JP2003201385A - Flame-retardant thermoplastic resin composition for office automation equipment and household electric appliance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a melt-dripping type flame-retardant thermoplastic resin composition for office automation equipment and a household electric appliance, having excellent transparency and laser marking properties. <P>SOLUTION: The composition is obtained by compounding (A) 100 pts.wt. of a thermoplastic resin composition mainly of a rubber-reinforced polymer (a) produced by graft-polymerizing a monomer component (styrene, acrylonitrile and the like) containing ≥50 wt.% of a (meth)acrylic ester compound (MMA or the like) in the presence of a rubbery polymer (polybutadiene or the like), (B) 5-20 pts.wt. of a phosphoric ester compound and/or condensed phosphoric ester compound and (C) 0-5 pts.wt. of a compound containing at least one selected from the group consisting of a polyether ester amide and polyether amide each containing 35-65 wt.% ethylene oxide unit, and a hydrogenated aromatic vinyl-conjugated diene block copolymer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition for office automation and home appliances, which has excellent transparency and laser marking property and has a melt dropping property.

[0002]

2. Description of the Related Art Conventionally, ABS resin with flame retardancy is
Due to its excellent moldability and mechanical properties, it is widely used in the electrical and electronic fields and OA equipment fields.
However, the ABS resin has a drawback that it easily burns, and in the field where flame retardancy is required, a flame retardant ABS resin composition containing a flame retardant, a flame retardant aid, etc. is generally used. . On the other hand, in recent years, the requirement for transparency has been increasing as a design requirement, but normally ABS resin is opaque, and a flame-retardant ABS resin composition obtained by adding a flame retardant to ABS resin is naturally opaque. . Further, when a flame retardant is simply added to a transparent ABS resin that has been conventionally used for transparency, flame retardancy is obtained, but transparency is impaired. Therefore, until now, there is no technique for making the ABS resin composition flame-retardant while maintaining the transparency. Further, there is known a laser marking technique in which when a resin material prepared by mixing a thermoplastic resin with a certain black compound is irradiated with laser light, the irradiated portion is changed to black, white or chromatic color. Such laser marking technology is used for key printing on keyboards, character printing on OA device panels such as FAX machines, etc., and does not use ink or coating materials, as compared with the tampo printing that has been used conventionally. It is excellent in terms of cost, durability of letters, and recyclability of resin. As described above, a flame-retardant ABS resin composition which is transparent and has excellent laser marking property has not been developed so far.

[0003]

DISCLOSURE OF THE INVENTION In view of the present situation, the present inventors have studied the development of materials, and as a result, have found that a resin composition having a specific constitution, a flame retardant having a specific structure, and a need. It has been found that a flame-retardant thermoplastic resin composition having a melt-dripping property, which is excellent in transparency and laser marking property, can be provided by blending a black compound accordingly, and has completed the present invention.

[0004]

The present invention is as follows. (1) A rubber-reinforced polymer (a) obtained by graft-polymerizing a monomer component containing 50% by weight or more of a (meth) acrylic acid ester compound in the presence of (A) a rubbery polymer is a main component. (B) to 100 parts by weight of the thermoplastic resin
5 to 20 parts by weight of the phosphoric acid ester compound represented by the general formula (I) and / or the condensed phosphoric acid ester compound represented by the general formula (II), and 35 to 65 parts by weight of the (C) ethylene oxide unit. %, At least one selected from the group consisting of polyether ester amides, polyether amides, and hydrogenated aromatic vinyl-conjugated diene block copolymers is blended in an amount of 0 to 5 parts by weight. A flame-retardant thermoplastic resin composition for office automation and home appliances (hereinafter, also simply referred to as "flame-retardant thermoplastic resin composition"). (2) The flame-retardant thermoplastic resin composition for office automation / home electric appliances according to the above (1), wherein the monomer component further contains a functional group-containing vinyl monomer. (3) 5 to 20 parts by weight of the component (B), 0 to 5 parts by weight of the component (C), and 0.01 to 5 parts by weight of the black compound (D) based on 100 parts by weight of the thermoplastic resin (A). The flame-retardant thermoplastic resin composition for office automation / home electric appliances according to the above (1) or (2), which comprises: (4) Various parts, housing, chassis, tray,
Above (1) used for buttons, switches or display frames
A flame-retardant thermoplastic resin composition for office automation / home appliances according to any one of (1) to (3).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) The thermoplastic resin of the present invention is
The rubber-reinforced polymer (a) is the main component. The rubber-reinforced polymer (a) is obtained by graft-polymerizing a monomer component containing 50% by weight or more of (meth) acrylic acid ester in the presence of a rubbery polymer. The rubber-reinforced polymer (a)
Can also be obtained by graft-polymerizing a (meth) acrylic acid ester compound simple substance onto the rubbery polymer, and further,
Mixture with at least one monomer selected from the group of monomers such as aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds and acid anhydrides, which are copolymerizable with (meth) acrylic acid ester compounds. It can also be obtained by graft polymerization of. The (A) thermoplastic resin may be the rubber-reinforced polymer (a) alone, or a polymer or copolymer of at least one monomer selected from the above-mentioned group of monomers may be separately produced. However, it may be produced by blending with the rubber-reinforced polymer (a) (graft copolymer).

