JPH0859947A - Thermoplastic resin composition and its synthetic resin composite - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin composition having balanced characteristics excellent in resistance to fluorocarbons, mechanical properties and vacuum forming property and a synthetic resin composite composed of molding of the thermoplastic resin composition and urethane foam, hardly causing environmental stress crack disruption in molding of the thermoplastic resin composition and suitable as a heat-insulating material, a vibration damping material and a sound insulating material, etc. CONSTITUTION: This thermoplasitic resin composition is composed of (A) 100 pts.wt. of a diene-based rubber-containing styrene-based resin, (B) 1-50 pts.wt. of a vinyl resin-containing acrylic rubber-like polymer obtained by polymerizing a vinylic monomer in the presence of an acrylic rubber-like polymer and (C) 0.75-48 pts.wt. of a polymer of a vinylic monomer and having >=200000 weight- average molecular weight, and the total amount of the components B+C is 5-60 pts.wt. A molding is obtained by using a synthetic resin composite consisting of the thermoplastic resin composition and urethane foam.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a styrene resin containing a diene rubber, an acrylic rubber polymer containing a vinyl resin obtained by polymerizing a vinyl monomer in the presence of an acrylic rubber polymer, and a weight average. Thermoplastic resin composition comprising a vinyl-based polymer having a molecular weight of 200,000 or more and having excellent CFC resistance and mechanical properties, and a synthetic resin composite comprising a molded product of the thermoplastic resin composition and a urethane foam. Regarding

[0002]

2. Description of the Related Art Styrene resins containing diene rubber represented by ABS resins are excellent in high impact resistance, rigidity, moldability, gloss and appearance, and are widely used as industrial parts and household electric appliances. . The ABS resin has environmental stress cracking resistance against CFC 11 which is a foaming agent of foamed urethane foam used for heat insulation between an outer box and an inner box of a household refrigerator, for example, and therefore has a refrigerator. It is used as a material for inner boxes.

Specified CFCs such as CFC11 currently used as a foaming agent are pointed out as substances causing ozone layer depletion, and their production is planned to be stopped from the viewpoint of global environment protection. Therefore, it is planned to use an alternative CFC having less possibility of environmental damage, but CFC 141b (ie 1,1-dichloro-1-fluoroethane) and CFC 123 (ie 1, 1, which are expected to be used as a foaming agent). 1
-Alternative CFCs such as dichloro-2,2,2-trifluoroethane) have a higher penetrating power into the resin than CFC-11, and therefore synthetic resin composites produced by using the alternative CFCs as a blowing agent. If ABS resin is used for the above, cracking is likely to occur.

Although there is a so-called high nitrile resin (Japanese Patent Laid-Open No. 62-228860) which has a significantly high content of acrylonitrile and is excellent in CFC resistance even in ABS resin, a resin having a high acrylonitrile content is Since it has a yellowish tint, the molded product also has a yellowish tint, and has problems such as poor thermal stability and vacuum formability.

[0005]

DISCLOSURE OF THE INVENTION The present inventors
Improvement of environmental stress crack resistance of diene rubber-containing styrene resin itself represented by resin, especially improvement of CFC substitute, and the above-mentioned related to a synthetic resin composite comprising a molded body and urethane foam using this resin. As a result of diligent study to solve the problem, styrene resin containing diene rubber,
A vinyl resin-containing acrylic rubber-like polymer obtained by polymerizing one or more vinyl monomers in the presence of an acrylic rubber-like polymer, and a vinyl polymer having a weight average molecular weight of 200,000 or more. The object was achieved by using a thermoplastic resin composition containing

[0006]

That is, the thermoplastic resin composition of the present invention is one kind in the presence of 100 parts by weight of a diene rubber-containing styrene resin << component (A) >> and an acrylic rubber polymer. A vinyl-based resin-containing acrylic rubber-like polymer << (B) component >> obtained by polymerizing 1 to 200 parts by weight of the above vinyl-based monomer, and a vinyl-based monomer having a weight average molecular weight of 200,000 or more. Polymer of polymer << (C)
Ingredients >>, and the proportion of each component is 100 parts by weight of the component (A) to 1 to 50 parts of the component (B).
Parts by weight, and 0.75 to 48 parts by weight of the component (C),
Moreover, the total amount of the component (B) + the component (C) is 5 to 60 parts by weight. Furthermore, it is to make a synthetic resin composite comprising a molded body of this thermoplastic resin composition and a urethane foam.

