JP2003138089A - Thermoplastic resin composition for hot plate welding, and resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for hot plate welding which is excellent in resistance to stringing and welding strength and ensures excellent mechanical characteristics and high-degree molding appearances in a hot plate welding method, and a resin molded article composed of the thermoplastic composition. SOLUTION: The thermoplastic resin composition for hot plate welding comprises (A) 20-70 wt.% of a graft polymer obtained by graft polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if required, other monomer copolymerizable therewith in the presence of a crosslinked rubbery polymer, which has a weight-average particle size of 100-300 nm, contains at most 15 wt.% of a particle having a particle size of less than 100 nm and at most 10 wt.%; of a particle having a particle size of more than 300 nm in a particle size cumulative weight fraction and has a gel content of 50-95 wt.%, and (B) 30-80 wt.% of a vinylic copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if required, other monomer copolymerizable therewith. The resin molded article is composed of the thermoplastic composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for hot plate welding in which two or more kinds of resin molded products are joined together by melting by using heated hot plates and then crimping the melted portions. The present invention relates to a thermoplastic resin composition for hot plate welding and a resin molded product joined by hot plate welding.

[0002]

2. Description of the Related Art Conventionally, there are roughly three types of methods for joining resin molded products, namely, a method using an adhesive (adhesion method), a method using friction heat (vibration welding method) and a method using heating ( Hot plate welding method).

Of these, the method using an adhesive has the drawbacks that it is environmentally unfavorable because it uses a solvent and the cycle time is long, and the vibration welding method uses a styrene resin-containing composition. , A part of the vibrated styrene-based resin composition is damaged to generate a powdery material having a fine particle diameter, and this powdery material is scattered in the air and enters the joint part, which results in high light transmittance. In applications where the above is required, the deterioration of the light transmission due to the adhered powdery matter has been a very serious problem.

Therefore, a hot plate welding method of melting a predetermined amount of a portion to be joined of a resin molded product by a heated hot plate and then crimping them together is an environmental problem due to the above-mentioned bonding method or a resin due to vibration welding method. It has been adopted as a countermeasure for the scattering problem.

However, in the hot plate welding method, when the molded products (parts) made of the same kind of thermoplastic resin are heat-welded to each other, the welding strength is increased, but the molded products (parts) made of different thermoplastic resins are made together. In the case of heat-welding, since the weldability (meltability) is not good, it may be a serious problem.

As an example thereof, there are lamp housings for automobiles including head lamps and rear combination lamps. In these resin molded products, polypropylene is used in terms of cost and chemical resistance, and two or more molded products are joined by a method called a hot melt method, but this method has a problem in adhesive strength. A styrene-based resin such as ABS, which has good thermoplastic resin weldability, has been adopted. However, with the recent improvement in the performance of automobile lamps, the temperature inside the lamp is in the high temperature range, so the shape and design of the molded product are greatly limited by these resins, and resins that can be used in the high temperature range are Required by the lamp industry.

To meet such demands, heat-resistant ABS resins and mixtures of these with polycarbonate resins have been proposed. However, in these resins, a resin molded product is melted by a heated hot plate during hot plate welding. After that, when the resin molded product is separated from the hot plate, the melted part of the resin is stretched into a thread shape (thread drawing phenomenon), and this adheres to the surface of the molded product of the lamp lens or lamp housing, resulting in poor appearance. May occur.

Therefore, there is a demand for a resin that does not cause stringing when heating the hot plate. Various proposals have been made to improve the stringing phenomenon.

Japanese Unexamined Patent Publication No. 9-12902 discloses a method of applying a resin composition obtained by adding a fluororesin such as polytetrafluoroethylene to a thermoplastic resin such as polycarbonate or ABS resin as a resin constituting a lamp body. Proposed. However, in the method described in the same issue,
Fluorine resin has strong external lubricity, so if the amount of addition is large, the resin discharged from the extrusion molding machine during extrusion manufacturing of molding pellets will suffer from a so-called surge, which is a corrugated discharge, and will only deteriorate productivity. However, when vacuum-depositing the inner surface of the molded lamp body or coating the outer surface of the lamp body, the adhesion of the deposited film or coating film was poor and the secondary workability was sometimes poor. In addition, since a fluororesin such as polytetrafluoroethylene is added, there is a problem that a molding defect called silver is likely to occur during molding.

