenol compound other than bisphenol A is, for example, a compound such as hydroquinone, 4,4 dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, or bis (4-hydroxyphenyl) ketone. is there. A homopolymer of these dihydric phenols, or
It may be a copolymer of two or more kinds or a blended product thereof.

Next, the composition and production method of the rubber-reinforced thermoplastic resin (B) of the present invention will be described. The rubber-reinforced thermoplastic resin can be obtained by graft-polymerizing a vinyl compound which is graft-polymerizable with a rubber-like polymer,
A vinyl polymer which is polymerized at the same time in this polymerization process may be included. Further, the vinyl polymer may be simultaneously or separately polymerized and blended.

The rubber-like polymer used in the present invention includes:
Polybutadiene, polyisoprene, polychloroprene,
Conjugated diene rubbers such as butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, ethylene-
Acrylic rubbers such as propylene rubber, ethyl acrylate, and butyl acrylate are preferable, and polybutadiene of a conjugated diene rubber, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer are preferable. These can be used in combination of two or more.

The content of the rubber-like polymer in the rubber-reinforced thermoplastic resin composition is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. If it is less than 5% by weight, impact resistance tends not to be obtained, and if it exceeds 60% by weight, fluidity and gloss during molding tend to be deteriorated, which is not preferable.

The preferred particle size of the rubber-like polymer in the rubber-reinforced thermoplastic resin composition is not particularly limited because it varies depending on the type of vinyl polymer used as the matrix. For example, in the case of ABS resin, the particle size is 150-150. 600
nm, preferably 200 to 500 nm, more preferably 250 to 450 nm. If the particle diameter is smaller than 150 nm, impact resistance cannot be obtained, and if it exceeds 600 nm, the gloss value decreases.

Examples of the vinyl compound which can be graft-polymerized on the rubber-like polymer particles used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate. Alkyl (meth) acrylates such as, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N Examples include maleimide-based monomers such as -phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but aromatic vinyl compounds and alkyl (meth) acrylates are preferable. ,cyan Vinyl compounds, a maleimide compound, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate.

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

Vinyl polymers which can be contained in the rubber-reinforced thermoplastic resin (B) include aromatic vinyl compounds such as styrene, α-methylstyrene, paramethylstyrene, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate. (Meth) acrylic acid such as acrylic acid and methacrylic acid, vinyl cyanide compound such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acid such as maleic anhydride, N-phenyl Maleimide,
Examples thereof include maleimide compounds such as N-methylmaleimide and N-cyclohexylmaleimide, and glycidyl group-containing compounds such as glycidyl methacrylate, but preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide compounds, Maleimide compounds, more preferably styrene, acrylonitrile,
It is a polymer composed of N-phenylmaleimide and butyl acrylate.

These vinyl compounds may be used alone or in combination of two or more, or may be used by copolymerization.

The method for producing the rubber-reinforced thermoplastic resin composition in the present invention is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization, and an emulsion method A two-stage polymerization method in which graft polymerization and solution polymerization or suspension polymerization are combined is exemplified. These can be any of a continuous type, a batch type, and a semi-batch type. Also, a graft polymer having a high rubber content is prepared in advance by the above method,
Later, a method of blending a thermoplastic resin containing a vinyl compound as a main component used at the time of graft polymerization produced by bulk polymerization, emulsion polymerization or suspension polymerization to obtain a desired rubber content is also used.

In the present invention, an emulsion graft system in which a vinyl compound is continuously added to a rubber-like polymer produced by emulsion polymerization together with an initiator, a molecular weight modifier and the like is preferable.

The pH during polymerization is not particularly limited, but a neutral pH (pH 7-9) is preferable from the viewpoint of graft reaction.