The diene rubber-containing styrene resin as the component (A) of the present invention comprises a diene rubber component and a resin component. Examples of the diene rubber component include conjugated diene monomers such as butadiene, isoprene, dimethylbutadiene, chloroprene, and cyclopentadiene, and non-conjugated diene monomer such as 2,5-norbornadiene, 4-ethylidenenorbornene, and 1,4-cyclohexadiene. A homopolymer such as a polymer,
Or a conjugated diene monomer or a non-conjugated diene monomer and styrene, α-methylstyrene, an aromatic vinyl monomer such as vinyltoluene, acrylonitrile, vinyl cyanide monomer such as methacrylonitrile, methyl acrylate, ethyl Acrylic ester monomers such as acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate Body, olefin monomers such as ethylene, propylene, 1-butene, isobutylene and 2-butene,
Maleimide-based monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide and N-phenylmaleimide, acid anhydride monomers such as maleic anhydride, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether. It is possible to use those obtained by copolymerizing vinyl ether monomers such as phenyl vinyl ether and glycidyl vinyl ether, and vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone.

Further, as the diene rubber component, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can be used as a crosslinking monomer. The polyfunctional vinyl monomer includes divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, allyl acrylate, allyl methacrylate, vinyl. Acrylate, vinyl methacrylate, glycidyl acrylate,
Examples thereof include glycidyl methacrylate.

Further, the diene rubber component used as the component (A) is required to have a graft active point,
Specifically, it is preferable that the rubber component has a carbon-carbon double bond.

The method of polymerizing the above-mentioned monomers is not particularly limited, and known techniques such as emulsion polymerization and solution polymerization can be used. Further, the diene rubber component as the component (A) does not have to be one type, and may be a mixture of two or more types of rubber components separately polymerized.

The diene rubber component in the component (A) is 1 to 40% by weight, preferably 3 to 30% by weight.
If it is less than 1% by weight, the impact strength is insufficient, and if it exceeds 40% by weight, the rigidity becomes insufficient.

The monomer constituting the resin component of the diene rubber-containing styrene resin as the component (A) of the present invention is an aromatic vinyl monomer such as styrene, α-methylstyrene, vinyltoluene or t-butylstyrene. Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile are essential, and these monomers may be used alone, but in addition to these, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate. Acrylic acid ester monomers such as octyl acrylate, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, acrylamide, meta Amide-based monomers such as rylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, olefin monomers such as ethylene, propylene, 1-butene, isobutylene and 2-butene, maleimide, N -Methylmaleimide, N-ethylmaleimide, N
-Maleimide-based monomers such as phenylmaleimide, acid anhydride monomers such as maleic anhydride, methyl vinyl ether,
Vinyl ether monomers such as ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and glycidyl vinyl ether, and vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone may be copolymerized alone or in combination. .

As described above, it is essential that the resin component (A) contains an aromatic vinyl monomer and a vinyl cyanide monomer, and further contains 20 to 50% by weight of the vinyl cyanide monomer. Preferably. Especially preferred is 25-4
It is 5% by weight. When it is less than 20% by weight, the CFC resistance of the synthetic resin composite is not sufficient, and when it exceeds 50% by weight, the thermoplastic resin composition is yellowed due to the heat history during molding.

The component (A) used in the present invention is composed of a diene rubber component and a resin component as described above, and is grafted to the interface between the diene rubber component having a particulate structure and the resin component which is a continuous phase. It is necessary to interpose the structure.
It is known that such a structure is achieved by a so-called graft polymerization method of polymerizing a part or all of the monomers constituting the resin component in the presence of the diene rubber component,
The component (A) of the present invention can also be produced by a known graft polymerization technique.

In order to adjust the content of the diene rubber component contained in the component (A), it is possible to mix the resin component separately polymerized with the component (A). The separately polymerized resin component does not have to have the same composition as the resin component obtained by graft polymerization. For example, the component (A) obtained by graft-polymerizing acrylonitrile and styrene in the presence of polybutadiene may be mixed with an acrylonitrile-styrene copolymer with a resin component, or acrylonitrile, styrene and α-methylstyrene may be separately added. It is also possible to mix an acrylonitrile-styrene-α-methylstyrene copolymer obtained by polymerizing.

The resin component in the component (A) is, as described above, a polymer which is graft-polymerized when polymerized in the presence of a diene rubber component, a polymer which is not graft-polymerized, and a diene. A polymer mixed to adjust the content of the rubber component.

Specific examples of the diene rubber-containing styrene resin as the component (A) used in the present invention include ABS (acrylonitrile-butadiene-styrene) resin and heat-resistant ABS.
(Acrylonitrile-butadiene-α-methylstyrene) resin, AES (acrylonitrile-EPDM-styrene) resin, MABS (methyl methacrylate-butadiene-styrene) resin and the like can be mentioned.

Next, the vinyl rubber-containing acrylic rubber polymer as the component (B) used in the present invention will be explained. The acrylic rubber-like polymer in the component (B) used in the present invention is, for example, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-
Ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate,
Stearyl acrylate, 2-ethoxyethyl acrylate, homopolymers or copolymers of acrylic acid ester monomers such as 2-hydroxyethyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hexadecyl methacrylate, dodecyl methacrylate, Decyl methacrylate, octadecyl methacrylate, homopolymer or copolymer of methacrylic acid ester monomer selected from stearyl methacrylate and pentyl methacrylate, and acrylic acid ester monomer and methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Examples thereof include rubbery polymers obtained by copolymerizing one or more monomers such as butyl methacrylate, cyclohexyl methacrylate, hydroxymethacrylate, and the above-mentioned methacrylic acid ester monomers.