JP-A-10-310676 discloses that in the presence of a rubbery polymer selected from crosslinked acrylic rubber and polyorganosiloxane, vinyl cyanide monomer, aromatic vinyl monomer, ) Disclosed is a thermoplastic resin composition for hot plate welding, which essentially comprises a graft polymer obtained by graft-polymerizing a monomer selected from acrylic acid ester monomers. Further, in the same publication, 10 to 80 parts by weight of the graft polymer and 20 to 90 of a polycarbonate resin.
Although a thermoplastic resin composition for hot plate welding consisting of parts by weight is also specifically disclosed, according to the resin composition described in the same item,
Regarding the stringing property during melt processing, there is some improvement effect, but it is not satisfactory because it does not prevent stringing at all, and the molding appearance is not good. When used for other purposes, there is a problem in that the appearance of metal vapor deposition, which is performed as a secondary process described later, is extremely poor.

Further, JP-A-11-199729 discloses that (A) 40 to 90% by weight of α-methylstyrene copolymer, (B) 5 to 80% by weight of rubbery polymer, α-methylstyrene monomer. A thermoplastic resin composition for hot plate welding, which contains 10 to 60% by weight of a styrene-based graft copolymer composed of 20 to 95% by weight of an aromatic vinyl monomer other than a monomer as an active ingredient, is disclosed. According to the resin composition described in No. 3, although there is some effect on the stringiness during melt processing, there is a problem that the welding strength, which is the bonding strength between molded products, is not sufficient.

Further, Japanese Patent Laid-Open No. 11-256044, which was filed by the applicant of the present application, discloses that the thermoplastic resin 10
A composition obtained by blending 0.05 to 5.0 parts by weight of a polymer of tetrafluoroethylene derivatives with respect to 0 part by weight, wherein the polymer of the tetrafluoroethylene derivatives is:
Disclosed is a thermoplastic resin composition for hot plate welding, which is wholly or partially contained by a polymer containing an aromatic vinyl monomer and a vinyl cyanide monomer. Further, a composition in which the thermoplastic resin is a mixture of a rubber-containing styrene-based resin and a polycarbonate resin is also disclosed, but the resin composition described in the same item has a great effect on stringiness. However, since a polymer of a special tetrafluoroethylene derivative is used, there is a slight problem in terms of cost. It was also found that a defective molding called silver may occur during molding.

On the other hand, in the case of a lamp housing or the like, the final product is often partially subjected to secondary processing such as painting, metal deposition, plating, etc. In order to adapt to these secondary processing, a molded product is required. The surface condition of (1) needs to be finished to a high degree. Therefore, unless the molding material has a very high surface condition (surface appearance) at the time of molding, the defective rate at the time of molding becomes extremely high. Therefore, when used for a lamp housing or the like, there has been a demand for a molding material that not only has no stringiness but also has a highly favorable surface appearance.

As described above, many proposals have been made for a resin composition applied to hot plate welding, but the so-called stringing phenomenon in which the molten portion of the resin at the time of hot plate welding is stretched into a thread shape does not occur. Mechanical properties such as impact resistance, heat distortion temperature, fluidity, etc., which are excellent in stringing resistance, have a welding strength between welded molded products, and are required as a material for a lamp housing like the above example. In spite of the demand for a molding material having characteristics, particularly, no stringing, high welding strength, and a high molding appearance, it has not yet been achieved.

[0015]

DISCLOSURE OF THE INVENTION An object of the present invention is to perform hot plate welding in a hot plate welding method, which is excellent in stringing resistance, welding strength, mechanical properties, and has a high molding appearance. It is intended to provide a thermoplastic resin composition and a resin molded article made of the thermoplastic composition.

[0016]

According to the present invention, the weight average particle size is 100 to 300 nm, and the cumulative particle weight fraction is less than 100 nm is 15% by weight or less and 300 n.
More than m is 10% by weight or less, and the gel content is 50 to 95.
Graft weight obtained by graft-polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, another copolymerizable monomer in the presence of a rubbery polymer having a cross-linkage of 1% by weight. A vinyl-based copolymer (B) obtained by polymerizing 20 to 70% by weight of the polymer (A), an aromatic vinyl monomer, a vinyl cyanide monomer, and another monomer copolymerizable as necessary. ) 3
Provided is a thermoplastic resin composition for hot plate welding, which comprises 0 to 80% by weight.