The emulsifier having a double bond capable of radical polymerization in the molecule (hereinafter abbreviated as a polymerizable emulsifier) used in the present invention has a hydrophilic group and a hydrophobic group in the compound, and a gas-liquid, Of the compounds capable of lowering the liquid-liquid and solid-liquid interfacial tension, the compound has one or more double bonds, and in particular, a conjugated diene rubber, an aromatic vinyl compound, a vinyl cyanide compound and / or Alternatively, it means one capable of radical polymerization with a (meth) acrylic acid ester compound. The hydrophilic group of the polymerizable emulsifier may be anionic, nonionic or cationic, but preferably has anionic properties, more preferably has both nonionic and anionic properties.

A non-polymerizable emulsifier may be used together with the polymerizable emulsifier during emulsion graft polymerization, but the total amount of the non-polymerizable emulsifiers derived from rubber is 4.0 parts by weight or less based on 100 parts by weight of the conjugated diene rubber. Should be. If it exceeds 4.0 parts by weight, the impact resistance of the rubber-reinforced thermoplastic resin composition is lowered, the rigidity is lowered, the gloss is lowered during high temperature molding, the mold is contaminated during molding, and the resin is colored, which is not preferable. . The non-polymerizable emulsifier referred to here may be an emulsifier generally used for emulsion polymerization, a rosin acid salt, a higher fatty acid salt,
Alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate,
Polyoxyethylene alkyl phenyl ether sulfate,
Examples thereof include anionic emulsifiers such as dialkylsulfosuccinates and nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers.

Examples of the polymerizable emulsifier used in the present invention include, but are not limited to, the following.

A polymerizable emulsifier represented by the following formula (1).

[0025]

Embedded image In the formula, X represents a (meth) allyl group, a (meth) acryloyl group or a (1-propenyl) vinyl group.

Y is hydrogen, or --SO ₃ M (M is hydrogen,
Sulfuric acid ester salt represented by alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, or -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon number) 1 to 4 hydroxyalkylammonium), or a phosphoric acid monoester salt represented by the following formula (1 ′).

[0027]

Embedded image (M ₁ and M ₂ are hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, and M ₁ and M ₂ may be different or the same.) R ₁ is An alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ₂ is hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ₃
Represents hydrogen or a propenyl group, A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and m represents an integer of 1 to 200.

Specific examples of the polymerizable emulsifier represented by the formula (1) include the following formulas (5) to (8).

[0029]

Embedded image (M represents an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkyl ammonium having 1 to 4 carbon atoms, and n represents a positive number of 1 to 100.)

[0030]

Embedded image (M represents an alkali metal or an alkaline earth metal, and n is 1
Represents a positive number from -100. )

[0031]

Embedded image (N represents a positive number of 10 to 200.)

[0032]

[Chemical 6] (M represents an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms, and n represents a positive number of 1 to 100.) (Meth) allyl represented by the following formula (2) Glycidyl ether derivatives and (meth) acrylic glycidyl ester derivatives.

[0033]

[Chemical 7] In the formula, X represents a (meth) allyl group or a (meth) acryloyl group.

Y is hydrogen, or --SO ₃ M (M is hydrogen,
Alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) or a sulfate ester salt represented by -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal) A carboxylic acid salt, a phosphoric acid monoester represented by the formula (1 ′), or a compound represented by the formula (1 ″) is shown.

[0035]

Embedded image (M ₁ is hydrogen, an alkali metal, an alkaline earth metal, ammonium, a hydroxyalkylammonium having 1 to 4 carbon atoms or an alkyl group having 8 to 30 carbon atoms which may have an alkylene oxide group having 2 to 4 carbon atoms. And M ₂ is hydrogen, an alkali metal, an alkaline earth metal, ammonium, or a hydroxyalkylammonium having 1 to 4 carbon atoms.) Z is an alkyl group having 8 to 30 carbon atoms, a substituted alkyl group, an alkenyl group, or a substituted alkenyl. A group, an alkylaryl group,
It represents a substituted alkylaryl group, an aralkylaryl group, a substituted aralkylaryl group, an acyl group or a substituted acyl group.

A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m is 0 to 100, and n is an integer of 0 to 50.

The following equations (9) to (15) are given as examples of equation (2).
An expression can be given.

