JP2003055527A - Thermoplastic resin composition for laser marking - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition for laser marking excellent in heat resistance and capable of providing molded articles on which clear white marking can be made to emerge by laser beam irradiation. SOLUTION: This thermoplastic resin composition for laser marking comprises (A) a rubber-reinforced resin composed of (A1) a rubber-reinforced vinyl-based resin obtained by polymerizing at least one kind of monomer selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and a (meth)acrylic acid ester monomer in the presence of a rubber-based polymer or a mixture of (A1) the rubber-reinforced vinyl-based resin with (A2) a (co)polymer obtained by polymerizing at least one kind of monomer selected from the group consisting of the aromatic vinyl monomer, the vinyl cyanide monomer and the (meth)acrylic acid ester monomer, and (B) a maleimide-based resin obtained by polymerizing a maleimide-based monomer with a (meth)acrylic acid ester monomer. In the resin composition, the content of (meth)acrylic acid ester monomer unit is 30-80 wt.% based on the total resin contained in the components A and B.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to laser light irradiation.
Therefore, clear white marking can appear on the molded product.
Thermoplastic for laser marking with excellent heat resistance
To a resin composition. [0002] Conventionally, (meth) acrylates
Laser blended with (co) polymer formed from monomer
Laser molding is applied to the molding material consisting of the resin composition for marking.
Is known to exhibit white color when irradiated
You. However, (meth) acrylic acid S
When a ter (co) polymer is blended, the heat resistance decreases,
It cannot be used in fields such as vehicle interior applications that require
No. Therefore, styrene was used for the resin for white laser marking.
・ Use of heat-resistant matrix such as phenylmaleimide copolymer
There is a technology to improve heat resistance by blending them.
Coloring when laser marking on molded material
The part is darkened and clear white marking cannot be obtained. [0003] The present invention relates to the above prior art.
Against the background of this issue.
Clear and clear white markings on molded products.
Thermoplastic for laser marking with excellent heat resistance
An object is to provide a resin composition. [0004] The present invention relates to [A] rubbery material
An aromatic vinyl monomer (b) in the presence of the polymer (a);
Vinyl cyanide monomer (c) and (meth) acrylic acid
At least one selected from the stele monomers (d1)
Rubber-reinforced vinyl resin (A1) obtained by combining
The rubber-reinforced vinyl resin (A1) and the monomer (b),
At least one selected from the group consisting of (c) and (d1)
Mixing with (co) polymer (A2) obtained by polymerizing one type
20 to 80 parts by weight of rubber reinforced resin
[B] maleimide monomer (e) and (meth) acrylic
Murray obtained by polymerizing a luic acid ester monomer (d2)
Laser mark containing 20 to 80 parts by weight of amide resin
A thermoplastic resin composition for packaging, comprising the component (A)
And (meth) a to all resins contained in the component (B).
The content of the acrylate monomer unit is 30 to 80% by weight.
%, And the content of the maleimide monomer unit is 5 times.
For laser marking characterized by being at least%
It is intended to provide a thermoplastic resin composition. DETAILED DESCRIPTION OF THE INVENTION The rubber-reinforced vinyl resin (A)
The rubbery polymer (a) forming 1) has rubber elasticity.
It is a polymer shown. Examples of this are polybutadiene,
Butadiene / styrene copolymer, butadiene / acrylo
Nitrile copolymer, styrene / butadiene / styrene
Rock copolymer, styrene / isoprene / styrene blow
Block copolymer, isobutylene / isoprene copolymer, etc.
Diene-based (co) polymers, these diene-based (co) polymers
Hydrogenated products, ethylene / propylene / (non-conjugated diene)
Copolymer, ethylene / butene-1 / (non-conjugated diene) copolymer
Polymer, polyurethane rubber, acrylic rubber, silicone
Rubber and the like. Of these, polybutadiene,
Tadiene / styrene copolymer, diene (co) polymer
Hydrogenated products, ethylene / propylene / (non-conjugated diene)
Copolymer, acrylic rubber and silicone rubber are preferred
No. When silicone rubber is used, it contains vinyl groups.
Having a graft crosslinking agent (for example, p-vinylphenylmeth
Tyldimethoxysilane, 2- (p-vinylphenyl) d
Tylmethyldimethoxysilane, 2- (p-vinylphenyl)
E) ethylene methyl dimethoxysilane)
Those co-condensed with siloxane are preferred. Polymerization in the presence of the rubbery polymer (a)
Examples of the aromatic vinyl monomer (b) include styrene,
α-methylstyrene, o-methylstyrene, p-methyl
Styrene, vinyl toluene, methyl-α-methylstyrene
And brominated styrene. Of these,
Tylene, α-methylstyrene and p-methylstyrene are preferred.
Good. The above vinyl cyanide monomer (c)
Is acrylonitrile, methacrylonitrile, etc.