According to the present invention, the weight average particle diameter is 1
0 to 300 nm, the particle size cumulative weight fraction is less than 15% by weight of less than 100 nm, less than 10% by weight of more than 300 nm, and the gel content is 50 to 95% by weight.
A graft polymer obtained by graft-polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, another copolymerizable monomer in the presence of a rubbery polymer having a crosslinkage of A) A vinyl-based copolymer (B) 10 obtained by polymerizing 10 to 70% by weight of an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomer as required. ~ 7
Provided is a thermoplastic resin composition for hot plate welding, which comprises 0% by weight and 20 to 80% by weight of a polycarbonate resin (C).

According to the present invention, there is also provided a resin molded product obtained by joining a molded product made of the above thermoplastic resin composition by hot plate welding.

Further, according to the present invention, there is provided a vehicle lamp resin composition comprising the above-mentioned thermoplastic resin composition.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

As a result of earnest studies by the present inventors, the rubber-containing graft polymer having a specific graft structure using a specific rubber-like polymer (particle size, particle size distribution, etc.) Blending with a vinyl-based copolymer,
Furthermore, by adding a polycarbonate resin, particularly in the particle size of the rubbery polymer, it has been found that, at an extremely small particle size that has not been heretofore conceived, an extremely unpredictable effect is exhibited. Invented.

The graft copolymer (A) used in the present invention has a weight average particle size of 100 to 300 nm, and the cumulative particle size particle diameter fraction is less than 100 nm.
5% by weight or less, more than 300 nm is 10% by weight or less,
In the presence of a rubbery polymer having a crosslinkage with a gel content of 50 to 95% by weight, an aromatic vinyl monomer and a vinyl cyanide monomer and, if necessary, other copolymerizable monomers are added. It is a graft polymer obtained by graft polymerization and / or a mixture of a homopolymer or a copolymer of the above monomers to be graft-polymerized on the rubbery polymer.

Graft polymer (A) used in the present invention
The rubber-like polymer is a polybutadiene, a copolymer of a vinyl monomer copolymerizable with butadiene, an acrylic ester polymer alone, or a vinyl monomer copolymerizable with the acrylic ester polymer. Copolymers and the like, and further, an ethylene-propylene rubbery polymer alone, a copolymer of the ethylene-propylene rubbery polymer with a vinyl monomer copolymerizable with the ethylene-propylene rubbery polymer, polyorganosiloxane and the like can be mentioned.

Further, as the monomer for producing the acrylic acid ester polymer, for example, methyl acrylate,
Examples thereof include ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate. More than one species can be used.

The ethylene-propylene rubber polymer component is 1,4-hexane or 5-ethylidene-
2-norbornene, 5-vinyl norbornene, dicyclopentadiene and the like are preferable.

The rubbery polymer of the graft copolymer is selected in such a manner that acrylic ester rubber or ethylene-propylene rubber is used when weather resistance and molding processability are required as required properties of the product to be used. Are preferred, and acrylic acid ester-based products are particularly preferred for products having chemical resistance.

The particle size of the rubbery polymer used in the rubbery graft polymer must be within a specific particle size range. That is, the weight average particle diameter of the rubbery polymer is 100 to 300 nm, preferably 100 to 2
00 nm. If it is less than 100 nm, the impact resistance is low, and the chemical resistance is deteriorated. If it exceeds 300 nm, the fluidity is deteriorated and the appearance of the product is remarkably deteriorated.

The rubber-like polymer in the rubber-containing graft polymer is controlled not only in particle size but also in distribution. That is, the rubber-like polymer in the rubber-containing graft polymer has a cumulative weight fraction of particles having a particle size of less than 100 nm of 15 or less.
The cumulative weight fraction of particle diameters of less than 100 wt% and more than 300 nm is 10 wt% or less, preferably the cumulative weight fraction of particle diameters of less than 100 nm is 5 wt% or less and 200 nm.
The cumulative weight fraction of particles having a diameter of more than 15% by weight or less,
More preferably, it is a rubbery polymer having a cumulative particle diameter of less than 100 nm of 5% by weight or less and a cumulative particle diameter of more than 200 nm of 5% by weight or less.