The acrylic rubber-like polymer in the component (B) may or may not use a polyfunctional vinyl monomer in the polymerization of the acrylic rubber-like polymer.
As the polyfunctional vinyl monomer, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycidyl methacrylate, divinylbenzene, allyl acrylate, allyl methacrylate, vinyl acrylate,
Examples thereof include vinyl methacrylate. When the polyfunctional vinyl monomer unit is present in the acrylic rubber polymer,
When a vinyl-based monomer is polymerized, it becomes a graft active point and a part is graft-polymerized. Further, even if the polyfunctional vinyl monomer unit is present, it is preferably 8% by weight or less (the following includes 0). If it exceeds 8% by weight, the chlorofluorocarbon resistance is lowered, which is not preferable.

The glass transition temperature of the acrylic rubber-like polymer is required to be 20 ° C. or lower, more preferably 10 ° C. or lower. Glass transition temperature is 2
If it exceeds 0 ° C, the CFC resistance and the impact resistance deteriorate.

Further, the above-mentioned acrylic rubber-like polymer is required to have a gel content of 70% or less, and a preferable gel content is 50% or less. If the gel content of the acrylic rubber-like polymer is more than 70%, the chlorofluorocarbon resistance is significantly deteriorated, which is not preferable.

The gel content referred to in the present invention means that about 1.0 g of the acrylic rubber-like polymer is precisely weighed (S ₀ g),
It is put in a basket made of 400-mesh stainless steel wire mesh, immersed in 100 g of toluene, left at 5 ° C. for 24 hours, then pulled out of the basket and air-dried at room temperature.
A value calculated by measuring ₁ g and following the general formula (I). (S ₁ / S ₀ ) × 100 (%) (I)

The component (B) of the present invention polymerizes a vinyl monomer in the presence of the above acrylic rubber-like polymer. Specifically, it is styrene, α-methylstyrene, vinyltoluene, t-butyl. Aromatic vinyl monomers such as styrene, acrylonitrile, vinyl cyanide monomers such as methacrylonitril, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, hexyl methacrylate, 2-
Methacrylic acid ester monomers such as ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethoxyethyl Acrylate, 2
Examples thereof include acrylic acid ester monomers such as ethoxyethyl acrylate and 2-hydroxyethyl acrylate, but are not limited thereto. In addition, (B)
The glass transition temperature of the vinyl resin component in the component vinyl resin-containing acrylic rubber polymer preferably exceeds 20 ° C.

The method for polymerizing the acrylic rubber-like polymer and the vinyl resin-containing acrylic rubber-like polymer as the component (B) of the present invention is not particularly limited, and emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization are carried out. Although known techniques such as the above can be used, production by emulsion polymerization is industrially most advantageous. This is because, in the present invention, when the thermoplastic resin composition containing the component (A), the component (B), and the component (C) is produced, (B)
This is because it is more preferable to mix and produce the polymer mixture obtained by mixing the emulsion of the component polymer and the emulsion of the component polymer (C) and the component (A).

The component (B) of the present invention is obtained by polymerizing 1 to 200 parts by weight of a vinyl monomer in the presence of 100 parts by weight of an acrylic rubber-like polymer having the above glass transition temperature and gel content. However, the preferred vinyl-based monomer is 50 to 160 parts by weight. If the amount of the vinyl monomer exceeds 200 parts by weight, the chlorofluorocarbon resistance becomes poor, and if it is less than 1 part by weight, the compatibility of the component (B) with the component (A) is insufficient.

Next, the vinyl monomer polymer as the component (C) of the present invention will be explained. Examples of the vinyl-based monomer that constitutes the component (C) of the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitr. Polymer, methyl methacrylate,
Methacrylic acid ester monomers such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate,
Acrylic ester monomers such as butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-hydroxyethyl acrylate, etc. Acrylamide, methacryl Amide-based monomers such as amides, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, olefin monomers such as ethylene, propylene, 1-butene, isobutylene and 2-butene, maleimide, N -Methylmaleimide,
Maleimide-based monomers such as N-ethylmaleimide and N-phenylmaleimide, acid anhydride monomers such as maleic anhydride, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether, glycidyl vinyl ether, etc. Vinyl ether monomers, vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone, and the like, but are not limited thereto.

The component (C) has a glass transition point of 20 ° C.
It is necessary to exceed. A more preferable glass transition point is 30 ° C or higher. When the glass transition point is 20 ° C. or lower, the heat resistance of the thermoplastic resin composition is lowered, which is not preferable.