[0038]

Embedded image (M is hydrogen or -SO ₃ M ₁ (M ₁ is an alkali metal,
Alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), Z ₁ represents an alkyl group having 8 to 30 carbon atoms, an alkylaryl group,
m shows the positive number of 0-100. )

[0039]

Embedded image (M represents an alkali metal or an alkaline earth metal, Z ₁ represents an alkyl group or an alkylaryl group having 8 to 30 carbon atoms, and m represents a positive number of 0 to 100.)

[0040]

Embedded image (Y ₁ represents the following formula (11 ′).)

[0041]

[Chemical 12] (M ₁ is an alkyl group having 8 to 30 carbon atoms which may have an alkylene oxide group having 2 to 4 carbon atoms, and M ₂ is alkali metal, alkaline earth metal, ammonium or hydroxy group having 1 to 4 carbon atoms. It is alkyl ammonium.)

[0042]

Embedded image (R represents an alkyl group having 4 to 30 carbon atoms and optionally having a substituent, and M represents an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkyl ammonium having 1 to 4 carbon atoms.)

[0043]

Embedded image A succinic acid derivative represented by the following formula (3).

[0044]

[Chemical 15] In the formula, X represents a (meth) allyl group or a (meth) acryloyl group.

B ₁ and B ₂ represent Y or Z shown below, and B ₁ and B ₂ are different from each other.

Y represents M or --SO ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms).

Z represents an alkyl group or an alkenyl group having 8 to 30 carbon atoms.

A is an alkylene group having 2 to 4 carbon atoms and an alkylene group having a substituent, and m and n are integers of 0 to 50.

As a concrete example of the expression (3), the following expression (1
6) to (19).

[0050]

Embedded image A compound represented by the following formula (4).

[0051]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group.

Y is hydrogen, or --SO ₃ M (M is hydrogen,
Sulfuric acid ester salt represented by alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, or -CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or carbon number) 1 to 4 hydroxyalkyl ammonium).

R ₁ and R ₃ are hydrogen or an alkyl group having 1 to 25 carbon atoms and may be the same or different,
R ₂ and R ₄ are each an alkyl group having 1 to 25 carbon atoms, a benzyl group,
Or a styryl group, which may be the same or different, and p represents an integer of 0 to 2.

A is an alkylene group having 2 to 4 carbon atoms or an alkylene group having a substituent, and m and n are integers from 0 to 50.

As a specific example of the equation (4), the following equation (2
0) and (21).

[0056]

Embedded image (M in the formula is hydrogen or alkali metal)

[0057]

Embedded image (M in the formula is hydrogen or an alkali metal) A (meth) allyl ether derivative and a (meth) acrylic ester derivative represented by the following formula (22).

[0058]

Embedded image In the formula, X represents a (meth) allyl group or a (meth) acryloyl group.

Y is hydrogen, a methyl group, or --SO
Sulfate ester salt represented by ₃ M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or -CH
₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or a phosphoric acid monoester salt represented by the formula (1 ′) Indicates.

Z represents an alkyl group having 8 to 30 carbon atoms.

A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m is 0 to 20, and n is an integer of 0 to 50.

As a specific example of the equation (22), the following equation (2)
3) and (24).

[0063]

[Chemical 21] A diol compound represented by the following formula (25).

[0064]

Embedded image In the formula, A is an alkylene group having 2 to 4 carbon atoms, R ₁ is a hydrocarbon group having 8 to 24 carbon atoms, R ₂ is hydrogen or a methyl group, and m and n have m + n of 0 to 100. And M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms.

As a specific example of the equation (25), the following equation (2
6) can be given.

[0066]

Embedded image A compound represented by the following formula (27).

[0067]

Embedded image In the formula, X represents a (meth) allyl group, a (meth) allyloxy group, a (meth) acryloyl group, a (meth) acryloyloxy group or the following formula (27 ′).

[0068]

Embedded image (R ₁ and R ₂ are hydrogen or a methyl group) Y is hydrogen or -SO ₃ M (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or a carbon number of 1 to 1).
4 hydroxyalkylammonium) or a carboxylic acid represented by —CH ₂ COOM (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms) A salt, a phosphoric acid monoester represented by the formula (1 ′), or a sulfosuccinic acid monoester salt represented by the formula (1 ″) is shown.