Particle diameter less than 100 nm Cumulative weight fraction is 1
If it exceeds 5% by weight, not only the hot plate welding strength is deteriorated, but also the product appearance and impact resistance are deteriorated, and it cannot withstand practical use.
If the cumulative weight fraction of particles having a particle size of more than 300 nm exceeds 10% by weight, the threading property and the product appearance are deteriorated.

Further, by setting the above-mentioned preferable particle size, the balance among impact resistance, fluidity and product appearance becomes extremely good. The gel content of the rubber polymer in the graft polymer (A) needs to be 50 to 95% by weight. When the gel content is less than 50% by weight or exceeds 95% by weight, impact resistance is deteriorated, and particularly when the gel content is low 5
If it is less than 0% by weight, the product appearance and mechanical strength are deteriorated.

The content of the rubbery polymer in the graft polymer (A) is preferably 20 to 90% by weight. If it is less than 20% by weight, the graft ratio becomes excessively large, and if it exceeds 90% by weight, the graft ratio is lowered, so that the impact resistance tends to be lowered in both cases.

Examples of the aromatic vinyl monomer component used in the production of the graft polymer (A) used in the present invention include styrene, α-methylstyrene, o-,
m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-ter
Examples thereof include t-butyl styrene, ethyl styrene and vinyl naphthalene, but styrene and α-methyl styrene are preferable, and one or more of these can be used. Examples of the vinyl cyanide monomer component used for producing the graft polymer (A) include acrylonitrile and methacrylonitrile, and one or more of these may be used. it can.

In the production of the graft polymer (A) used in the present invention, in addition to the above aromatic vinyl monomer component and vinyl cyanide monomer component, a monomer copolymerizable with them is used. It can be used within a range that does not impair the object of the invention. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl (meth) acrylate (“(meth) acrylate”).
Represents “acrylate and methacrylate”), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth)
Α, β-unsaturated carboxylic acid esters such as acrylate and 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide, N-methylmaleimide, N-ethyl Examples thereof include imide compounds of α, β-unsaturated dicarboxylic acid such as maleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide. Use of one or more of these monomers You can

The method for producing the rubbery polymer used for the graft polymer (A) and the method for controlling the particle size are not particularly limited, and any polymerization method and control method can be adopted. The particle size of the rubber-like polymer used for the graft polymer (A) is relatively small, but for example, a rubber-like polymer having an extremely small particle size (for example, about 80 nm) obtained by an emulsion polymerization method is used. Using a known particle size enlargement method such as a chemical coagulation method using an acid or a physical coagulation method using a homomixer,
Examples include a method of growing the particle size to obtain a large particle size over a long period of time in emulsion polymerization.

The rubber-like polymer used in the graft polymer (A) is obtained by controlling the amount of sodium pyrophosphate added as an electrolyte component in the emulsion polymerization. It is also possible to adjust the weight average particle size of the coalescence. That is, when the addition amount is large, the weight average particle diameter of the obtained rubbery polymer is large, and when the addition amount is small, the weight average particle diameter becomes small. Further, the gelation rate can be adjusted by a crossing agent.

The rubbery polymer used in the graft polymer (A) is not necessarily monomodal as long as it has a specific particle size and particle size distribution, and is multimodal in each rubbery polymer. However, from the viewpoint of production efficiency and the like, monomodality is preferable as much as possible.

The rubbery polymer used for the graft polymer (A) is preferably a rubbery polymer produced by emulsion polymerization using a carboxylic acid emulsifier. By using the carboxylic acid emulsifier, the particle size can be easily controlled and the weather resistance can be improved.

As the graft polymerization method of the graft polymer (A), generally known polymerization methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization can be adopted.
Rubber polymer component at this time, aromatic vinyl monomer component,
The compounding ratio of the vinyl cyanide monomer component and the other copolymerizable monomer component used as necessary is not particularly limited, and each component is appropriately blended depending on the application.