Examples of the rubbery polymer include polybutadiene, hydrogenated products of polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer,
Ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene-1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene- Examples thereof include isoprene-styrene block copolymers, hydrogenated diene-based (block, random, and homo) polymers such as SEBS, polyurethane rubber and silicone rubber. Examples of the styrene-butadiene copolymer include a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, and the like.
Further, the hydrogenated product of the styrene-butadiene block copolymer includes, in addition to the hydrogenated product of the block copolymer, a hydrogenated product of a styrene block and a styrene-butadiene random copolymer. The rubbery polymer of the present invention may be used alone, or
It is also possible to use a mixture of two or more species.

The average particle size of the rubbery polymer is preferably 150 to 500 nm, more preferably 150.
˜400 nm, particularly preferably 200 to 350 nm. When the average particle diameter is less than 150 nm, the resulting flame-retardant thermoplastic resin composition has low impact resistance, while 500 nm
If it exceeds, the transparency of the resin composition, especially the haze value (Haz
e) is reduced. The above rubbery polymers may be used alone or as a mixture of two different rubbery polymers having different average particle sizes.

The amount of the rubbery polymer contained in the rubber-reinforced polymer (a) is preferably 5 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight. When the compounding amount of the rubbery polymer is less than 5% by weight,
When the impact strength is lowered, on the other hand, when it exceeds 40% by weight, the rigidity and the flammability are deteriorated.

Examples of the (meth) acrylate compound used in the rubber-reinforced polymer (a) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate,
Acrylic esters such as octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2
Examples thereof include methacrylic acid esters such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Among these, methyl acrylate, butyl acrylate, and methyl methacrylate are preferable.

The compounding amount of the (meth) acrylic acid ester compound in the rubber-reinforced polymer (a) is 50 in all the monomer components.
The amount is at least wt%, preferably 50 to 90 wt%, more preferably 55 to 80 wt%. The amount of the (meth) acrylic acid ester compound is 50% by weight based on the total amount of the monomer components.
When it is above, the transparency and the laser marking property are excellent, but when it is less than 50% by weight, the transparency is lowered.

Examples of the monomer component copolymerizable with the (meth) acrylic acid ester include aromatic vinyl compounds, vinyl cyanide compounds, acid anhydrides and maleimide compounds. As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene,
Methyl-α-methylstyrene, divinylbenzene, 1,
1-diphenyl styrene, N, N-diethyl-p-aminoethyl styrene, N, N-diethyl-p-aminomethyl styrene, vinyl pyridine, vinyl xylene and the like can be mentioned, in particular styrene, α-methyl styrene, p-methyl. Styrene is preferred. When 10 to 50% by weight, preferably 20 to 30% by weight, of α-methylstyrene is used in the monomer component, heat resistance can be imparted to the flame-retardant thermoplastic resin composition of the present invention.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and maleic anhydride is preferable. Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide. And N-phenylmaleimide is preferred. These monomer components may be used alone or in admixture of two or more.

Further, a vinyl monomer having a functional group may be copolymerized with the above-mentioned monomer component, if necessary. Specific examples of the functional group-containing vinyl monomer include:
Glycidyl acrylate, glycidyl methacrylate,
Epoxy group-containing unsaturated compounds such as allyl glycidyl ether; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene,
Trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Unsaturated hydroxyl group-containing compounds such as hydroxystyrene; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; amino group-containing unsaturated compounds such as acrylamine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate and aminostyrene. Unsaturated acids such as acrylic acid and methacrylic acid; unsaturated compounds containing an oxazoline group such as vinyloxazoline. The above functional group-containing vinyl monomers may be used alone or in admixture of two or more. By copolymerizing these functional group-containing vinyl monomers, when other resins are blended, the interface adhesion (compatibility) with the resins can be increased. The amount of the functional group-containing vinyl monomer in the rubber-reinforced polymer (a) is preferably 0.1 to 15% by weight, more preferably 0.5% by weight in the monomer component.
~ 12% by weight.

The content of the monomer component other than the (meth) acrylic acid ester compound in the rubber-reinforced polymer (a) is 50.
It is less than 40% by weight, preferably less than 40% by weight and more preferably less than 40% by weight and more than 20% by weight. When the content of the monomer component other than the (meth) acrylic acid ester compound is 50% by weight or more, the transparency is lowered. The compounding amount of all the monomer components in the rubber-reinforced polymer (a) is preferably 95 to 60% by weight, more preferably 95 to 70% by weight, and particularly preferably 90 to 70% by weight. If the amount of all the components of the monomers is more than 95% by weight, the impact strength is lowered, while if less than 60% by weight, the rigidity and the flammability are deteriorated.