Z represents an alkylene group having 6 to 30 carbon atoms which may have a substituent.

A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n and m are integers from 0 to 50.

As a specific example of the expression (27), the following expression (2
8) to (30).

[0072]

[Chemical formula 26] Of these polymerizable emulsifiers, the formula (1) is preferred,
It is a polymerizable emulsifier represented by formula (2), (3) or (4), and particularly preferably a polymerizable emulsifier represented by formula (1).

Among the polymerizable emulsifiers represented by the formula (2),
Preferred structures are the polymerizable emulsifiers represented by formulas (9) and (11). As more preferred specific examples of formula (9), formulas (31) to (34) are more preferred of formula (11). As specific examples, formulas (35) and (36) can be exemplified.

[0074]

Embedded image

[0075]

Embedded image The polymerizable emulsifier represented by the formula (1) is particularly preferable, and as specific examples, the following formulas (37) to (41) are particularly preferable.

[0076]

[Chemical 29]

[0077]

Embedded image The polymer latex obtained by the present invention is usually coagulated with an inorganic salting-out agent and dehydrated and recovered. The salting-out agent used is not limited, but specific examples include aluminum sulfate, magnesium sulfate, calcium chloride, sulfuric acid and the like. It is preferable that the amount of the component derived from the residual salting-out agent contained in the resin after the dehydration and recovery be smaller.

The ratio of the polycarbonate resin (A) to the rubber-reinforced thermoplastic resin composition (B) is determined according to the required mechanical strength, rigidity, moldability and heat resistance,
It is necessary that (A) is 5 to 98 parts by weight and (B) is 2 to 95 parts by weight. The component (A) is preferably 20 to 80 parts by weight, the component (B) is 20 to 80 parts by weight, and more preferably the component (A) is 25 to 75 parts by weight and the component (B) is 75 to 25. Parts by weight.

The flame retardant (C) in the present invention is a so-called general flame retardant, and in addition to phosphorus compounds and halogen organic compounds, nitrogen-containing organic compounds such as melamine, magnesium hydroxide, aluminum hydroxide and the like. Inorganic compounds, antimony oxide, bismuth oxide and the like can be mentioned. Further, zinc oxide, metal oxides such as tin oxide, red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid,
Inorganic phosphorus compounds such as phosphoric anhydride, carbon fibers, fibers such as glass fibers, expanded graphite, silica, silica glass melts and the like are used, but preferably phosphorus compounds, or halogen organic compounds and halogens. It is a combined use of a system organic compound and antimony oxide.

The halogen-based organic compound includes general halogen-based flame retardants and halogen-containing phosphates in general. For example, examples of the halogen-based organic compound include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, and hexabromodiphenyloxide. Bromobutene, hexabromocyclododecane and the like are preferable, and a halogen-based organic compound having the structure of the following (42) is preferable, and a halogen-based organic compound of the following (43) is particularly preferable.

[0081]

[Chemical 31] n = 0 or a natural number, X independently represents chlorine or bromine, i, j, k, and l are each an integer of 1 to 4, and R
And R'independently represent hydrogen, a methyl group, the following epoxypropyl group,

[0082]

Embedded image Phenyl group or the following formula (where m represents 0, 1, 2, or 3)

[0083]

[Chemical 33]

[0084]

Embedded image n = 0 or a natural number, R and R ′ are both the following epoxypropyl groups,

[0085]

Embedded image Phenyl group or the following formula (where m represents 0, 1, 2, or 3)

[0086]

Embedded image On the other hand, as the halogen-containing phosphate ester, tris / chloroethyl phosphate, tris / dichloropropyl phosphate, tris / β-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneophosphate) are used. Pentyl phosphate) and condensed phosphoric acid esters thereof, etc., but preferably tris (tribromoneopentyl phosphate), tris (tribromophenyl) phosphate, tris (dibromophenyl)
It is a phosphate. These halogen-based organic compounds can be used alone or in combination of two or more.