In the above graft polymerization method, for example, first,
A rubbery polymer produced by emulsion polymerization is charged into a reactor equipped with a stirring blade and a jacket, and then the whole amount or a part of the vinyl-based monomer to be graft-polymerized is divided into several times and batched or continuously. While dripping and stirring, at 40 to 70 ° C,
After standing for 5 to 60 minutes, more initiator is added. As a result, the added monomer is impregnated in the rubbery polymer and becomes a polymer in the rubbery polymer.

The vinyl-based copolymer (B) used in the present invention is an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomers which are optionally used. Which are obtained by grafting an aromatic vinyl monomer, a vinyl cyanide monomer, and optionally other copolymerizable monomers to the graft polymer (A). A monomer similar to the monomer to be polymerized can be used.

Here, when the required product is used for a vehicle housing such as a headlight or a winker,
Considering the bondability because the partner to be bonded is a polycarbonate resin or PMMA, and since heat resistance is particularly required in this application, styrene and α-methyl are used as the aromatic vinyl monomer. Acrylonitrile is used as the styrene and vinyl cyanide monomers, and maleimide compounds are used as the other copolymerizable monomers that are optionally used, and N-phenylmaleimide is particularly preferably used.

In the present invention, the blending ratio of the graft polymer (A) and the vinyl copolymer (B) is 20 to 70% by weight of the graft polymer (A) and the vinyl copolymer (B). ) 80 to 30% by weight, particularly preferably 30 to 50% by weight of the graft polymer (A) and 70 to 50% by weight of the vinyl copolymer (B) from the viewpoint of physical properties. If the content of the graft polymer (A) is less than 20% by weight, the impact resistance will be lowered, and if it exceeds 70% by weight, the fluidity and the product appearance will be deteriorated.

Examples of the polycarbonate resin (C) used in the present invention include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dimethylphenyl) propane and bis (4-hydroxyphenyl) phenylmethane, and carbonic acid esters such as phosgene (phosgene method) or diaryl carbonate (transesterification method)
Examples thereof include bis (hydroxyaryl) alkane-based polycarbonate resins obtained from the above, and these may be used alone or in combination of two or more.

The physical properties of the polycarbonate resin (C) used in the present invention are not particularly limited, but those having a viscosity average molecular weight (solution viscosity method) of 18,000 to 26,000 are preferable. That is, the viscosity average molecular weight is 18,0
When it is less than 00, the fluidity is good, but when it is used in a lamp housing or the like, it is required to have chemical resistance since it is used in the engine room, and this chemical resistance tends to be poor. However, when the viscosity average molecular weight exceeds 26,000, the fluidity is deteriorated, which is also not preferable.

Graft polymer (A) used in the present invention
In the blend of the vinyl copolymer (B) with the polycarbonate resin, the blending ratio is the graft polymer (A).
10-70% by weight, vinyl copolymer (B) 10-70
%, The polycarbonate resin is 20 to 80% by weight. When the polycarbonate resin is less than 20% by weight, impact resistance is lowered, and when it exceeds 80% by weight, fluidity is deteriorated.

Graft polymer (A) used in the present invention
And vinyl-based copolymer (B), and graft polymer (A)
The vinyl copolymer (B) and the polycarbonate resin (C) can be mixed with a Banbury mixer, a kneader, or a melt kneader such as a single-screw or twin-screw extruder to obtain a uniform composition. You can In addition to the graft polymer (A), the vinyl copolymer (C), and the polycarbonate resin, the thermoplastic resin composition for hot plate welding of the present invention may contain an antioxidant, a heat stabilizer, and a light stabilizer, if necessary. Agents, lubricants, plasticizers, flame retardants, antistatic agents, inorganic or organic colorants may be contained.

[0047]

EXAMPLES The present invention will be described in more detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. still,
In the following, "part" means "part by weight", and the particle size of the rubber-like polymer is the same as that of Nikkiso Co., Ltd.
It was determined by the dynamic light scattering method using trac Model: 9230UPA. The values obtained are the weight average (volume) particle size and the particle size distribution, and the cumulative weight distribution of the particle size distribution.
The weight average molecular weight of the vinyl polymer was calculated by a standard polystyrene conversion method using GPC (gel permeation chromatography) manufactured by Tosoh Corporation.