The graft ratio of the rubber-reinforced polymer (a) is preferably 10 to 100%, more preferably 15.
˜90%, particularly preferably 20 to 70%. If the graft ratio is less than 10%, the resulting flame-retardant resin composition has an unsatisfactory appearance and a decrease in impact strength, which is not preferable. on the other hand,
If it exceeds 100%, the moldability is poor. Here, the graft ratio (%) is a value obtained by the following equation, where x is the weight of the rubber component in 1 g of the rubber-reinforced polymer and y is the weight of the methyl ethyl ketone insoluble matter. Is. Graft ratio (%) = [(y−x) / x] × 100

Also, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the methyl ethyl ketone soluble component which is the matrix component of the rubber-reinforced polymer (a) of the present invention.
Is preferably 0.1 to 1.0 dl / g, more preferably 0.2 to 0.9 dl / g, and particularly preferably 0.3 to
It is 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the flame-retardant thermoplastic resin composition of the present invention having excellent impact resistance and molding processability (fluidity) can be obtained. The graft ratio (%) and the intrinsic viscosity [η] can be easily controlled by changing the type and amount of the polymerization initiator, chain transfer agent, emulsifier, solvent, etc., and further the polymerization time, the polymerization temperature, etc. You can

The difference between the refractive index of the rubber-like polymer (rubber component) of the rubber-reinforced polymer (a) of the present invention and the refractive index of the matrix resin is preferably 0.05 or less, more preferably 0. 02 or less, particularly preferably 0.01 or less. When the difference in the refractive index is within the above range, the flame-retardant thermoplastic resin composition of the present invention having good transparency can be obtained.

Further, the haze value (Haze) of the rubber-reinforced polymer (a) of the present invention is preferably 15 or less, when a molded product (thickness 2.4 mm) of a flame-retardant thermoplastic resin composition is used, It is preferably 10 or less, particularly preferably 8 or less. The total light transmittance (Tt) of the rubber-reinforced polymer (a) of the present invention is preferably 75% or more, when a molded product (thickness 2.4 mm) of a flame-retardant thermoplastic resin composition is used, Preferably 80% or more, particularly preferably 85
% Or more.

The rubber-reinforced polymer (a) of the present invention is a known emulsion polymerization, suspension polymerization or solution of a monomer component containing 50% by weight or more of an acrylic ester compound in the presence of a rubbery polymer. Radical graft polymerization such as polymerization and bulk polymerization can be carried out for production. At this time, for emulsion polymerization,
A polymerization initiator, a chain transfer agent (molecular weight modifier), an emulsifier, water and the like are used. The rubber-like polymer and the monomer component used for producing the rubber-reinforced polymer (a) may be polymerized by adding the monomer component at once in the presence of the total amount of the rubber-like polymer. Alternatively, the polymerization may be carried out in divided or continuous addition. Moreover, you may superpose | polymerize by the method which combined these. Further, all or a part of the rubbery polymer may be added during the polymerization to polymerize.

As the polymerization initiator, organic hydroperoxides represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like and sugar-containing pyrophosphate prescription, sulfoxylate prescription and the like are represented. Redox system by combination with a reducing agent, or persulfates such as potassium persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO),
Peroxides such as lauroyl peroxide, t-butyl peroxylaurate and t-butyl peroxymonocarbonate are used. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% of the total amount added.
It is not more than 25% by weight, preferably not more than 25% by weight.
Furthermore, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator used is usually 0.1 to 1.5% by weight, preferably 0.2 to 0.7% by weight, based on the monomer components.

Known chain transfer agents can be used.
Specifically, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethyl thiuram sulfide, and tetraethyl thiuram sulfide. Hydrocarbon salts such as carbon chloride, ethylene bromide and pentaphenylethane, terpenes, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, α-methylstyrene and the like can be mentioned. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to
2.0% by weight is used.

As the emulsifier used in the emulsion polymerization, known emulsifiers can be used. Specifically, sulfuric acid esters of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, anionic surface active agents such as phosphoric acid Agents, nonionic surfactants such as an alkyl ester type of polyethylene glycol and an alkyl ether type. These may be used alone or in combination of two or more. The amount of emulsifier used is usually
It is usually 0.3 to 5.0% by weight based on the monomer component.

When the rubber-reinforced polymer (a) is produced by emulsion polymerization, it is usually purified by washing the powder obtained by coagulating with a coagulating agent and then drying. As the coagulant, calcium chloride, magnesium sulfate, magnesium chloride, inorganic salts such as sodium chloride, sulfuric acid,
Acids such as hydrochloric acid can be used.

The thermoplastic resin (A) of the present invention may be the above-mentioned rubber-reinforced polymer (a) alone or, if necessary, a (co) polymer may be added to the rubber-reinforced polymer (a). . Here, the (co) polymer may have the same composition as the monomer component of the rubber-reinforced polymer (a) or may have a different composition. Further, the (co) polymer may be a combination of several (co) polymer components. (A) In the thermoplastic resin,
The content of the (co) polymer other than the rubber-reinforced polymer (a) is
It is less than 50% by weight, preferably 0 to 40% by weight, more preferably 0 to 30% by weight in the component (A).

Typical examples of the thermoplastic resin (A) include the following compositions, but the scope of rights of the present invention is:
Unless the scope of the claims is exceeded, the examples are not limited to the following examples. A grafted with methyl methacrylate (MMA)
BS resin MMA graft polymerized ABS resin / MMA-styrene (ST) -acrylonitrile (AN) terpolymer MES graft polymerized AES resin Styrene-butadiene rubber graft polymerized MMA-ST-AN resin styrene -MMA for hydrogenated butadiene copolymer
-ST-AN graft polymerized resin

Next, the flame retardant (B) of the present invention is a phosphoric acid ester compound represented by the general formula (I) and / or a condensed phosphoric acid ester compound represented by the general formula (II). .