However, acrylonitrile is preferred. The above (meta)
As the acrylate monomer (d1), acrylic acid
Methyl, ethyl acrylate, butyl acrylate, methacrylate
Methyl acrylate, ethyl methacrylate, butyl methacrylate
And the like. Of these, methyl methacrylate
Are preferred. Polymerized in the presence of the rubbery polymer (a)
To form the above rubber-reinforced vinyl resin (A1)
The aromatic vinyl monomer (b) and the cyan
Vinyl monomer (c) and the above (meth) acrylic acid ester
At least one or more of the teller monomers (d1), preferably
Using two or more, particularly preferably all of these,
Therefore, the sharpness of the white marking can be improved.
Wear. The preferred combination is a monomer
(B) is styrene, monomer (c) is acrylonitrile,
A combination of the monomer (d1) with methyl methacrylate,
Monomer (b) is α-methylstyrene, monomer (c) is
Acrylonitrile, monomer (d1) is methyl methacrylate
And the like. Production of the rubber reinforced vinyl resin (A1)
The aromatic compound in the presence of the rubbery polymer (a)
Vinyl monomer (b), vinyl cyanide monomer (c)
And the above (meth) acrylate monomer (d1)
The copolymer composition at the time of polymerization is usually the above-mentioned rubbery polymer.
(A) is 5 to 70% by weight (preferably 10 to 70% by weight)
%, More preferably 20 to 60% by weight)
The total amount of (b), (c) and (d1) is 30 to 95 weight
% (Preferably 30 to 80% by weight, more preferably 30%
７０70% by weight). However, (a) + (b) + (c)
+ (D1) = 100% by weight. The rubber-reinforced vinyl resin (A1) is
Even if the rubber-reinforced vinyl resin has one composition,
A blend of two or more rubber-reinforced vinyl resins
Is also good. Production of the above rubber-reinforced vinyl resin (A1)
The polymerization method used for emulsion polymerization, solution polymerization, bulk polymerization
Polymerization and suspension polymerization. When manufacturing by emulsion polymerization
Uses a polymerization initiator, a chain transfer agent, an emulsifier and water.
It is. The rubbery polymer (a) used in the production and the above
The above monomers (b), (c) and (d1) are
In the presence of the total amount of the union (a), the monomers (b) and (c)
And (d1) may be added at once and polymerized.
Alternatively, polymerization may be performed by continuous addition. Also, combine these
Polymerization may be performed by a combined method. In addition, the above rubbery polymerization
The whole or a part of the body (a) is added during the polymerization and polymerized.
You may. As the polymerization initiator, for example, cumene high
Dropper oxide, diisopropylbenzene hydropa
-Oxide, potassium persulfate, azobisisobutyronito
Ryl, benzoyl peroxide, lauroyl peroxy
, T-butylperoxylaurate, t-butylperoxy
Oxymonocarbonate and the like can be mentioned. As the chain transfer agent, for example, octylme
Lcaptan, n-dodecyl mercaptan, t-dodecyl
Mercaptan, n-hexyl mercaptan, tetraethyl
Ruthiuram sulfide, acrolein, methacrolein
, Allyl alcohol, 2-ethylhexyl thioglyco
And the like. The emulsifier used in the emulsion polymerization includes:
For example, sulfate ester of higher alcohol, dodecylben
Alkyl benzene sulfo such as sodium benzene sulfonate
Aliphatic sulfonic acid such as sodium phosphate and sodium lauryl sulfate
Salt, higher aliphatic carboxylate, rosinate, phosphoric acid, etc.
Anionic surfactants. [0015] In the emulsion polymerization, coagulation is usually carried out by a coagulant.
The resulting powder is washed with water and dried to obtain a rubber
A powder of a vinyl chloride resin is obtained. As this coagulant
Are calcium chloride, magnesium sulfate, magnesium chloride
Inorganic salts such as uranium, or acids such as sulfuric acid.
Wear. Of these coagulants, sulfuric acid is preferred. In the presence of the rubbery polymer (a),
Obtained by polymerizing monomers (b), (c) and (d1)
The rubber-reinforced vinyl resin (A1) contains the above monomer
(B), (c) and (d1) are added to the rubbery polymer (a).
Rafted copolymer and the above monomers (b), (c) and
(D1) is not grafted on the rubbery polymer (a).
Graft component [the above monomers (b), (c) and (d1)
Of copolymers]. In addition, the above-mentioned go according to the present invention.
Rubber reinforced resin [A]
In addition to (A1), this and the above monomers (b), (c) and
And (d1) are obtained by (co) polymerizing at least one of them.
It may be a mixture with the (co) polymer (A2). the above
The above-mentioned monomer (b) forming a (co) polymer (A2),
(C) and (d1) are the monomers exemplified above alone.
Alternatively, two or more kinds can be used in combination.
The rubber reinforced resin [A] is the rubber reinforced vinyl resin
(A1) and the above (co) polymer (A2)
Forming the (co) polymer (A2) in the above case
The amount of (b) used is preferably from 10 to 70% by weight, more preferably
It is preferably 10 to 60% by weight, and the monomer (c) is preferred.