<Synthesis Example 1>: Synthesis of acrylic ester rubbery polymer The following materials were charged in a pressure resistant container, and semi-cured tallow soda soap 1.5 parts sodium pyrophosphate 0.3 part deionized water 200 parts nitrogen Under a stream of air, the temperature was raised to 80 ° C., butyl acrylate 100 parts potassium persulfate 0.3 part triallyl cyanurate 0.3 part was added dropwise over 4 hours, and polymerization was performed. After completion of dropping, 1
After standing for a period of time, the reaction was terminated by cooling. The obtained latex (Lx-1) had a solid content of 32.5% by weight and an average particle diameter of 85 nm.

(Experimental Example 1) Acrylic ester type rubbery polymer latex (Lx-1) 1 obtained in Synthesis Example 1
00 parts (solid content) and 0.15 part of sodium dodecylbenzene sulfonate were added. Thereafter, a 5% aqueous solution of acetic acid was continuously added dropwise over a period of 30 minutes to a total of 60 parts of the aqueous solution of acetic acid. After the dropwise addition of the acetic acid aqueous solution, a 10% aqueous sodium hydroxide solution was continuously added dropwise over 10 minutes.
The rubbery polymer in the latex after the dropwise addition had an average particle diameter of 150 nm, and the agglomerate was 0.05% by weight (BLx-1).

(Experimental Example 2) In Experimental Example 1, the amount of the acetic acid aqueous solution, the amount of sodium hydroxide and the like were adjusted to be enlarged, and the average particle diameter of the rubbery polymer in the latex was 180 nm, and the agglomerates were 0. It was 08% by weight (BLx-2).

<Synthesis Example 2>: Synthesis of Graft Polymer (A-1) Using the latex (BLx-1) obtained in Experimental Example 1, a graft polymer was synthesized with the following formulation.

Deionized water 240 parts Semi-hardened tallow soda soap 1.5 parts Potassium hydroxide 0.05 parts BLx-1 60 parts Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.25 parts Ferrous sulfate 0.004 Parts Sodium pyrophosphate 0.02 parts Crystalline glucose 0.2 parts Autoclave deionized water, semi-hardened tallow soda soap,
Charge potassium hydroxide and polybutyl acrylate latex, and after heating to 60 ° C, add ferrous sulfate, sodium pyrophosphate and crystalline glucose and keep styrene, acrylonitrile and cumene hydroperoxide for 2 hours while maintaining at 60 ° C. Continuous addition over 70
The temperature was raised to ℃ and kept for 1 hour to complete the reaction. The polymer obtained by such a reaction is coagulated with sulfuric acid, washed thoroughly with water,
It was dried to obtain a graft copolymer (A-1).

<Synthesis Example 3> Synthesis of Graft Polymer (A-2) Synthesis Example 1 except that the rubbery polymer latex (BLx-2) synthesized and enlarged in Experimental Example 2 was used. Synthesis was performed in the same manner to obtain a graft polymer (A-2).

<Synthesis Example 4>: As a synthetic rubbery polymer of the graft polymer (A-3), EPDM latex (BLx-
Synthesis was performed in the same manner as in Synthesis Example 1 except that 3) was used to obtain a graft polymer (A-3).

<Synthesis Example 5>: As a synthetic rubbery polymer of the graft polymer (A-4), EPDM latex (BLx-
Synthesis was performed in the same manner as in Synthesis Example 1 except that 4) was used to obtain a graft polymer (A-4).

<Synthesis Example 6>: As a synthetic rubbery polymer of the graft polymer (A-5), polybutadiene latex (BL
x-5) was used and synthesized in the same manner as in Synthesis Example 1 to obtain a graft polymer (A-5).

<Synthesis Example 7>: As a synthetic rubbery polymer of the graft polymer (A-6), polybutadiene latex (BL
x-6) was used and synthesized in the same manner as in Synthesis Example 1 to obtain a graft polymer (A-6).

<Synthesis Example 8>: Synthesis example 1 of the graft polymer (A-7), except that a synthetic and enlarged rubbery polymer latex (BLx-7) was used as the synthetic rubbery polymer. A graft polymer (A-7) was obtained in the same manner as described above.

<Synthesis Example 9>: Synthesis Example 1 of the graft polymer (A-8) except that a synthetic and enlarged rubbery polymer latex (BLx-8) was used as the rubbery polymer. A graft polymer (A-8) was obtained in the same manner as described above.