Specific examples of the phosphoric acid ester compound represented by the general formula (I) include bis- (phenyl)-
Methyl phosphate, bis- (ethyl) -phenyl phosphate, bis- (ethyl) -2,6-dimethylphenyl phosphate, bis- (phenyl) -ethyl phosphate, bis- (phenyl) -butyl phosphate, bis- (neopentyl)- Phenyl phosphate, bis-
(4-methylphenyl) -2-ethylhexyl phosphate, bis- (2-ethylhexyl) -phenyl phosphate, bis- (phenyl) -2-ethylhexyl phosphate, bis- (phenyl) -octyl phosphate, bis- (octyl) phenyl phosphate , Screw-
(3,5,5-Trimethylhexyl) phenyl phosphate, bis- (2,5,5-trimethylhexyl) -4
-Methylphenyl phosphate, bis- (phenyl)-
Isodecyl phosphate, bis- (dodecyl) -4-methylphenyl phosphate, bis- (dodecyl) phenyl phosphate, tris- (phenyl) phosphate,
Tris- (2-methylphenyl) phosphate, tris- (4-methylphenyl) phosphate, bis- (2-
Methylphenyl) phenyl phosphate, bis- (4-
Methylphenylphenyl) phenyl phosphate, bis- (phenyl) -2-methylphenylphosphate, bis- (phenyl) -4-methylphenylphosphate,
Tris- (isopropylphenyl) phosphate, bis- (isopropylphenyl) phenylphosphate, bis- (phenyl) -isopropylphenylphosphate, tris- (nonylphenyl) phosphate, tris- (2,6-dimethylphenyl) phosphate, bis-
(2,6-dimethylphenyl) phenyl phosphate,
Bis- (2,6-dimethylphenyl) -2,6-dimethylphenyl phosphate, bis- (2,6-dimethylphenyl) -4-t-butylphenyl phosphate, bis- (2,6-dimethylphenyl) -4 -Methylphenyl phosphate, bis- (2,6-dimethylphenyl)-
They are 3-methylphenyl phosphate, bis- (2,6-dimethylphenyl) -4-isopropylphenyl phosphate, and bis- (2,6-dimethylphenyl) -2-isopropylphenyl phosphate.

The condensed phosphorus represented by the general formula (II)
The acid ester compound can be one compound or two
With a mixture of different condensed phosphate compounds
Any of these forms can be used. blend
In the case of, the value of N is the mixture of condensed phosphoric acid ester compounds.
It represents the average value in the product. R which is an aryl group^Four, R⁵, R
⁶And R⁷Is preferably a cresyl group, a phenyl group,
Xylenyl group, propylphenyl group, butylphenyl
From the group of groups and their chlorinated or brominated derivatives
At least one selected. The aryl group is
Hydrogen atom of is replaced by halogen atom or alkyl group
It may have been done. The arylene group X is, for example, a resor
Shinol, hydroquinone, bisphenol A and this
Dihydroxy compounds such as their chlorinated and brominated compounds
It is a group derived from a thing. These compounds are
The body is well known. The above condensations, each having a different N value
A mixture of phosphate ester compounds should also be easy to use
You can Condensed phosphoric acid ester compound preferably used
Is j, k, l, and m are all 1 and R^Four,
R ⁵, R⁶And R⁷Are all phenyl groups, and X is
A general formula in which N is 1.2 to 1.7, which represents a phenylene group.
A condensed phosphoric acid ester compound represented by (II) or
It is a mixture of acid ester compounds.

The flame retardant (B) of the present invention is 5 to 20 parts by weight, preferably 5 to 17 parts by weight, more preferably 6 to 15 parts by weight, and particularly preferably 100 parts by weight of the thermoplastic resin (A). Is used in an amount of 8 to 13 parts by weight. The component (B) can be arbitrarily blended within an amount of 5 to 20 parts by weight with respect to 100 parts by weight of the component (A), and if the amount is less than 5 parts by weight, the flammability is reduced. descend. on the other hand,
Use of the component (B) more than necessary is negative in terms of cost and physical properties, and especially when the amount used exceeds 20 parts by weight, the impact resistance decreases.

The flame-retardant thermoplastic resin composition of the present invention comprises
For the purpose of improving impact resistance, a polyether ester amide, a polyether amide, and an aromatic vinyl-conjugated diene-based block copolymer containing (C) ethylene oxide units in an amount of 35 to 65% by weight are added, if necessary. At least one selected from the group of hydrogenated compounds can be blended. Examples of the polyether ester amide include a combination of polyamide / terephthalic acid, isophthalic acid, or aliphatic (or aromatic) dicarboxylic acid such as adipic acid / aliphatic diol such as ethylene glycol,
Examples thereof include graft reaction products and block reaction products in combination with polyamide ester and ethylene oxide. Examples of the polyether amide include a mixture of a salt of dicarboxylic acid such as hexamethylene diamine and adipic acid salt and diamine, or a graft reaction product or a block reaction product of lactam and ethylene oxide. The refractive index of the above polyether ester amide or polyether amide is preferably 1.49 to 1.53, more preferably 1.51 to 1.52.

The content of ethylene oxide unit in the polyether ester amide or polyether amide constituting the component (C) is 35 to 65% by weight, preferably 40 to 60% by weight. When the content of the ethylene oxide unit is less than 35% by weight, the transparency is lowered, while when it exceeds 65% by weight, impact strength and thermal stability are lowered.