Examples of the phosphate ester flame retardant include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylate. There are phosphoric acid esters such as nyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, and compounds obtained by modifying these with various substituents.

The condensed phosphoric acid ester flame retardant in the composition of the present invention has the general formula (46).

[0089]

Embedded image In the formula, R is a group selected from the following formulas A1 to A4

[0090]

Embedded image (In the formula, n is a positive number of 1 to 10 and Ar1 to Ar4 are each independently a phenyl group, a tolyl group or a xylyl group. When n is 2 or more, a plurality of Ar4's may be the same. May be different)), and preferably

[0091]

Embedded image (In the formula, Ar1 to Ar3 are the same or different and each is a phenyl group, a tolyl group, or a xylyl group other than the 2,6-xylyl group, and R = A4). It is a compound, and this phosphoric acid ester compound has particularly good flame retardant effect and heat resistance.

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

The blending amount of the flame retardant is determined according to the required level of flame retardancy, but it is necessary that the total amount of the resin composition is 0.1 to 30 parts by weight based on 100 parts by weight. . If the amount is less than 0.1 part by weight, the required flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered. It is preferably in the range of 1 to 25 parts by weight, and particularly preferably in the range of 3 to 22 parts by weight.

When a halogen-based compound is used as the flame retardant, a flame retardant aid can be used to enhance the flame retardant effect. The flame retardant aid is preferably a compound containing an element belonging to VB in the periodic table of elements, and specifically, a nitrogen-containing compound, a phosphorus-containing compound, antimony oxide, bismuth oxide and the like can be mentioned. Further, metal oxides such as iron oxide, zinc oxide and tin oxide are also effective. Of these, antimony oxide is particularly preferable, and specific examples thereof include antimony trioxide and antimony pentoxide. These flame-retardant aids may be those which have been subjected to a surface treatment for the purpose of improving dispersion in the resin and / or improving the thermal stability of the resin.

The amount of the flame retardant aid added is preferably 0.5 to 20 parts by weight. When the amount is less than 0.5 part by weight, the effect of the flame retardant aid is not sufficient, and when it exceeds 20 parts by weight, the resin is added. Mechanical strength and working fluidity of the are decreased. More preferably 1
15 parts by weight, particularly preferably 1 to 10 parts by weight.

Polytetrafluoroethylene as the anti-dripping agent of the present invention is not particularly limited, but fine powder or dispersion is preferable. The compounding amount in the resin needs to be in the range of 0.01 to 3 parts by weight.

Examples of the filler of the present invention include glass fiber, glass flake, carbon fiber, talc and mica. These types may be determined according to the required mechanical strength, rigidity, moldability and heat resistance. In addition, the blending amount is (A), (B) and (C)
1 to 50 parts by weight with respect to 100 parts by weight in total.

Further, it is optional to add known additives such as an antioxidant, an ultraviolet absorber, a lubricant, a release agent, an antistatic agent and a colorant to the resin composition of the present invention.

Further, the molding method of the molded article made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding and the like, and is not particularly limited. Examples of molded articles include wheel caps, spoilers, instrument panels of automobiles, and the like.

[0100]

The present invention will be described below in more detail with reference to examples. The present invention is not limited by the embodiments. The parts used below are parts by weight.

(Polycarbonate resin PC-1) Polycarbonate resin having a weight average molecular weight of 24,500.

(Production Method of Conjugated Diene Rubber): (Rubber Latex (S-1)) A substance (based on solid content) having the following composition was placed in a 50 liter autoclave whose inside was evacuated to a vacuum, and the temperature was raised to 65 ° C. Polymerization was carried out.

1,3-Butadiene 97.0 parts Acrylonitrile 3.0 parts t-Dodecyl mercaptan 0.2 parts Potassium rosinate 0.7 parts Beef tallow saponified fossil 0.3 parts Sodium persulfate 0.25 parts Sodium hydroxide 0.1 part Sodium hydrogen carbonate 0.35 part Deionized water 60.0 parts Polymerization was continued while continuously adding a solution having the following composition to the autoclave between 10 and 20 hours after the start of polymerization.