<Synthesis Example 10>: Synthesis Example 1 of the graft polymer (A-9), except that a latex of a rubbery polymer (Lx-1) that does not enlarge as the rubbery polymer was used. Synthesis was performed in the same manner to obtain a graft polymer (A-9).

Table 1 shows the particle size and particle size distribution of the rubber polymer and the graft polymer.

[0062]

[Table 1]

<Synthesis Example 11>: Synthesis of vinyl-based polymer (B-1) 120 parts of water, 0.002 part of sodium alkylbenzene sulfonate, 0.5 part of polyvinyl alcohol, and 0 part of azoisobutyronitrile were placed in a nitrogen-substituted reactor. .3 parts, and a monomer mixture consisting of 35 parts of acrylonitrile and 65 parts of styrene was added and heated at a starting temperature of 60 ° C. for 5 hours and then 1
The temperature was raised to 20 ° C., and after reacting for 4 hours, a polymer was taken out.
The conversion rate was 96% and the weight average molecular weight was 96,000.

<Synthesis Example 12>: Synthesis of vinyl polymer (B-2) Synthesis Example 11 except that a monomer mixture consisting of 25 parts of acrylonitrile and 75 parts of α-methylstyrene was used.
Polymerization was carried out in the same manner as in. The obtained polymerized product had a conversion rate of 98% and a weight average molecular weight of 108,000.

<Synthesis Example 13>: Synthesis of hard polymer (B-3) except that a monomer mixture consisting of 28 parts of acrylonitrile, 24 parts of styrene, 35 parts of α-methylstyrene and 13 parts of N-phenylmaleimide was used. Polymerization was carried out in the same manner as in Synthesis Example 11. The obtained polymer has a conversion rate of 9
It was 7% and the weight average molecular weight was 126,000.

The graft polymer (A), the vinyl copolymer (B) and / or the polycarbonate resin (C) obtained in the above-mentioned Production Example are used in the proportions shown in Tables 2 and 3.
Then, 0.5 part of an alcohol-based lubricant and 0.3 part of a phenol-based antioxidant were added, and the mixture was uniformly kneaded with a Banbury mixer, and then pelletized by a pelletizer. The required pellets were produced from the obtained pellets using an injection molding machine.

As the polycarbonate resin, Iupilon S- manufactured by Mitsubishi Engineering Plastics Co., Ltd.
3000 was used. It is shown as C-1 in Tables 2 and 3.

Various properties of the obtained molded product were tested under the following conditions and methods, and the results are shown in Tables 2 and 3.

<Test Evaluation> Izod impact strength: ASTM-D256 (normal temperature)
(J / m) Melt flow index: ASTM-D1238
(230 ° C / 10kg load) (g / 10min.)-Heat deformation temperature: ASTM-D648 (1.8MPa load) (° C)

63 ± 3 ° C., sprayed using a sunshine weatherometer (Suga Test Instruments Co., Ltd .: Sunshine Super Long Life Weatherometer WEL-6XS-HCH-B) as a weathering and discoloration acceleration tester 2000 with weather resistance test
The color tone change (ΔE) after irradiation was measured for a period of time.

-Appearance of test piece Using a digital goniophotometer UGV-5D manufactured by Suga Test Instruments Co., Ltd., the appearance state is measured for glossiness at an incident angle of 60 ° and a reflection angle of 60 °.

After forming a test piece having a diffuse reflectance of 180 × 35 × 2 mm, aluminum was vapor-deposited according to a conventional method. The 45 ° diffuse reflectance of this vapor-deposited molded product was measured by a digital reflectometer (TR-
1100AD; manufactured by Tokyo Denshoku Center). Here, the higher the diffuse reflectance, the better the appearance of the product, the less likely diffused reflection occurs, for example, it is preferably used for a vehicle lamp housing, but when the diffuse reflectance is low, diffused reflection easily occurs (that is, Product appearance is poor),
It cannot be used as a lamp housing.