0-30% by weight, more preferably 0-20% by weight
And the monomer (d1) is preferably 10 to 90% by weight.
%, More preferably 20 to 80% by weight. the above
The (co) polymer (A2) is a (co) polymer having a single composition.
The blend of two or more (co) polymers having different compositions
May be used. The rubber-reinforced resin [A] is
Mixing of the vinyl resin (A1) and the (co) polymer (A2)
The content ratio (A1) / (A2) in the case of a compound is (A1)
When the total of 1) and (A2) is 100% by weight, it is preferable.
1 to 100/99 to 0 (% by weight), more preferably
Preferably 10-90 / 90-10 (wt%), more preferably
Or 20 to 80/80 to 20 (% by weight). the above
If the content of the component (A1) is too small, the impact strength is reduced.
Not preferred. The rubber in the rubber-reinforced vinyl resin (A1)
Of the monomers (b), (c) and (d1) to the polymer
The raft rate is usually 10 to 200%, preferably 50 to 200%.
150%, more preferably 60-130%, even more preferred
Or 65 to 120%. If the graft ratio is too small
Impact strength decreases, while too high reduces fluidity
You. In producing the (co) polymer (A2),
Examples of the polymerization method include emulsion polymerization and solution polymerization.
For producing the above rubber-reinforced vinyl resin (A1)
Except that the rubbery polymer (a) is not used.
It can be manufactured by the following methods. The limiting viscosity of the rubber reinforced resin [A] is as follows:
Usually, 0.2 to 1.0 dl / g, preferably 0.2 to 0.1 dl / g.
8 dl / g, more preferably 0.3 to 0.7 dl / g
is there. If the intrinsic viscosity is too low, the impact strength will decrease,
On the other hand, if it is too large, the fluidity decreases. In forming the maleimide resin [B],
As the maleimide-based monomer (e), maleimide, N
-Methylmaleimide, N-phenylmaleimide, N-
(2-methylphenyl) maleimide, N- (4-hydroxide)
(Ciphenyl) maleimide, N-cyclohexyl maleimi
And N-phenylmaleimi among these.
And N-cyclohexylmaleimide are preferred, and N-
Phenylmaleimide is particularly preferably used. In forming the maleimide resin [B],
As the (meth) acrylate monomer (d2)
Forms the rubber-reinforced vinyl resin (A1)
(T) In the description of the acrylate monomer (d1)
What was illustrated can be used. In addition, the above copolymerization
As the monomer for forming the body [B],
Monomer (e) and the above (meth) acrylate
In addition to the monomer (d2), copolymerizable with these monomers
A vinyl monomer (f) can be used. The monomer (e) and the monomer (d2) are
As the polymerizable vinyl monomer (f), for example,
Saturated dicarboxylic anhydride, vinyl carboxylic acid compound, etc.
Is mentioned. As the above unsaturated dicarboxylic anhydride
Is maleic anhydride, itaconic anhydride, citracone anhydride
Acids and the like. The above vinyl carboxylic acid compound
And acrylic acid, methacrylic acid and the like. In producing the above maleimide resin [B]
The maleimide monomer (e) and the (meth) acrylic
Luric ester monomer (d2) and copolymerized with these monomers
The (co) polymerizable composition of the monomer (f) that can be mixed is, for example,
If the amount of the monomer (e) is 10 to 50% by weight (preferably 20
To 50% by weight, more preferably 30 to 50% by weight).
The monomer (d2) is 50 to 90% by weight (preferably 5 to 90% by weight).
0-80% by weight, more preferably 60-80% by weight)
And the monomer (f) is 0 to 30% by weight (preferably
Is 0 to 20% by weight, more preferably 0 to 15% by weight)
is there. However, (e) + (d2) + (f) = 100% by weight
It is. Maleimide in the maleimide resin [B]
If the content of the monomer unit is too small, the heat resistance will be poor. one
On the other hand, if the amount is too large, the laser marking property is inferior. The maleimide resin [B] has heat resistance,
For the purpose of improving impact resistance, etc.,
Obtained by copolymerization with acrylonitrile and / or styrene
May be used. In this case, acrylonitrile or
Irradiated the laser if too much styrene was used
Occasionally promotes carbonization. Also, styrene or
If the copolymerization amount of acrylonitrile is too large,
There is a tendency for the sharpness of white marking
You. The thermoplastic resin composition of the present invention is characterized in that
Contains reinforced resin [A] and maleimide resin [B]
However, the content ratio [A] / [B] is preferably 2
0 to 80/80 to 20 (parts by weight), more preferably 30
~ 80/70 ~ 20 (parts by weight), more preferably 30 ~
70/70 to 30 (parts by weight). The above rubber reinforced resin
The content of [A] is too large or the maleimide type
If the content of the resin [B] is too small, the effect of improving the heat resistance may be reduced.
On the other hand, the content of the rubber-reinforced resin [A] is insufficient.