Potassium rosinate 0.3 part Beef tallow fossil soap 0.1 part Sodium persulfate 0.1 part Sodium hydroxide 0.05 part Sodium hydrogen carbonate 0.15 part Deionized water 50.0 parts After continuous addition is completed Then, the polymerization system was heated to 80 ° C. and cooled 26 hours after the initiation of the polymerization to complete the polymerization. After the polymerization, unreacted butadiene was removed. The weight average particle diameter of the latex determined by electron micrograph was 0.28 microns.
The latex had a pH of 10.1.

(S-2 to S-3) The operations were performed in the same manner as S-1 except for those described in Table 1. The results are summarized in Table 1.

[0106]

[Table 1] The rubber-reinforced resins R-1 to R-5 were obtained by the following method.

(R-1) 40 parts of rubber latex S-1 (solid content), 100 parts of ion-exchanged water, and 0.3 parts of potassium rosinate were placed in a 10-liter reactor, and the gas phase was replaced with nitrogen. The initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the following composition, a monomer mixture (E), and an aqueous solution (D) containing a polymerizable emulsifier represented by the formula (38) were continuously fed into a reactor for 5 hours. Was added. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows.

Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Ethylenediaminetetraacetic acid disodium (EDTA) 0.04 part Ion-exchanged water 50 parts The composition of the aqueous solution (D) is as follows. Is the street.

Polymerizable emulsifier Formula (37) 1.0 part Ion-exchanged water 20 parts The composition of the monomer mixture (E) is as follows.

Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 0.6 part Cumene hydroperoxide (CHP) 0.1 part Next, an antioxidant was added to the prepared graft polymer latex. Then, aluminum sulfate was added to coagulate, washed with water, dehydrated, and dried by heating to obtain a graft copolymer powder.

(R-2) R-1 except that the polymerizable emulsifier contained in the aqueous solution (D) in R-1 is the one shown in Table 2.
-1 was polymerized in the same manner.

(R-3) Polymerizable emulsifier (37) in rubber
40 parts (solid content) of rubber latex S-2 containing the formula and 100 parts of ion-exchanged water were put in a 10 liter reactor,
Carbon dioxide gas was bubbled in the reactor to adjust the pH to about 7. After further substituting the gas phase with nitrogen, the initial solution
The temperature was raised to 0 ° C.

Next, an aqueous solution (C) having the following composition
The monomer mixture (E), and the aqueous solution (D) containing the polymerizable emulsifier represented by the formula (37) were continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows.

Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Disodium ethylenediaminetetraacetate (EDTA) 0.04 part Ion-exchanged water 50 parts The composition of the aqueous solution (D) is as follows. Is the street.

Polymerizable emulsifier Formula (37) 1.0 part Ion-exchanged water 20 parts The composition of the monomer mixture (E) is as follows.

Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 1.0 part Cumene hydroperoxide (CHP) 0.1 part (R-4) The emulsifier in the rubber is a polymerizable emulsifier (37). 40 parts (solid content) of the rubber latex S-3 which is
Polymerization was carried out in the same manner as in R-1 except that the other conditions were shown in Table 2.

(R-5) 40 parts of rubber latex S-1 (solid content), 100 parts of ion-exchanged water, and 0.3 parts of potassium rosinate were placed in a 10-liter reactor, and the gas phase was replaced with nitrogen. The initial solution was heated to 70 ° C. Next, an aqueous solution (C) having the composition shown below, a monomer mixture solution (E), and an aqueous solution (D) were continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.

The composition of the aqueous solution (C) is as follows.

Ferrous sulfate 0.005 part Sodium formaldehyde sulfoxylate (SFS) 0.1 part Disodium ethylenediaminetetraacetate (EDTA) 0.04 part Ion-exchanged water 50 parts The composition of the aqueous solution (D) is as follows. Is the street.

Potassium rosinate 2.0 parts Ion-exchanged water 20 parts The composition of the monomer mixture liquid (E) is as follows.