The component (C) of the present invention is required to have a weight average molecular weight of 200,000 or more as measured by gel permeation chromatography (GPC) using standard polystyrene as a calibration curve. A more preferable weight average molecular weight is 300,000 or more. When the weight average molecular weight is less than 200,000, the thickness of the thermoplastic resin composition tends to be non-uniform during vacuum forming.

The method for producing the component (C) polymer of the present invention is not particularly limited, and emulsion polymerization, suspension polymerization, solution polymerization,
Although known techniques such as bulk polymerization can be used, production by emulsion polymerization is industrially most advantageous. This is because, in the present invention, it is convenient in the present invention when mixing the emulsions of the component (B) and the component (C). It is because a polymer having a molecular weight can be easily produced.

In producing the component (C) polymer of the present invention, the vinyl monomer is selected such that the glass transition temperature and the weight average molecular weight of the obtained component (C) polymer satisfy the requirements of the present invention. It is optional as long as it does.

It is possible to use a chain transfer agent for the purpose of controlling the molecular weight of the component (C) polymer. The chain transfer agent that can be used is not particularly limited, and examples thereof include octyl mercaptan, decyl mercaptan, dodecyl mercaptan,
Examples thereof include thioglycolic acid, ethyl thioglycolate, ethyl o-mercaptobenzoate, halogen compounds such as carbon tetrachloride, hydrocarbons such as limonene and terpinolene, nitro compounds such as trinitrobenzene, and benzoquinone.

In the present invention, 1 to 50 parts by weight of the component (B) and 0.7 of the component (C) are used with respect to 100 parts by weight of the component (A).
A thermoplastic resin composition is produced by containing 5 to 48 parts by weight and mixing them so that the total amount of the component (B) + the component (C) is 5 to 60 parts by weight. More preferably, with respect to 100 parts by weight of component (A), 1.5 to 35 parts by weight of component (B), 1.8 to 37.5 parts by weight of component (C), and (B)
The total amount of the component + (C) component is 6 to 50 parts by weight.
When the amount of the component (B) is less than 1 part by weight relative to 100 parts by weight of the component (A), the CFC resistance of the thermoplastic resin composition becomes insufficient, and the total of the component (B) + the component (C) When the amount is less than 5 parts by weight, the vacuum moldability of the thermoplastic resin composition is inferior, and when it exceeds 60 parts by weight, peeling property tends to occur.

The thermoplastic resin composition of the present invention can be obtained by melt mixing the components (A), (B) and (C), but the method is not particularly limited. For example, after blending with a Henschel mixer or a tumbler, it can be obtained using a known melt mixing method such as a screw type extruder, a Brabender, a Banbury mixer, a cokneader, a mixing roll and the like.

Further, as a preferred method of mixing the components (A), (B), and (C), there are (B)
A desirable method is to mix the emulsion of the component polymer with the emulsion of the component polymer (C), and then mix the polymer mixture obtained by separation with component (A).

In the case of the mixture, 1 to 50 parts by weight of the component (B) and 0.75 to 48 parts by weight of the component (C) are added to 100 parts by weight of the component (A), and the component (B) + ( 20% to 85% by weight of the emulsion of the component (B) polymer (as the solid content of the polymer) and (C) the component polymer under the condition that the total amount of the component C) is 5 to 60 parts by weight. Emulsion 15-80
% By weight (as the solid content of the polymer) are mixed in an emulsion state and then separated to obtain a polymer mixture, which is mixed with the component (A) by the mixing method described above. Further, as the solid content of the polymer, the emulsion of the component (B) polymer is 25 to 7
0% by weight, emulsion of component (C) polymer 30 to 75% by weight
Is. Further, the emulsion of the component (B) polymer is 20% by weight.
If less than 8, the CFC resistance of the thermoplastic resin composition is inferior, and
If it exceeds 5% by weight, a molded article made of the thermoplastic resin composition causes a delamination phenomenon.

In the present invention, the emulsion of the component (B) polymer and the emulsion of the component (C) are mixed, but when the component (B) or the component (C) is produced by emulsion polymerization. Is
The emulsion obtained by emulsion polymerization can be used as it is, but when it is produced by another polymerization method, a step of emulsifying the obtained polymer is required. The emulsification method of the polymer is not particularly limited, and any known technique can be used.
For example, a method of removing the solvent after mixing and stirring the polymer solution with an emulsifier and water to form an emulsion, a method of mixing and stirring fine powder obtained by pulverizing the polymer with an emulsifier and water to form an emulsion, There is a method of pulverizing a polymer in the presence of an emulsion and water to prepare an emulsion, but the method is not limited to these.

An emulsion polymer of component (B) or component (C),
Alternatively, the type of emulsifier used for emulsifying the polymer is not particularly limited, and can be arbitrarily selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants, but anionic Surfactants can be used most advantageously.