[0032] Aromatic vinyl - The hydrogenated product of the conjugated diene block copolymer, derivatives obtained a block copolymer having a composition represented by the general formula X _{p ·} Y q · Z _r hydrogenated Is. However, X is a polymer block of an aromatic vinyl compound, Y is an elastomer polymer block of a conjugated diene, Z is a coupling agent residue such as Sn and Si, and p and q are integers of 0 to 5, respectively. And r is 0 or 1. The aromatic vinyl compound constituting X is preferably styrene, α-methylstyrene, vinyltoluene, etc., and styrene is particularly preferable. As the conjugated diene constituting Y above, butadiene and isoprene are preferable. The refractive index of the hydrogenated product of the aromatic vinyl-conjugated diene block copolymer is
It is preferably 1.49 to 1.53, and more preferably 1.50 to 1.52.

The blending amount of the component (C) in the flame-retardant thermoplastic resin composition of the present invention can be 5 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A), and within this range. If so, impact strength can be significantly improved while maintaining transparency. The blending amount of the component (C) is preferably 0.5.
-3 parts by weight, more preferably 1-3 parts by weight. If the blending amount exceeds 5 parts by weight, flame retardancy and transparency are deteriorated, which is not preferable.

5 to 20 parts by weight of the component (B), 0 to the component (C) per 100 parts by weight of the thermoplastic resin (A) of the present invention.
When 5 parts by weight and 0.01 to 5 parts by weight of the black compound (D) are blended, a flame-retardant thermoplastic resin composition having a laser marking property is obtained. The black compound (D) used in the present invention is 4 if it is represented by a wavelength-reflectance curve.
The reflectance is 1 for the entire range of wavelengths from 00 to 700 nm.
It is 0% or less, preferably 5% or less. That is, any compound that absorbs light having a wavelength in the entire region of 400 to 700 nm can be used as the component (D) of the present invention.

Examples of the black compound (D) include carbon black, black iron oxide, titanium black, black dye,
Examples include graphite. As carbon black, any of acetylene black, channel black, furnace black, Ketjen black and the like can be used. The preferred particle size of carbon black is 10 to 80 n.
m, and more preferably 12 to 40 nm. The smaller the particle size, the better the dispersibility in the resin, and the better the laser marking color development. Further, the preferred specific surface area of carbon black is 20 to 1,500 m ² / g, the preferred oil absorption is 35 to 300 ml / 100 g, and the preferred pH is 2.
It is -10.

Black iron oxide is Fe ₃ O ₄ or FeO.
- iron oxide black represented by _Fe 2 _{O 3.} The preferable particle size of the black iron oxide is 0.3 to 0.8 μm, more preferably 0.4 to 0.6 μm, and its shape may be spherical, cubic, needle-like, etc. ,
Cubic is preferred. Furthermore, titanium black is a compound obtained by reducing titanium dioxide.
The preferable particle size of titanium black is 0.1 to 60 μm,
More preferably, it is 1 to 20 μm.

When the flame-retardant thermoplastic resin composition of the present invention is used as a laser marking thermoplastic resin composition, dyes, organic pigments and the like may be added.
By combining these dyes, organic pigments, and the like with a black compound, laser marking properties exhibiting a chromatic color can be obtained. If the above dyes and organic pigments are represented by a wavelength-reflectance curve, the reflectance is partially 40% or more in the wavelength range of 400 to 700 nm, preferably 5%.
It is a dye / organic pigment having an area of 0% or more. By properly selecting these dyes and organic pigments, yellow,
It can produce chromatic colors such as red, blue, green, and purple in bright colors. Basically, the colors of the dyes and organic pigments to be blended are
The irradiated part is colored when the laser light is irradiated.

Dyes usable in the present invention include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes,
Ketoimine dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, thiazole dye, indamine dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone dye,
Examples thereof include anthraquinone dyes and indigoid dyes.

Specific examples of these dyes include Mord.
ant Green 4, Disperse Yell
ow 14, Disperse Yellow 31,
Acid Yellow 2, Direct Yell
ow 59, Basic Yellow 2, Basi
c Orange 23, Direct Orange
71, Direct Red 28, Acid Re
d 52, Solvent Blue 22, Acid
Blue 59, Modern Blue 10, A
cid Blue 45, Vat Blue 41, Toluidine Maroon, Permanent Red AG, Hansa Yellow G, Hansa Yellow 10G, Benzidine Orange 2G
And so on.

As the organic pigment, those generally used can be used. Among them, the coordinating metal is calcium, nickel, iron, barium, sodium,
Copper, molybdenum, cobalt, manganese, zinc, titanium,
Those such as magnesium and potassium are preferable. Specific organic pigments include Watching Red (Ca), Green Gold (Ni), Pigment Green B (F)
e), Pigment Scarlet 3B (Ba), Fast Sky Blue (Ba), Phthalocyanine Green (F)
e), phthalocyanine blue (Cu), brilliant carmine 6B (Ca), bordeaux 10B (Na), resole red R (Na), lake red D (Na), brilliant scarlet G (Ca), manganese violet (Mn), cobalt Examples include violet (Co). The elements contained in the organic pigment are shown in parentheses after these names.