Is too small or the above maleimide resin [B]
If the content is too large, the impact properties decrease. [0027] Included in the thermoplastic resin composition of the present invention
Containing (meth) acrylate monomer units in resin
The amount is 30 to 80% by weight, preferably 40 to 70% by weight.
%, More preferably 45 to 65% by weight. the above
Low content of (meth) acrylate monomer units
If it is too long, clear white marking by laser irradiation
I can't get it. Also, if too much is obtained using this composition
The heat resistance of the molded article is inferior. [0028] Included in the thermoplastic resin composition of the present invention
The content of the maleimide monomer unit in the resin is 5% by weight.
And preferably 5 to 30% by weight, more preferably 7 to 30% by weight.
-20% by weight. Including the maleimide monomer unit
If the amount is too small, the heat resistance is inferior, while if it is too large,
Poor impact resistance, fluidity and appearance of molded products. As the black colorant, carbon black is used.
Black iron oxide, titanium black, graphite, etc.
You. As the above carbon black, acetylene black
Channel, channel black and furnace black
I can do it. The preferred average particle size of the carbon black is 10
８０80 nm, more preferably 12-40 nm
is there. If the average particle size is within the above range, dispersion in the present composition
Good coloring and good laser marking coloring
You. Further, the preferred specific surface area is 20 to 1500 m ² /
g, the preferred oil absorption is 35-300 ml / 100 g,
The preferred pH is 2-10. The black iron oxide is Fe ₃ O ₄ Or Fe
O ・ Fe ₂ O ₃ Is a black iron oxide. Like
The preferred particle size is 0.3 to 0.8 μm, more preferably
0.4 to 0.6 μm. Spherical and cubic
And needle-shaped, but cubic is preferred
No. The above titanium black can reduce titanium dioxide
Is a compound obtained by The above titanium black
The preferred particle size is 0.1-0.8 μm, more preferably
It is 0.2 to 0.6 μm. The above black dress
Coloring agents can be used alone or in combination of two or more.
Can be. Of these, carbon bras
Are particularly preferred. The compounding amount of the above black colorant is the same as the above rubber strength.
Resin [A] and the maleimide resin [B] in total of 1
0.05 to 0.8 parts by weight, based on 00 parts by weight
Parts, more preferably 0.05 to 0.6 parts by weight, even more preferably
Or 0.1 to 0.5 parts by weight. The above black colorant
If the blending amount is too small, the coloring of laser marking
Insufficient, on the other hand, if too much, the impact properties are reduced. The thermoplastic resin composition of the present invention contains a dye,
Pigments and the like can be blended. As the above dye,
Ring dyes, nitroso dyes, nitro dyes, monoazo
Dyes, disazo dyes, perylene dyes, perinone dyes
Dyes, thioindigo dyes, stilbene azo dyes,
Tomine dyes, triphenylmethane dyes, xanthe
Dyes, acridine dyes, quinoline dyes, methine
Dyes, thiazole dyes, indamine dyes, azines
Dyes, oxazine dyes, thiazine dyes, sulfur dyes
Dyes, aminoketone dyes, anthraquinone dyes, etc.
I can do it. Further, among the above pigments, as an organic pigment,
Means monoazo, condensed azo, disazo, anthrac
Non-based, isoindolinone-based, heterocyclic-based, perinone-based,
Azomethine, quinacridone, perylene, dioxa
Gin-based, phthalocyanine-based and the like. Also coordinate
Metals that are calcium, nickel, iron, barium,
Sodium, copper, molybdenum, cobalt, manganese, sub-
Organic pigments such as lead, titanium, magnesium, potassium, etc.
Can be preferably used, specifically,
Gred (Ca), Green Gold (Ni), Pigme
Green B (Fe), Pigment Scar Red 3B
(Ba), First Sky Blue (Ba), Phthalasi
Anine green (Fe), phthalocyanine blue (C
u), Brilliant Carmine 6B (Ca), Bordeaux 1
0B (Na), Risorret R (Na), Rakelet
Do C (Ba), Lake D (Ba), Brilliant
Car red G (Ca), manganese violet (M
n), cobalt violet (Co) and the like.
The parentheses indicate the metal elements contained in each organic pigment.
You. Further, among the above pigments, as an inorganic pigment,
Means titanium oxide, titanium yellow, zinc oxide,
, Zinc sulfide, iron oxide, composite oxide pigment, ultramarine,
Baltic blue and the like. The above dyes and pigments are
Use one kind alone or two or more kinds in combination
Can be The amounts of the dyes and pigments are
Of the rubber-reinforced resin [A] and the maleimide-based resin [B].
It is preferably 0.01 to 100 parts by weight in total.
To 0.8 parts by weight, more preferably 0.01 to 0.6 parts by weight
Parts, more preferably 0.01 to 0.5 parts by weight. Up
If the amount of the dye or pigment is too small,
Coloring is insufficient, while too much
Decreases. The thermoplastic tree for laser marking of the present invention
The fat composition includes a filler, a weathering agent, an antistatic agent, a flame retardant,
Flame retardant, antioxidant, plasticizer, lubricant, coloring other than the above
Agents, coupling agents, silicone oil, etc.