Acrylonitrile 24 parts Styrene 36 parts t-Dodecyl mercaptan (t-DM) 0.6 part Cumene hydroperoxide (CHP) 0.1 part (Vinyl polymer (B-1)) in copolymer B-1 The composition of was determined by IR spectrum to be 40% by weight of acrylonitrile, 60% by weight of styrene, and intrinsic viscosity measured in methyl ethyl ketone (copolymer B-1, 0.617% by weight).
Medium, 30 ° C.) was 0.41.

[0124]

[Table 2] (Flame Retardant FR-1) Represented by Formula (43), n = 0 or a natural number, R and R ′ are compounds represented by the group represented by Formula (45), and the softening temperature is 105 ° C. Flame retardants.

(Flame retardant FR-2) triphenyl phosphate.

(Flame retardant FR-3) represented by the formula (46),
R = A4, the average value of n is 1.5, and Ar1 to Ar4
Flame retardant where is a phenyl group.

(Flame Retardant FR-4) A condensed phosphoric acid ester flame retardant containing the formula (47) as a main component, synthesized by the following method.

114 g (0.5 mol) of bisphenol A, 154 g (1.0 mol) of phosphorus oxychloride, and 1.4 g (0.015 mol) of anhydrous magnesium chloride were charged into a 500 ml four-necked flask equipped with a stirrer / reflux tube. ,
It was made to react at 70-140 degreeC under nitrogen stream for 4 hours. After completion of the reaction, the flask was evacuated to a pressure of 200 mmHg or less by a vacuum pump while maintaining the reaction temperature, and unreacted phosphorus oxychloride was collected by a trap. The flask was then cooled to room temperature, 61 g (0.5 mol) of 2,6 xylenol,
And anhydrous aluminum chloride 2.0 g (0.015 mol)
Was added, and the mixture was heated to 100 to 150 ° C. and reacted for 4 hours.

Then, the flask was cooled to room temperature, 141 g (1.5 mol) of phenol was added, and the mixture was heated to 100 to 150 ° C.
And kept for 4 hours to complete the reaction. The pressure was reduced to 1 mmHg at the same temperature, and unreacted phenols were distilled off. Hydrogen chloride gas generated during the reaction was collected with an aqueous sodium hydroxide solution, and the amount of the generated hydrogen chloride was measured by neutralization titration to monitor the progress of the reaction. After the generated crude phosphate was washed with distilled water, the solid content was removed with a filter paper (# 131 manufactured by Advantech). Vacuum drying gave a pale yellow, clear purified product.

As a result of GPC measurement (LC-10A manufactured by Shimadzu, column: Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the purity of the component of formula (47) was 63% by weight.

(Flame Retardant FR-5) Phosphate ester flame retardant containing formula (48) as a main component, synthesized by the following method.

192 g of phosphorus oxychloride in the first reaction step
(1.25 mol), flame retardant FR-4 except that 122 g (1.0 mol) of 2,6-xylenol was used in the second reaction step and phenol 94 (1.0 mol) was used in the third reaction step.
A light yellow transparent purified product was obtained in the same manner as.

As a result of GPC measurement (LC-10A manufactured by Shimadzu, column: Toso TSKgel ODS-80T, solvent: methanol / water 90/10), the purity of the component of formula (48) was 75% by weight.

(Dripping inhibitor) -PTFE (polytetrafluoroethylene) Average particle size (measured according to ASTM-D1457) is 5
00 μm, melting point (measured according to JIS-K6891)
At 327 ° C.

(Glass Fiber) A glass fiber having a diameter of 13 μm which has been subjected to silane coupling treatment.

(Other Additives) EBS is ethylenebisstearylamide.

Examples 1 to 20 and Comparative Examples 1 to 6 The resins prepared as described above were blended with the compositions (units are parts by weight) listed in Tables 3 to 4, and the cylinder temperature was 240 ° C.
Twin screw extruder set to (ZSK-25, W & P)
Were kneaded and granulated in order to obtain pellets, and the following evaluations were performed.