The method for mixing the above-mentioned emulsions is not particularly limited, and mixing can be performed using a fixed container type mixing device, a rotary container type mixing device, a pipeline mixer, a static mixer and the like.

From the above-mentioned mixed emulsion, the components (B) and (C)
The method of separating the polymer mixture consisting of components is not particularly limited, the emulsion, hydrochloric acid, sulfuric acid, phosphoric acid, acids such as acetic acid, sodium chloride, calcium chloride, aluminum chloride, sodium sulfate, an electrolyte such as magnesium sulfate, Polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, a method of adding a precipitant such as a water-soluble polymer such as carboxymethyl cellulose, a method of freezing the emulsion and destructing the emulsion, a method of heating the emulsion in a high temperature gas An example is a method of incandescence.

The polymer mixture separated from the mixed liquid of the component (B) polymer emulsion and the component (C) polymer emulsion can be further fed to a melt kneader to be melt-kneaded.
Examples of the melt-kneading device that can be used include a Banbury mixer, an intensive mixer, a cokneader, an extruder, and a roll. Further, it is also possible to use a melt-kneading device having a dehydration mechanism, but in the case of using the device, an emulsion and a precipitating agent are continuously supplied to the device, and mixing, emulsion destruction, dehydration and drying are performed. It is also possible to carry out melt-kneading continuously in the same device.

In addition, the thermoplastic resin composition of the present invention may contain other thermoplastic resins, dispersants, lubricants, antioxidants, antibacterial agents, pigments and the like, if necessary.

The thermoplastic resin composition of the present invention has excellent properties in which flon resistance, impact strength and vacuum moldability are well balanced, and therefore it can be used as a synthetic resin composite.

Next, a synthetic resin composite comprising a molded product using the thermoplastic resin composition of the present invention and a polyurethane foam will be described. The synthetic resin composite of the present invention is produced by reacting a mixture containing a polyisocyanate, a polyol, and a foaming agent as main components in the presence of a preformed molding product using the thermoplastic resin composition. However, the composition and manufacturing method of the urethane foam of the present invention are not particularly limited.

Specific examples of polyisocyanates used in the production of urethane foams include tolylene diisocyanate,
o-Tolylene diisocyanate, diphenylmethane-
4,4-diisocyanate, 1,3-xylylene diisocyanate, naphthylene-1,5-diisocyanate,
1-methylcyclohexane-2,4-diisocyanate and the like. Specific examples of the polyol include 1,4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, poly (ethylene oxide-propylene oxide) copolymer, α, ω-polycaprolactone diol,
There are diols such as α, ω-polybutadiene diol, triols such as glycerin and trimethylolpropane, pentaerythritol, methylglycoside, sorbitol, sucrose, etc., and addition products of ethylene oxide or propylene oxide with these polyols Can be mentioned.

As the foaming agent, CFC 11 and CFC 1
2, CFC 113, CFC 123, CFC 141b, methylene chloride and the like.

It is known to use water, which acts as a chemical blowing agent, an organic tin compound, a catalyst typified by tertiary amines, and a surfactant, which acts as a bubble stabilizer, in the production of urethane foams. Although a number of techniques for using these have been disclosed, the urethane foaming formulation is not particularly limited in the present invention.

[0047]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The parts and% in the examples are shown by weight.

First, the thermoplastic resin composition will be described. (1) Component (A) The ABS resin powder shown in Table 1 and the AS resin were mixed in the proportions shown in Table 1 to obtain the components (A) A-1 to A-4. The AS resin used as the component (A) had a weight average molecular weight by GPC of less than 200,000.

(2) Component (B) Experimental Example 1: Preparation of component (B) (a) Acrylic rubbery polymer 120 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate were charged into an autoclave and stirred. 65 ° C
Heated to. Here, ferrous sulfate heptahydrate 0.005
Parts, ethylenediaminetetraacetic acid tetrasodium dihydrate 0.
An aqueous solution prepared by dissolving 01 part and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added. Then, 20% of 100 parts of the monomer mixture having the composition shown in Table 2 was poured into the autoclave, and 2.5 parts of 0.2% potassium persulfate aqueous solution was added to initiate polymerization. Simultaneously with the start of polymerization, the remaining amount of the monomer mixture was continuously added over 4 hours. Simultaneously with the start of polymerization, an aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 20 parts of pure water was continuously added over 6 hours. After the addition of the potassium persulfate solution was completed, the contents of the autoclave were cooled to complete the polymerization and obtain (a) -1 to (a) -6. The properties of the obtained acrylic rubber-like polymer are also shown in Table 2.