Can be. As the filler, glass fiber, carbon fiber
Wei, wollastonite, talc, mica, glass fray
Fiber, milled fiber, zinc oxide whisker, titanic acid
Calcium whiskers and the like. These are single types
Can be used alone or in combination of two or more
You. By blending the above filler, the heat
Giving rigidity to molded products obtained using plastic resin compositions
Can be Preferred size of glass fiber and carbon fiber
The fiber diameter is 6-20μm and the fiber length is 30μm or more
It is. Also, matte by blending talc etc.
Properties can be imparted. The amount of the above filler is
The rubber reinforced resin [A] and the above maleimide resin [B]
Is preferably 1 to 50 parts by weight based on 100 parts by weight of
Parts, more preferably 2 to 30 parts by weight. The above filler
If the amount is too large, the laser marking property is impaired. As the weathering agent, an organic phosphorus compound,
Organic sulfur compounds, organic compounds containing hydroxyl groups
Objects are preferred. In addition, as the antistatic agent, poly
Ethers, sulfonates having an alkyl group, and the like.
It is. The amount of the weathering agent and the antistatic agent is
The rubber reinforced resin [A] and the maleimide resin, respectively.
Preferably, 0.1 to 100 parts by weight of [B] in total.
10 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.
You. The above-mentioned "flame retardant (C)" includes bromine-based flame retardants.
Flame retardants, phosphorus-based flame retardants, and the like. Uses phosphorus-based flame retardants
When used, it is preferable in terms of environmental problems. On the other hand, smell
If an elementary flame retardant is used, heat
The heat resistance of the molded article of the plastic resin composition is increased. Of the present invention
In a thermoplastic resin composition, a brominated flame retardant and phosphorus
A combination of flame retardants may be used. As the "brominated flame retardant", tetrabromo
Bisphenol-A oligomers (ie, brominated epoxy
Epoxy resin; epoxy group at the end or epoxy group
The tribromophenol, methyl alcohol, ethyl alcohol
(It may be sealed with alcohol, etc.), brominated polystyrene
Oligomer, brominated polycarbonate oligomer, tetrabromide
Mobisphenol-A, brominated triazine and the like.
You. Of these, tetrabromobisphenol-A
Oligomers (brominated epoxy resins) are preferred (preferred)
Molecular weight of 1,000 to 6,000, more preferably
1,500 to 4,500), and the terminal is
Those sealed with phenol are preferred. Also, bromine-based
The preferred bromine concentration of the flame retardant is 30 to 65% by weight, more preferably.
Preferably it is 45 to 60% by weight. Further preferred softening
The point (melting point) is 100 to 180 ° C, more preferably 110
~ 140 ° C. As the “phosphorous flame retardant”, triphenyl
Phosphate, Trixylenyl phosphate, Tri
Cresyl phosphate, trixylenyl thiophosph
Of phosphate, hydroquinone and diphenyl phosphate
Condensate of resorcinol and diphenyl phosphate
Condensate, resorcinol and dixylenyl phosphate
Condensates, oligomers of triphenyl phosphate,
Bisphenol A-bis (diphenyl phosphate)
G), bisphenol-A and dixylenyl phosphate
And the like. Among these, Trife
Nil phosphate, resorcinol and dixylenyl
Condensate of phosphate (average degree of condensation: 1-2), trif
Bisphenol A, an oligomer of phenyl phosphate
With diphenyl phosphate (average degree of condensation: 1
To 2) are preferred. The preferred phosphorus concentration of the phosphorus-based flame retardant is
4 to 30% by weight, more preferably 6 to 25% by weight
You. Oligomeric or condensed phosphorus flame retardants (per molecule
Use two or more phosphorus elements) to suppress mold contamination
The resulting thermoplastic resin composition is obtained. Phosphorus flame retardants
And those which are liquid at room temperature can also be used. Phosphorus-based flame retardant
In the case of liquid, when melt-kneading with an extruder,
Feeding is preferred. When the above-mentioned flame retardant is blended, its blending amount
Are the rubber-reinforced resin [A] and the maleimide-based resin
Preferably 3 to 4 parts by weight based on 100 parts by weight of [B].
0 parts by weight, more preferably 3 to 30 parts by weight. Flame retardant
If the amount of the agent is too small, the effect of imparting flame retardancy is small,
If the amount is too large, the impact strength of the obtained molded article is impaired. When the above flame retardant is blended, a flame retardant auxiliary
Can be used in combination. As this flame retardant,
For example, antimony compounds, polytetrafluoroethylene
(PTFE) and the like. When using brominated flame retardants
Uses an antimony compound as a flame retardant
Use polytetrafluoroethylene when using flame retardants
Is preferred. The above "antimony compound" includes triacid
And antimony pentoxide. Ma
In addition, “polytetrafluoroethylene” is
This has the effect of preventing tapping (melt dripping). Preferred
Weight average molecular weight is 500,000 or more, more preferably 1,000,000
That is all. Polytetrafluoroethylene with other components
The preferred average particle size for mixing and kneading is 90 to 60.