· Hot plate welding property (stringing property) 280 is a 3.2 mm thick flat plate molded product obtained by injection molding.
Pressed into a hot plate heated to 300 ° C, 300 ° C, and 330 ° C for 8 seconds so that the pressing amount becomes 1 mm, and 500 mm /
min. The state of stringing that occurred on the welded surface when separated at the speed of was observed. The evaluation was performed as follows. ◎: No thread pulling ○: Thread pulls little, △: Long thread, thread pulling ×: Thread pulling is bad

Hot plate weldability (welding strength) PM obtained by injection molding the same flat plate as the above-mentioned molded product at 240 ° C.
A tensile tester (manufactured by SHIMADZU: AUTOGRAPHAG-20, manufactured by welding MA under the hot plate condition)
kNG) and a pulling speed of 1.0 mm / min. The tensile strength of the welded portion (MPa) was measured by pulling with a load cell 5000N.

[0075]

[Table 2]

[0076]

[Table 3]

The following can be seen from Tables 2 and 3.

Examples include ABS resin systems having poor weather resistance, but basically, any rubbery polymer can be used for hot plate welding, but in particular, applications requiring weather resistance,
In particular, it is preferable to select a lamp housing having better weather resistance.

A thermoplastic resin composition for hot plate welding using a rubbery polymer having a specific particle size and particle size distribution specified in the present invention has hot plate weldability (no stringing and good welding strength). ), The surface appearance, fluidity, impact resistance and the like are well balanced, and it is clear that it has extremely excellent characteristics.

[0080]

Industrial Applicability As described above, the thermoplastic resin composition for hot plate welding of the present invention uses mechanical properties such as impact resistance by using a rubbery polymer having a specific particle size and particle size distribution. In addition, it has an excellent balance in molding processability such as fluidity, surface appearance of molded products, and significantly suppresses stringing that occurs during hot plate welding, so it is a lamp housing for automobiles such as head lamps and rear combination lamps. It is suitable as a material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F21V 15/01 F21W 101: 12 // F21W 101: 10 101: 14 101: 12 F21M 3/02 A 101: 14 (72) Inventor Yasuyuki Hiromoto 525-14 Oki Ube, Ube City, Yamaguchi Prefecture F-Term inside Ube Factory of Ube Silicon Co., Ltd. (reference) TC08 TC14 TD07 TH06 TN07 4J002 BC06X BN06W BN12W CG00Y GN00

Claims (6)

[Claims] 1. The weight average particle diameter is 100 to 300 nm, and the cumulative weight fraction of particle diameter is less than 100 nm is 1
5% by weight or less, more than 300 nm is 10% by weight or less,
In the presence of a rubbery polymer having a crosslinkage with a gel content of 50 to 95% by weight, an aromatic vinyl monomer and a vinyl cyanide monomer and, if necessary, other copolymerizable monomers are added. 20 to 70% by weight of a graft polymer (A) obtained by graft polymerization, and an aromatic vinyl monomer, a vinyl cyanide monomer, and other monomers copolymerizable as necessary are polymerized. A thermoplastic resin composition for hot plate welding, which comprises 80 to 30% by weight of a vinyl-based copolymer (B). 2. The weight average particle diameter is 100 to 300 nm, and in the cumulative particle diameter particle size fraction, less than 100 nm is 1
5% by weight or less, more than 300 nm is 10% by weight or less,
In the presence of a rubbery polymer having a crosslinkage with a gel content of 50 to 95% by weight, an aromatic vinyl monomer and a vinyl cyanide monomer and, if necessary, other copolymerizable monomers are added. 10 to 70% by weight of the graft polymer (A) obtained by graft polymerization, and an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, other copolymerizable monomers are polymerized. A thermoplastic resin composition for hot plate welding, comprising 10 to 70% by weight of a vinyl copolymer (B) and 20 to 80% by weight of a polycarbonate resin (C). 3. The rubber polymer used in the graft polymer (A) is an acrylic ester rubber, ethylene-
The thermoplastic resin composition for hot plate welding according to claim 1 or 2, containing at least one propylene-based rubber. 4. The vinyl polymer (B) is a vinyl polymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and a maleimide compound. A thermoplastic resin composition for hot plate welding. 5. A resin molded product, characterized in that a molded product comprising the thermoplastic resin composition according to any one of claims 1 to 4 is joined by hot plate welding. 6. A resin composition for a vehicle lamp, comprising the thermoplastic resin composition according to any one of claims 1 to 4.