Examples 21 to 22 and Comparative Example 7 The resins prepared as described above were blended in the compositions (units are parts by weight) listed in Tables 3 to 4 and the cylinder temperature was 240 ° C.
Twin screw extruder set to (ZSK-25, W & P)
Kneaded and granulated. However, the glass fiber was side-fed from near the tip of the extruder. The pellets thus obtained were evaluated as follows.

The measuring method in the examples of the present invention is as follows.

(Physical Property Evaluation Method) (1) IZOD Impact Strength Pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain test pieces. The test was carried out on a test piece having a notch of 1/2 inch × 1/4 inch × 5/2 inch based on ASTM-D256.

(2) Retention IZOD Impact Strength Pellets were retained in a molding machine at 260 ° C. for 20 minutes and then molded at a mold temperature of 65 ° C. to obtain test pieces. The test is A
Based on STM-D256, a test piece having a notch of ½ inch × 1/4 inch × 5/2 inch was used.

(3) Residence Coloring Degree The pellets were molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. to obtain reference test pieces. Subsequently, a test piece was obtained by allowing it to stay in the molding machine at 240 ° C. for 20 minutes and molding in the same manner.

Test piece: length 216 mm × width 12.6 mm
× Thickness 3.2 mm The test was carried out by using Suga Test Instruments Co., Ltd. SM color computer, model SM-5, and the yellow index (YI of the sample before retention) of the test sample relative to the reference test sample- (after retention) The sample was measured for YI) (ΔYI). The sample was measured at the center.

(4) Flame Retardancy Measurement based on UL94 standard vertical combustion test (thickness 1/16 inch).

The results are summarized in Tables 3-4.

[0146]

[Table 3]

[0147]

[Table 4] The following is clear from the examples and comparative examples.

The rubber-reinforced thermoplastic resin and the polycarbonate-based resin composition (Examples 1 to 22) using the graft copolymer all have impact resistance (IZOD impact strength).
Excellent in suppressing the coloration during impact and the decrease in impact strength,
It has excellent mechanical strength and recyclability.

[0149]

INDUSTRIAL APPLICABILITY According to the present invention, the free residual emulsifier of the rubber-reinforced thermoplastic resin is extremely unlikely to diffuse into the polycarbonate resin to be blended, and the thermal decomposition of the thermoplastic resin composition hardly occurs. As a result, during kneading, It is possible to obtain a thermoplastic resin composition in which thermal deterioration of the resin during molding is suppressed and which has excellent mechanical strength and recyclability.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08L 69/00 LPP C08L 69/00 LPP // (C08L 69/00 27:18 51:04)

Claims (7)

[Claims] 1. (A) Polycarbonate resin 5 to 98
By weight, (B) an emulsifier used for emulsion graft polymerization in the process of producing a graft polymer obtained by graft-polymerizing one or more vinyl compounds graft-copolymerizable with the rubber-like polymer on the rubber-like polymer. 2) A rubber-reinforced thermoplastic resin composition containing a graft polymer, at least one of which is an emulsifier having a radically polymerizable double bond in the molecule
To 95 parts by weight, and 0.1 to 30 parts by weight of the flame retardant (C) based on 100 parts by weight of the components (A) and (B) in total, and a flame retardant thermoplastic resin composition. . 2. The flame-retardant thermoplastic resin composition according to claim 1, wherein the flame retardant is a halogen-based flame retardant. 3. The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant is a phosphoric acid ester flame retardant. 4. The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant is a condensed phosphoric acid ester flame retardant. 5. A flame-retardant thermoplastic resin prepared by blending 0.01 to 3 parts by weight of polytetrafluoroethylene with respect to 100 parts by weight of the flame-retardant thermoplastic resin composition according to claim 1. Composition. 6. A flame-retardant thermoplastic resin composition containing 0.1 to 50 parts by weight of a filler with respect to 100 parts by weight of the flame-retardant thermoplastic resin composition according to claim 1. 7. A molded article comprising the flame-retardant thermoplastic resin composition according to claim 1.