0 μm, more preferably 100 to 500 μm, even more preferably
Or 120 to 400 μm. In addition, mixed with other components
The average particle size of the kneaded polyfluoroethylene is
0.1-100μm granular material or finer
Dispersed as fibers. Also, polytetrafluoroethylene
The preferred specific gravity when mixing the len with other components is 1.5 to
2.5, more preferably 2.1 to 2.3, preferably
The new bulk density is 0.5 to 1 g / ml, more preferably 0.1 g / ml.
6-0.9 g / ml. Polytetrafluoroethylene
Blending can prevent dripping during combustion.
Therefore, a higher flame retardant level can be achieved.
Solvents such as polytetrafluoroethylene etc.
Agents (polyethylene wax, organic acid, stearyl acid
Disperse in organic metal salts such as magnesium)
John-type polytetrafluoroethylene can also be used. When the above-mentioned flame retardant is used, its compounding amount
Are the rubber-reinforced resin [A] and the maleimide-based resin
With respect to the total 100 parts by weight of [B], preferably 2-3
0 parts by weight, more preferably 3 to 25 parts by weight. Flame retardant
If the amount of the auxiliary agent is too small, the effect of imparting flame retardancy is small.
The impact strength and molding processability of the molded product obtained when too much
Impair. The thermoplastic tree for laser marking of the present invention
Depending on the application required for the fat composition, other thermoplastic
A thermosetting resin and a thermosetting resin can be blended. That
Examples are polycarbonate, polyamide, polyethylene
Ren, polypropylene, polyester, polysulfone,
Polyether sulfone, polyphenylene sulfide, liquid
Crystalline polymer, polyvinylidene fluoride, polytetrafluoro
Ethylene, styrene / vinylidene acetate copolymer, poly
Amide elastomer, polyamide imide elastomer,
Polyester elastomer, polyetherester
, Phenolic resin, epoxy resin, novolak resin, etc.
Is mentioned. Of these, polyamide, polyethylene
More clear by blending
Laser marking properties can be exhibited. these
The compounding amount of the resin is the above-mentioned rubber reinforced resin [A] and the above
With respect to 100 parts by weight of the total amount of the reimide resin [B].
Preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight.
Parts by weight. Further, among the thermoplastic resins exemplified above,
Polyamide elastomer, polyetheresteramide
To provide permanent antistatic properties by blending
Can be. The compounding amount of these resins is
[A] and the maleimide-based resin [B] in total 100 weights
Parts by weight, preferably 1 to 30 parts by weight, more preferably
Or 2 to 20 parts by weight. The thermoplastic tree for laser marking of the present invention
The fat composition is extruder, Banbury mixer, kneader
-By kneading each component using a roll, etc.
can get. A preferred production method is a method using a twin-screw extruder.
It is. When kneading each component, knead all at once
May be kneaded in a multi-stage addition system. The thermoplastic tree for laser marking of the present invention
The fat composition can be obtained by injection molding, sheet extrusion, vacuum molding,
OA products, home appliances, vehicles
Various molded products such as components, housings and switches
Can be. Sills and windows used as building materials
It can also be used for frames and handrail materials. The surface of these products
Develop clear white by irradiating laser light
be able to. Printing part colored by laser marking
Minutes have better weather resistance than those obtained by printing,
In addition, because it has excellent wear resistance, it is much more practical than printing
Above. The present invention will now be described in more detail with reference to the following examples.
As will be described in detail, the present invention is described below unless departing from the gist thereof.
The present invention is not limited to the embodiments described below. In addition,
In Examples and Comparative Examples, parts and% are not particularly specified.
As far as possible, they are parts by weight and% by weight. 1. Evaluation method The evaluation method used in this example is as follows.
is there. (1) A 1 g sample of the graft ratio of the rubber-reinforced vinyl resin was precisely weighed, and 20 cc of acetone was added thereto.
For 10 hours, and then rotate at 20,000 rpm
m and centrifuged to separate soluble and insoluble components. Insoluble matter
Drying with a vacuum drier yielded insolubles and solubles. 1g sample
X (g) the weight of the rubber component in the
Assuming that the weight of the dissolved component is y (g), the graft ratio is
It is obtained by the above calculation formula. Graft ratio (%) = {(y−x) / x} × 100 (2) Intrinsic viscosity The soluble matter obtained above was dissolved in methyl ethyl ketone,
It measured with the Ubbelohde viscometer under the temperature condition of ° C. (3) Molding of 40 mm x 80 mm x 30 mm by total light transmittance injection molding
Product and purchased from Big Gardner Co., Ltd.