(B) Acrylic rubber-like polymer containing vinyl resin Acrylic rubber-like polymer latex 100 shown in Table 2
Parts (as solid content), 2 parts of potassium stearate and 50 parts of pure water were charged into an autoclave and stirred to 50
Heated to ° C. Here, ferrous sulfate heptahydrate 0.005
Parts, ethylenediamine tetraacetic acid tetrasodium salt dihydrate 0.
An aqueous solution prepared by dissolving 01 parts and 0.3 parts of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was added. Then, to 100 parts of the vinyl-based monomer mixed solution shown in Table 3, 0.1 parts of tertiary-butyl peracetate was added.
A mixed solution in which parts were dissolved was continuously added over 5 hours. After the addition of the monomer mixture was completed, 0.1 part of tertiary-butyl peracetate was added, the temperature was raised to 70 ° C., and the mixture was further stirred for 2 hours to complete the polymerization and complete B-1 to B-1. B-8 was obtained. Table 4 shows the proportions of the acrylic rubber-like polymer and the vinyl-based monomer mixture of the obtained vinyl-based resin-containing acrylic rubber-like polymer.
It was shown to.

(3) Component (C) Experimental Example 2: Production of component (C) 150 parts of pure water and 2 parts of potassium stearate were charged into an autoclave and heated to 50 ° C with stirring. 0.005 parts of ferrous sulfate heptahydrate, 0.01 part of ethylenediaminetetraacetic acid tetrasodium dihydrate, and 0.01 part of sodium formaldehyde sulfoxylate dihydrate.
An aqueous solution obtained by dissolving 3 parts in 10 parts of pure water was added. Next, 100 parts of the vinyl monomer mixed solution having the composition shown in Table 5 was continuously added over 4 hours. After completion of the addition of the monomer mixture, 0.1 part of diisopropylbenzene hydroperoxide was added, the system was heated to 70 ° C. and stirred for 2 hours to complete the polymerization, and C-1 to C -3 was obtained. The weight average molecular weight and glass transition temperature of the obtained vinyl polymer are shown in Table 5 together.

(4) Polymer mixture based on mixing both emulsions of component (B) and component (C) Experimental example 3: Obtained by mixing both emulsions of component (B) and component (C) Production of Polymer Mixture (D) The emulsion liquid of the component (B) polymer and the emulsion liquid of the component (C) polymer were mixed at the compounding ratio shown in Table 6 (as the solid content of the polymer),
An aqueous solution obtained by dissolving 5 parts of calcium chloride / dihydrate in 400 parts of pure water was heated to 80 to 95 ° C., and the mixed emulsion described above was added thereto with stirring to deposit. The obtained slurry was filtered, washed with water, and dried in an atmosphere of 70 ° C. to obtain polymer mixtures D-1 to D-16 shown in Table 6.

(5) Production of Thermoplastic Resin Composition Example 1 Table 1 shows an ABS resin powder composed of 50% polybutadiene, 15% acrylonitrile and 35% styrene and an AS resin composed of 70% acrylonitrile and 30% styrene. D-2 of the polymer mixture (D) obtained from the mixed state of 100 parts of the component (A) component A-1 and the emulsion of Table 6 blended in proportion.
5 parts of the above were mixed and melt-kneaded at 230 ° C. in a twin-screw extruder to obtain a thermoplastic resin composition. Using the obtained thermoplastic resin composition, a sample for evaluation was prepared with an injection molding machine, and the physical properties were measured. The results are shown in Table 7.

Examples 2 to 17 100 parts of the component (A) having the composition shown in Table 1 and the polymer mixture (D) shown in Table 6 were blended in the proportions shown in Tables 7 and 8 to prepare a biaxial mixture. It was melt-kneaded at 230 ° C. in an extruder to obtain a thermoplastic resin composition. Using the obtained thermoplastic resin composition, a sample for evaluation was prepared with an injection molding machine, and the physical properties were measured. The results are shown in Tables 7 and 8.

Example 18 100 parts of (A) -1 as component (A), 9 parts of (B) -2 as component (B), and (C)-as component (C)-
A mixture obtained by mixing 6 parts of 1 was melt-mixed at 230 ° C. of a twin-screw extruder to obtain a thermoplastic resin composition. Using this thermoplastic resin composition, a sample for evaluation was prepared with an injection molding machine and physical properties were measured. The evaluation results are shown in Table 9.

Example 19 100 parts of (A) -3 as the component (A), 9 parts of (B) -2 as the component (B), and (C)-as the component (C)-
A mixture obtained by mixing 6 parts of 1 was melt-mixed at 230 ° C. of a twin-screw extruder to obtain a thermoplastic resin composition. Using this thermoplastic resin composition, a sample for evaluation was prepared with an injection molding machine and physical properties were measured. The evaluation results are shown in Table 9.

Comparative Examples 1-10 100 parts of the component (A) having the composition shown in Table 1 and the polymer mixture (D) shown in Table 6 were blended in the proportions shown in Table 10 to prepare a twin-screw extruder 230. Melt kneading at 0 ° C. to obtain a thermoplastic resin composition. Using the obtained thermoplastic resin composition, a sample for evaluation was prepared by an injection molding machine, and the physical properties were measured. The results are shown in Table 10.