The blending amount of the component (D) in the flame-retardant thermoplastic resin composition having the laser marking property of the present invention is
(A) 0.01 to 5 with respect to 100 parts by weight of the thermoplastic resin
Parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 1 part by weight. When the content of the component (D) is less than 0.01 part by weight, the laser marking color development is poor, while when it exceeds 5 parts by weight, the laser marking color development and impact resistance are poor.

The flame-retardant thermoplastic resin composition having a laser marking property of the present invention is capable of brightly coloring the irradiated portion by irradiating the surface of the molded product with laser light. Here, the laser light is He-N
Examples thereof include gas lasers such as e, Ar lasers, CO ₂ lasers, and excimer lasers, solid-state lasers such as YAG lasers, semiconductor lasers, and dye lasers. Among them, CO ₂ lasers and YAG lasers are preferable.
The wavelength of the YAG laser light is 1,054 nm.

When the molding surface of the flame-retardant thermoplastic resin composition having the laser marking property of the present invention is irradiated with laser light, the laser light-irradiated portion is usually a foaming phenomenon due to the laser light irradiation, and is slightly rather than the unirradiated portion. Get excited. The preferable height of the raised portion is 1 to 100 μm.
Although it is about m, about 10 to 80 μm is preferable because the laser marking color development and the recognition of the irradiated (character) portion are clear. It is also possible to produce a braille molded product by using this character height. Incidentally, of course,
The laser light irradiation causes a foaming phenomenon inside the resin surface.

The flame-retardant thermoplastic resin composition of the present invention comprises
If necessary, one kind or a combination of two or more kinds of fillers such as glass fiber, carbon fiber, wollastonite, talc, mica, glass flake, milled fiber, zinc oxide whiskers, potassium titanate whiskers and the like. You can By blending these fillers, rigidity can be imparted to the flame-retardant thermoplastic resin composition of the present invention. Further, by blending talc or the like, the flame-retardant thermoplastic resin composition of the present invention can be provided with matting properties. The glass fiber and carbon fiber preferably have a fiber diameter of 6 to 20 μm and a fiber length of 30 μm or more. The content of these fillers is preferably 1 to 5 with respect to 100 parts by weight of the flame-retardant thermoplastic resin composition of the present invention.
It is 0 part by weight, more preferably 2 to 30 parts by weight.
If the content of the filler exceeds 50 parts by weight, the laser marking property, the appearance of the molded product, and the practical impact resistance are impaired.

Further, the flame-retardant thermoplastic resin composition of the present invention includes a flame-retardant aid such as an antimony compound, a known coupling agent, an antibacterial agent, an antifungal agent, an antioxidant, a weathering (light resistance) agent. , Plasticizers, colorants (pigments, dyes, etc.), lubricants, antistatic agents, silicone oils, and other additives can be added within a range that does not impair the required performance.

Furthermore, in the flame-retardant thermoplastic resin composition of the present invention, another thermoplastic resin may be added depending on the required performance.
Other (co) polymers such as thermosetting resins can be blended. Here, other polymers include polycarbonate, polyethylene, polypropylene, polyamide, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, polytetrafluoroethylene, styrene-vinyl acetate copolymer, polyamide. Elastomers, polyamideimide elastomers, polyester elastomers, phenol resins, epoxy resins, novolac resins and the like can be mentioned. Among these, polyamide, polyethylene,
By blending polypropylene or the like, it is possible to make the laser marking color more bright.

The flame-retardant thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. A preferred manufacturing method is a method using an extruder or a Banbury mixer. Moreover, when kneading each component, you may knead each component collectively, and may add and knead several times. The kneading may be carried out in a multi-stage addition system with an extruder, or may be carried out with a Banbury mixer, a kneader or the like, and then pelletized with an extruder.

The flame-retardant thermoplastic resin composition of the present invention thus obtained is injection molded, sheet extruded, vacuum molded, profiled, foam molded, injection pressed,
Various molded articles can be molded by press molding, blow molding, or the like.

The various molded articles obtained by the above-mentioned molding method are excellent in flame retardancy (melt-dripping property), transparency, and have practical impact resistance and heat distortion temperature, and are It can be used in various fields such as a computer field and PPC that require transparency, housings, chassis, trays, buttons, switches and display frames. Further, the flame-retardant thermoplastic resin composition having excellent laser marking property of the present invention is applied to OA equipment such as FAX, printer, computer, remote controller, vacuum cleaner, microwave oven, home electric appliance such as air conditioner, and the like. Laser marking technology can be used to display the manufacturer's name, numbers, alphabets, barcodes, quality, etc. The character portion colored by laser marking is superior to the printed character portion in weather resistance and abrasion resistance, and is therefore far more preferable in practical use than printing.

[0050]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are measured as follows. Graft ratio described in the text

Intrinsic viscosity [η] The rubber-reinforced polymer is put into methyl ethyl ketone and shaken for 6 hours on a shaker. Centrifuge (rotation speed 2
Centrifuge at 3,000 rpm) for 60 minutes to separate insoluble matter and soluble matter. The soluble component is sufficiently dried with a vacuum dryer. This soluble component is dissolved in methyl ethyl ketone to make 5 different concentrations. Using an Ubbelohde viscosity tube,
The intrinsic viscosity [η] was determined from the result of measuring the reduced viscosity of each concentration at 30 ° C. The refractive index sample was formed into a film and measured with an Abbe refractometer.