And the total light transmittance was measured. (4) Izod impact strength Measured according to ASTM D256. Measured with notch
Specified. (5) Heat resistance The heat distortion temperature was measured according to ISO75. Test pieces
The thickness is 4mm and the load is 18.6kg / cm ² It is. (8) Evaluation of laser marking properties Plate-like molding by injection molding using a thermoplastic resin composition
I got the goods. The surface of the molded product is manufactured by Carl Basel
"Laser Marker Star Mark 65W (YAG Ray
Laser marking). Irradiate
The sharpness of the colored part and the color of the marking
It was judged visually. The criteria for determining sharpness are shown below. ◎: Very clear. ：: Clear. ×: Poor definition. 2. Preparation of rubber reinforced resin [A] 2-1. Production of rubber-reinforced vinyl resin (A1-1) 7-liter glass flask equipped with a stirrer
, 100 parts of ion-exchanged water, dodecylbenzene sulfone
Sodium acid 1.5 parts, t-dodecyl mercaptan 0.1 part.
1 part, a rubbery polymer having an average particle diameter of 300 nm
Butadiene latex 40 parts (solid content conversion), styrene
Add 15 parts and 5 parts of acrylonitrile and stir
The temperature rose. When the temperature reaches 45 ° C, ethylene
0.1 parts of sodium sodium tetraamine, 0.003 ferrous sulfate
Part, formaldehyde sodium sulfoxylate.2
Activator consisting of 0.2 part of hydrate and 15 parts of ion-exchanged water
Aqueous solution and diisopropylbenzene hydroperoxide
0.1 part of oxide was added and the reaction was continued for 1 hour. That
After that, 50 parts of ion-exchanged water, dodecylbenzenesulfonic acid
1 part of sodium, 0.1 part of t-dodecyl mercaptan,
0.2 parts of diisopropyl hydroperoxide, polystyrene
Ink consisting of 30 parts of acrylonitrile and 30 parts of acrylonitrile
Mental polymerization component is added continuously over 3 hours to polymerize
The reaction continued. After the addition was completed, stirring was continued for 1 hour.
Then, 2,2-methylene-bis- (4-ethylene-6-t
-Butylphenol) and the reaction product was
Removed from Rusco. Chloride reaction product latex
Coagulated with 2 parts of calcium, and the reaction product was thoroughly washed with water
After drying at 75 ° C. for 24 hours,
/Styrene/acrylonitrile=41.2/44.2
/14.6(%) rubber-reinforced vinyl with copolymer composition
A system resin (A1-1) was obtained. The polymerization conversion rate is 97.2%,
The graft ratio is 75% and the intrinsic viscosity is 0.44 dl / g.
Was. 2-2. Rubber reinforced vinyl resin (A1-
2) Production of 35) Butadiene latex in a glass flask, styrene
Add 15 parts of styrene and 5 parts of acrylonitrile,
Uses 45 parts of methyl methacrylate as a mental polymerization component
Polymerization was carried out in the same manner as (A1-1) except that
Butadiene / styrene / methyl methacrylate
Salt / acrylonitrile = 35.7 / 15 / 44.5 /
Rubber-reinforced vinyl resin having a copolymer composition of 4.8%
A fat (A1-2) was obtained. Graft ratio is 80%, intrinsic viscosity
Was 0.50 dl / g. 2-3. Preparation of (co) polymer (A2) The following polymers A2-1 to A4-2 were obtained by solution polymerization. A2-1: Acrylonitrile (AN) / styrene (S
T) Copolymer composition; AN / ST = 25/75 (%) Intrinsic viscosity; 0.5 dl / g A2-2; Acrylonitrile (AN) / styrene (S
T) / methyl methacrylate (MMA) copolymer composition; AN / ST / MMA = 6/27/67 (%) intrinsic viscosity; 0.3 dl / g A2-3; polymethyl methacrylate intrinsic viscosity; 0.3 dl / G refractive index; 1.49 A2-4; acrylonitrile (AN) / α-methyls
2. Tylene (AMS) copolymer composition; AN / AMS = 28/72 (%) intrinsic viscosity; 0.58 Preparation of maleimide resin [B] The following polymers B-1 to 6 by emulsion polymerization or solution polymerization
Obtained. B-1: Methyl methacrylate (MMA) / N-phenyl
Lumareimide (PMI) / styrene (ST) copolymer composition; MMA / PMI / ST = 63/12/25 (%) Glass transition temperature; 144 ° C. Weight average molecular weight; 85,000 B-2; Methyl methacrylate (MMA )/styrene
(ST) / cyclohexylmaleimide (CHMI)
Combined composition; MMA / ST / CHMI = 82/6/12 (%) Glass transition temperature; 125 ° C. Weight average molecular weight; 75,000 B-3; Methyl methacrylate (MMA) / phenylmer
Reimide (PMI) copolymer composition; MMA / PMI = 60/40 (%) Glass transition temperature: 145 ° C. Weight average molecular weight: 90,000 B-4; Methyl methacrylate (MMA)
/ Phenylmaleimide (PMI) / Styrene (ST) /
Acrylonitrile (AN) copolymer composition; MMA / PMI / ST / AN = 15/40/20