The physical properties of the examples and comparative examples were determined by the following methods. (1) Glass transition temperature The solid obtained by dropping the component (B) or the component (C) emulsion into the methanol is dried, and is a DuPont-type measuring machine 9
It was measured using a 10 differential scanning calorimeter and a 990 thermal analyzer. (2) Weight average molecular weight Two GMH-6 type columns manufactured by Tosoh Co., Ltd. HLC-802A type gel permeation chromatography were serially measured. A refractometer was used as the detector, and tetrahydrofuran was used as the solvent. The sample is
A solid obtained by precipitating an emulsion of the component (C) polymer into methanol was used. (3) Gel content The solid obtained by dropping the emulsion of the component (B) polymer or the component (C) polymer into methanol was dried. About 1.0 g thereof was precisely weighed and measured and calculated by the method described above. However, the solvent used is different between the component (B) polymer and the component (C) polymer, and methyl ethyl ketone,
Toluene was used as the component (C).

(4) Izod impact strength: ASTM D
-256, and the thickness was measured on a test piece with a 1/4 inch notch. (5) Melt flow rate: Measured at a temperature of 220 ° C. and a load of 10 kgf according to JIS K-6874. (6) Freon resistance: 1/4 of Bergen
Evaluation was performed according to the ellipse method. That is, 200 × 200 × 2
mm test samples were prepared by press molding at 230 ° C., fixed on a 1/4 elliptical jig, and allowed to stand in a Freon 141b atmosphere for 24 hours. Then, the minimum strain (critical strain) in which cracks occurred was determined. . (7) Peelability: Using a Toshiba IS50EP injection molding machine, a flat plate of 50 mm × 100 mm × 2 mm was molded under the conditions of molding temperature of 230 ° C., injection speed of 70%, and mold temperature of 50 ° C. The gate portion of the molded product was folded and the peeled state of the cut surface was visually observed. The case where peeling did not occur in the surface layer on the flat plate surface near the gate was evaluated as ◯, the case where slight peeling was observed in the surface layer was evaluated as Δ, and the case where peeling occurred in the surface layer was evaluated as x.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

[Table 8]

[0068]

[Table 9]

[0069]

[Table 10]

The symbols of the monomers in each table indicate the following. SM is styrene, AN is acrylonitrile, P
Bd is polybutadiene, n-BA is normal butyl acrylate, iso-BA is yl butyl acrylate, EA is ethyl acrylate, MMA is methyl methacrylate, and EDMA is ethylene glycol dimethacrylate.

Next, a synthetic resin composite composed of a molded product using the thermoplastic resin composition and a urethane foam will be described. Example 20 Acrylic rubbery polymer (B) -2 formed by polymerizing the monomer having the composition of (b) -1 shown in Table 3 in the presence of the acrylic rubber latex of (a) -1 shown in Table 2 Twin screw extruder 230 by mixing 5 parts of the polymer mixture (D) -2 obtained by mixing the emulsion and the emulsion of (C) -1 in the emulsified state and 100 parts of (A) -1. The mixture was melt-mixed at 0 ° C. to obtain a thermoplastic resin composition. The following vacuum moldability was evaluated using this thermoplastic resin composition. The thermoplastic resin composition was supplied to a single-screw extruder equipped with a T-die, melted at 220 ° C., and processed into a flat plate having an average wall thickness of 1 mm. The obtained flat plate is pre-dried, and is formed by controlling the surface temperature of the flat plate to about 160 ° C. by a plug-assist type pressure air vacuum forming machine to form the open-ended box-shaped thermoplastic resin composition shown in FIG. Got the body
At this time, the wall thickness of the molded product was uniform by visual observation.

Further, the above-mentioned vacuum molded body was combined with the steel box-shaped molded body of the open box shown in FIG. 1, and 110 parts of tolylene diisocyanate, methyl glycoside and propylene oxide were filled in the space surrounded by both molded bodies. 100 parts of adduct (hydroxyl equivalent 110), 30 parts of freon 41b, water 3.
5 parts, 0.4 parts of di-n-octyltin laurate, 0.2 parts of tetramethylguanidine were injected,
The reaction was carried out at 50 ° C. for 30 minutes to obtain a synthetic resin composite. Next, a thermal cycling test was conducted using this synthetic resin composite. The resulting synthetic resin composite is placed in a constant temperature bath, -1
A cooling / heating cycle of 0 ° C./3 hours to 40 ° C./3 hours was repeated twice. The molded body of the thermoplastic resin composition was removed from the synthetic resin composite after the thermal cycle test and the appearance was observed, but no cracks or the like were observed.

The dimension of the synthetic resin composite shown in FIG.
It is 75 mm × length 256 mm × height 30 mm, and the thickness of the urethane foam is 5 mm.