Impact resistance (Izod impact strength) Using an injection molding machine J100E-C5 manufactured by Japan Steel Works, Ltd., with a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C., JI
A No. 2 type test piece of SK7110 was molded and Izod impact strength was measured. The unit is J / m. Fluidity (melt flow rate) Measured according to ASTM D1238. Measurement temperature is 2
The temperature is 20 ° C., the load is 10 kg, and the unit is g / 10 minutes.

Heat deformation temperature A test piece having a width of 6.4 mm, a length of 128 mm and a thickness of 12.8 mm was used, and the bending stress was measured according to JIS K7207 at a bending stress of 18.5 kgf / cm ² . Flammability (flame retardancy) 5 "length x 1 width by the method specified in UL94 standard
A vertical combustion test was conducted on a test piece of "2" x thickness 1/12 ". In the present invention, UL94 standard V-2 rank is defined as having melt-dripping property. Regarding the evaluation result, B is
Burning indicates a V-2 incompatibility.

Transparency [Haze] Using a test piece having a thickness of 2.4 mm, ASTM D100
It measured based on 3. The unit is%. Total light transmittance (Tt) Using a test piece having a thickness of 2.4 mm, ASTM D100
It measured based on 3. The unit is%.

A laser-markable flame-retardant thermoplastic resin composition was used to prepare a plate-shaped molded product using an injection molding machine. The surface of the molded product is a laser marker manufactured by Carl Basel (Star Mark 65W; YAG
Laser marking was performed using (laser light). By irradiating, the color-developing property, the recognizability, and the sharpness of the color-developed part were visually judged, and expressed by the following evaluation criteria. ◯: Good (when clear and recognizable character coloring is exhibited) Δ: Good (when either the sharpness or the recognizability is poor) X: Inferior (when both the sharpness and the recognizability are poor)

Reference Example 1 [Rubber-reinforced polymer (a-1) to
Preparation of (a-2)] In a glass flask having an internal volume of 7 liter equipped with a stirrer, polybutadiene 15 parts (solid content conversion), sodium dodecylbenzenesulfonate 1.5 parts, t-dodecyl mercaptan 0.1 part, And 100 parts of ion-exchanged water were mixed, and 5 parts of styrene, 5 parts of acrylonitrile and 10 parts of methyl methacrylate were added. After heating to 45 ° C with stirring, ethylenediamine tetrasodium acetate 0.1
Part, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water, and 0.1 part of diisopropenebenzene hydroperoxide. It was added and the reaction was continued for 1 hour.

Thereafter, 10 parts of styrene, 5 parts of acrylonitrile, 50 parts of methyl methacrylate, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropylbenzene hydroperoxide, and 50 parts of ion-exchanged water. The incremental polymerization component consisting of parts was continuously added over 3 hours to continue the polymerization reaction. After the addition was completed, stirring was continued for another hour, and then 2,2-methylene-bis- (4-ethylene-6-
0.2 part of (t-butylphenol) was added, and the reaction product was taken out of the flask. The reaction product latex was coagulated with 2 parts of calcium chloride, the reaction product was thoroughly washed with water, and then dried at 75 ° C. for 24 hours to obtain a white powder of a rubber-reinforced polymer (a-1). The polymerization conversion rate is 98.5%, the graft rate is 40%, and the intrinsic viscosity [η] is 0.40 dl /
It was g. The rubber component had a refractive index of 1.513, and the matrix resin had a refractive index of 1.517. By the same method, as shown in Table 1, the rubber-reinforced polymer (a-2) was obtained by changing the type and formulation of the monomer components, the amount of the chain transfer agent used, the polymerization temperature, the polymerization time, and the like. It was

Reference Example 2 [Preparation of Copolymer (a-3)] Further, a rubber-reinforced polymer (a) component was prepared by the same method with the types and compounding recipes of the monomer components shown in Table 1. Separately, the monomer component of was separately polymerized to obtain an MMA-styrene-acrylonitrile terpolymer (a-3). Table 1 shows the graft ratio, intrinsic viscosity [η], and refractive index of the obtained components (a-1) to (a-3).

Reference Example 3 [Rubber-reinforced polymer (a-4), A
Preparation of S Resin] A rubber-reinforced polymer (a-4) and an AS resin were obtained in the same manner as in (a-1), except that the monomer components and amounts shown in Table 1 were changed.

[0060]

[Table 1]

Reference Example 3 [Flame Retardants (B-1) to (B-3)]
Preparation] The flame retardants (B-1) to (B-2) and the comparative flame retardant (B-3) shown below were used. (B-1); a condensed phosphoric acid ester compound represented by the above general formula (II) (provided that R ⁴ , R ⁵ , R ⁶ and R ^{7 are present.}
Represents a 2,6-dimethylphenyl group, X represents an arylene group, j, k, l, and m are each 1 and N is 1. ), Manufactured by Daihachi Chemical Industry Co., Ltd. (trade name; PX200) (B-2); triphenyl phosphate (a phosphoric acid ester compound represented by the above general formula (I), R ¹ ,
R ² and R ³ represent a phenyl group. ), A flame retardant for comparison (B-3) manufactured by Daihachi Chemical Industry Co., Ltd .; an oligomer (brominated epoxy resin) in which at least 80% or more of both ends of tetrabromobisphenol A and epichlorohydrin are sealed with tribromophenol. , Bromine content 56
%, Molecular weight about 2,000

Reference Example 4 [Preparation of component (C)] As the component (C), the following polyether ester amide was used. Polyether ester amide; Nylon 6 block / Polyethylene oxide = 50/50
(%), Refractive index 1.513 nylon 6 and polyethylene oxide were esterified with terephthalic acid.