/ 25 (%) Glass transition temperature; 135 ° C Weight average molecular weight: 80,000 B-5; Methyl methacrylate (MMA) / phenylmer
Reimide (PMI) copolymer composition; MMA / PMI = 25/75 (%) Glass transition temperature; 180 ° C. Weight average molecular weight: 18,000 B-6; Styrene (ST) / phenylmaleimide (P
3. MI) Copolymer composition; ST / PMI = 50/50 (%) Glass transition temperature: 200 ° C. Weight average molecular weight: 100,000 Carbon black having an average particle diameter of 30 nm for the laser absorbing material was used. 5. Colorant [C] The following was used as the colorant. C-1; manufactured by Sumitomo Chemical Color Co., Ltd., trade name "Sumiplast
"Yellow HLR"C-2; manufactured by Sumitomo Chemical Color Co., Ltd., trade name "Sumiplast"
Orange HRP "C-3; manufactured by Bayer AG, trade name" Macro Rex Bull
-RR "C-4; manufactured by Bayer AG, trade name" Macrolex Bay
Oret R "C-5; manufactured by Nippon Kayaku Co., Ltd., trade name" Kayaset Red A "
2G ”C-6; manufactured by Mitsubishi Chemical Corporation, trade name“ Diaresin Black ”
B "C-7; manufactured by Bayer AG, trade name" Macrolex Gris
G "6. Examples 1 to 8, Comparative Examples 1 to 5 Ingredients [A] to [C] were mixed in the formulation shown in Tables 1 and 2.
And melted at a temperature of 220-240 ° C using an extruder
It was kneaded, and an evaluation sample was obtained by injection molding. This review
The above-mentioned various evaluations were performed using the valency sample, and Tables 1 and 2
It was also described in. [Table 1] [Table 2] 7. From the effect table 2 of the example, the comparative example not containing the maleimide resin [B]
In No. 1, Izod impact strength and laser marking properties
, But poor heat resistance. Comparative Examples 2 and 3
The (meth) acrylate monomer unit amount is within the scope of the present invention.
Out of the box, poor laser marking properties. Comparison
In Example 3, the Izod impact strength was also poor. Comparative Example 4
Is a rubber-reinforced resin [A] and a maleimide-based resin [B].
Content is out of the range of the present invention, heat resistance and laser
Excellent marking performance, but poor Izod impact strength
I have. Comparative Example 5 shows that B as maleimide resin [B]
-6 is male with no MMA copolymer as heat resistant matrix
It is an imide polymer, and a (meth) acrylic acid ester monomer
Laser marking, when the body weight is outside the scope of the invention
Poor sex. On the other hand, Examples 1 to 8
-A good white color is formed in the marking property evaluation, and
In addition, it exhibited heat resistance that can be used in practical use. The thermoplasticity for laser marking of the present invention
The resin composition has excellent resistance to molded products obtained using the same.
Clear white mark by laser light irradiation while giving thermal properties
The King can come out.

Continuation of front page    (72) Inventor Masahiko Noro             Techno, 1-1-18 Kyobashi, Chuo-ku, Tokyo             Polymer Co., Ltd. (72) Inventor Akiko Goto             Techno, 1-1-18 Kyobashi, Chuo-ku, Tokyo             Polymer Co., Ltd. (72) Inventor Mitsuru Kawakita             4-6 Tomari Koyanagicho, Yokkaichi-shi, Mie Japan             Laling Co., Ltd. F-term (reference) 2H086 AA05                 4J002 BC03X BC08X BC09X BC11X                       BG04X BG04Y BG05X BG06X                       BG10X BH02Y BN14W BN15W                       BN16W FD010 FD040 FD090                       FD130 GP00 GR00 GT00                 4J026 AA17 AA49 AA67 AA68 AA69                       BA05 BA06 BA27 BA31 DB02                       DB04 DB05 DB13 DB14 DB15                       GA01

Claims (1)

Claims: [A] In the presence of a rubbery polymer (a),
Aromatic vinyl monomer (b), vinyl cyanide monomer (c) and (meth) acrylate monomer (d1)
Or a group consisting of the above-mentioned rubber-reinforced vinyl resin (A1) and the above-mentioned monomers (b), (c) and (d1). 20 to 80 parts by weight of a rubber-reinforced resin composed of a mixture with a (co) polymer (A2) obtained by polymerizing at least one selected from the group consisting of (B) maleimide monomers (e) and (B). Maleimide resins 20 to 8 obtained by polymerizing (meth) acrylic acid ester monomer (d2)
A thermoplastic resin composition for laser marking containing 0 parts by weight, wherein the content of the (meth) acrylate monomer unit is based on the total resin contained in the component (A) and the component (B). Is 30 to 80% by weight, and the content of the maleimide monomer unit is 5% by weight or more.