Examples 21 to 36 Component (A) and polymer mixture (D) were melt-mixed at a composition ratio shown in Table 11 at 230 ° C. in a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated for vacuum formability and a thermal cycle test in the same manner as in Example 20. The evaluation results are shown in Table 11 together with the composition ratio of the thermoplastic resin composition.

The vacuum formability was evaluated by visually observing the thickness after vacuum forming to determine whether or not it was uniform. When it was uniform, it was evaluated as ◯, and when it was slightly nonuniform, it was evaluated as Δ, and nonuniform. When it was, it evaluated as x and the uniform product was accepted. Also,
The cooling / heating cycle test removes the molded product of the thermoplastic resin composition from the synthetic resin composite after the test, observes the appearance thereof, and shows a good appearance without cracks, whitening, etc., and when there is a crack or a whitened portion. Is x.

Example 37 100 parts of (A) -1 as component (A), 9 parts of (B) -2 as component (B), and (C)-as component (C)-
A mixture obtained by mixing 6 parts of 1 was melt-mixed at 230 ° C. of a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated for vacuum formability and a thermal cycle test in the same manner as in Example 20. The open-walled box-shaped thermoplastic resin molded product had a uniform thickness, and no cracks were observed in the thermoplastic resin molded product in the cooling / heating cycle test.

Example 38 100 parts of (A) -3 as the component (A), 9 parts of (B) -2 as the component (B), and (C)-as the component (C)-
A mixture obtained by mixing 6 parts of 1 was melt-mixed at 230 ° C. of a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated for vacuum formability and a thermal cycle test in the same manner as in Example 20. The open-walled box-shaped thermoplastic resin molded product had a uniform thickness, and no cracks were observed in the thermoplastic resin molded product in the cooling / heating cycle test.

Comparative Examples 11 to 20 Component (A) and component (D) were melt-mixed in a twin-screw extruder at 230 ° C. in the proportions shown in Table 12 to obtain thermoplastic resin compositions. These thermoplastic resin compositions were prepared according to Example 2 respectively.
Evaluation was performed in the same manner as 0. The evaluation results are shown in Table 12 together with the composition ratio of the thermoplastic resin composition.

Comparative Example 21 100 parts of (A) -1 as the component (A), 9 parts of (B) -1 as the component (B), and (C)-as the component (C)-
The mixture obtained by mixing 6 parts of 3 was melt mixed at 230 ° C. of the twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 20. The open-walled box-shaped thermoplastic resin molded product had an uneven wall thickness, and no cracks were observed in the thermoplastic resin molded product in the cooling / heating cycle test.

[0080]

[Table 11]

[0081]

[Table 12]

[0082]

As described above, a diene rubber-containing styrene resin, a vinyl resin-containing acrylic rubber-like polymer,
And a thermoplastic resin composition comprising a vinyl-based polymer having a weight average molecular weight of 200,000 or more has excellent impact resistance and flon resistance in a balanced manner, and has good vacuum moldability. Since the molded resin used and the synthetic resin composite consisting of urethane foam suppress the occurrence of cracks in the use environment such as a cooling / heating cycle, a heat insulating material, a vibration damping material,
Effective for applications such as sound insulation.

[Brief description of drawings]

FIG. 1 (a) shows a cross-sectional view of a molded body of a thermoplastic resin composition. (B) shows a top view of the synthetic resin composite.
(C) shows the AA 'cross section figure of the synthetic resin composite of said (b).

[Explanation of symbols]

 1: molded product of thermoplastic resin composition 2: molded product of steel 3: urethane foam

Claims (4)

[Claims] 1. The following component (A), component (B) and (C)
Ingredients) and the proportion of each ingredient is (A) ingredient 100
1 to 50 parts by weight of component (B) and (C) relative to parts by weight
0.75 to 48 parts by weight of the component, and (B) component +
The total amount of the component (C) is 5 to 60 parts by weight, which is a thermoplastic resin composition. Component (A): Styrene resin containing diene rubber (B) Component: Acrylic rubber polymer Obtained by polymerizing 1 to 200 parts by weight of one or more vinyl monomers in the presence of 100 parts by weight. Acrylic rubber-like polymer containing vinyl resin (C) component: Polymer of vinyl monomer having a weight average molecular weight of 200,000 or more 2. A polymer mixture obtained by mixing an emulsion of a vinyl resin-containing acrylic rubber-like polymer as the component (B) and an emulsion of a polymer as the component (C), and separating the mixture ( The thermoplastic resin composition according to claim 1, which is obtained by mixing the diene rubber-containing styrene resin as the component (A). 3. A synthetic resin composite comprising a molded product of the thermoplastic resin composition according to claim 1 and a urethane foam. 4. A heat insulating steel sheet-synthetic resin laminate comprising the synthetic resin composite according to claim 3 and a steel sheet.