Reference Example 5 [Preparation of component (D)] The black compounds (D-1) to (D-2) shown below were used. (D-1); carbon black manufactured by Degussa Co., Ltd.

Examples 1 to 6 and Comparative Examples 1 to 6 The above components were mixed for 3 minutes with a Henschel mixer at the blending ratios shown in Tables 2 and 3 and then, using an NVC type 50 mm vent extruder manufactured by Nakatani Machinery Co., Ltd. Melt-kneading and extrusion were performed at a cylinder setting temperature of 220 ° C. to obtain pellets. The obtained pellets were sufficiently dried and injection-molded using an injection molding machine J100E-C5 manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. to obtain test pieces. This test piece was used and evaluated by the above evaluation method. The evaluation results are shown in Tables 2-3.

[0065]

[Table 2]

[0066]

[Table 3]

As is clear from Examples 1 to 6, the flame-retardant thermoplastic resin compositions of the present invention all have practical levels of impact strength, fluidity, flame retardancy and transparency, and are excellent. It was a material. Further, in Examples 3 and 6, black compounds were blended within the scope of the present invention to prepare test pieces,
When irradiated with YAG laser light, the irradiated portion exhibited a clear white color. Thus, the flame-retardant thermoplastic resin composition of the present invention is suitable for laser marking applications by using an appropriate colorant.

On the other hand, Comparative Example 1 is an example in which the blending amount of the component (B) exceeds the range of the present invention, and the impact resistance and transparency are poor. In Comparative Example 2, the component (B) is not the flame retardant of the present invention, but the transparency (cloudiness value) and the total light transmittance (Tt) are poor. In Comparative Example 3, the monomer blending ratio of the component (a) is outside the range of the present invention, and the transparency is poor. In Comparative Example 4, the content of the component (C) exceeds the range of the present invention, and the flame retardancy, heat distortion temperature, and transparency are poor. In Comparative Example 5, the blending amount of the component (B) is less than the amount specified in the present invention, and the flame retardancy and transparency are poor. In Comparative Example 6, the blending amount of the component (D) exceeds the range of the present invention, and the flame retardancy and the laser marking property are poor.

[0069]

The flame-retardant thermoplastic resin composition of the present invention comprises
It has excellent flame retardancy (melt-dripping property), transparency, and has practical impact resistance and heat distortion temperature, and is required to have a wide range of applications, such as transparency in OA / home electric appliances and PPC. It is useful for various parts, housings, chassis, trays, buttons, switches, display frames, etc. Further, the flame-retardant thermoplastic resin composition of the present invention containing a black compound is excellent in laser marking property, and laser marking is performed on the above-mentioned various molded products such as manufacturer name, number, alphabet, bar code, and quality display. Technology is available.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) (C08L 51/04 53:02) (72) Inventor Hiroyuki Ito 1-1-18 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F term (reference) 4J002 BN141 BP012 CL082 CL092 EW046 EW126 FD136 GG00 GQ00 4J026 AA67 AA68 AA69 BA27 DB02 DB03 DB04 DB05 GA09

Claims (4)

[Claims] 1. A rubber-reinforced polymer (a) obtained by graft-polymerizing a monomer component containing 50% by weight or more of a (meth) acrylic acid ester compound in the presence of (A) a rubbery polymer. With respect to 100 parts by weight of the thermoplastic resin as a component, (B) a phosphoric acid ester compound represented by the following general formula (I) and / or a condensed phosphoric acid ester compound represented by the following general formula (II) 5 to 20 parts by weight and (C) an ethylene oxide unit in an amount of 35 to 65% by weight, selected from the group of polyether ester amides, polyether amides, and hydrogenated aromatic vinyl-conjugated diene block copolymers. 0 to at least one
A flame-retardant thermoplastic resin composition for office automation and household appliances, characterized by containing 5 parts by weight. [Chemical 1] (However, R1, R2, and R3 each independently represent an alkyl group having 1 to 8 carbon atoms or an optionally substituted alkyl group having 6 to 20 carbon atoms, and n is 0. Or it is 1.) [However, R4, R5, R6, and R7 each independently represent an aryl group or an alkaryl group, X represents an arylene group, and j, k, l, and m are independent of each other. And is 0 or 1, and N is an integer of 1 to 5, but in the case of a mixture of phosphoric acid ester compounds, N represents an average value (1 ≦ N ≦ 5). ] 2. The flame-retardant thermoplastic resin composition for office automation / home appliances according to claim 1, wherein the monomer component further contains a functional group-containing vinyl monomer. 3. The component (B) in an amount of 5 to 20 parts by weight and the component (C) in an amount of 0 to 5 relative to 100 parts by weight of the thermoplastic resin (A).
The flame-retardant thermoplastic resin composition for office automation / household appliances according to claim 1 or 2, which comprises 0.01 to 5 parts by weight of (D) black compound. 4. The flame-retardant thermoplastic resin for office automation / home appliances according to claim 1, which is used for various parts, housings, chassis, trays, buttons, switches or display frames. Composition.