JP3487646B2 - Synthetic resin composite - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic resin composite comprising a molded product of a specific thermoplastic resin composition and a urethane foam and having excellent CFC resistance and mechanical properties, and a synthetic resin composite and a steel sheet. Heat insulating steel sheet-synthetic resin composite. More detail certain thermoplastic resin composition, the diene rubber containing a styrene - acrylonitrile resin, an acrylic rubber polymer, and the weight average molecular weight of Ri than 200,000 der, aromatic vinyl monomer and a cyan Vinyl chloride monomer
And a vinyl polymer whose main component is the total amount of

[0002]

2. Description of the Related Art A synthetic resin composite having a heat insulating property, which is composed of a diene rubber-containing styrene resin represented by an ABS resin and a urethane foam, is well known and is widely used, for example, in household refrigerators. Such a synthetic resin composite is produced by reacting a mixture containing a polyisocyanate, a polyol and a foaming agent as main components in the presence of an ABS resin molding. Fluorocarbon, that is, chlorofluorocarbon, is generally used as the foaming agent.

However, in the synthetic resin composite thus obtained, cracks may occur in the ABS resin molded body due to the environmental stress cracking phenomenon. The cause is that the CFC used as a foaming agent for urethane penetrates from a large number of minute voids formed in the ABS resin molding due to the stress applied during the manufacturing process of the synthetic resin composite, and breaks the polymer chain. It is believed that.

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 thus synthetic resin composites produced using the alternative CFCs as a blowing agent. In the above, the possibility of causing cracks in the ABS resin molded body is higher than that in the case of using Freon 11.

Therefore, there is also a method of producing a heat insulating material for a refrigerator excellent in CFC resistance by using a so-called high nitrile resin in which the content of acrylonitrile is remarkably increased.
No. 2-228860), a resin having a high acrylonitrile content has problems such as yellowish resin and poor thermal stability. Further, there is a drawback that the thickness becomes uneven during vacuum forming.

[0006]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies made by the present inventors to solve the above-mentioned problems associated with a synthetic resin composite comprising a diene rubber-containing styrene -acrylonitrile resin molding and a urethane foam. diene rubber-containing styrene - acrylonitrile resin, an acrylic rubber polymer, and the weight average molecular weight of Ri der 200,000 or more,
Total amount of aromatic vinyl monomer and vinyl cyanide monomer
The object was achieved by producing a urethane foam and a synthetic resin composite using a molded body of a thermoplastic resin composition containing a vinyl polymer as a main component .

[0007]

Means for Solving the Problems That is, the present invention is based on a styrene-acrylonitrile resin containing a diene rubber (component (A)), a glass transition temperature of 20 ° C. or lower, and a gel content of 70.
% Or less and the solubility parameter is 8.4 to 9.8.
Acrylic rubbery polymer << component (B) >> having (cal / cc) ^1/2 , a glass transition point of more than 20 ° C., a weight average molecular weight of 200,000 or more, and an aromatic vinyl monomer.
Of a thermoplastic resin composition containing a polymer and a vinyl monomer polymer (component (C)) whose main component is the total amount of vinyl cyanide monomer , and urethane foaming It is obtained by using a synthetic resin composite body. This thermoplastic resin composition comprises 50 to 99.5% by weight of component (A), (B)
0.1 to 40% by weight of component, and 0.1 to 45 of component (C)
% By weight, and the total amount of the component (B) + the component (C) is 0.5 to 50% by weight.

First, the styrene -acrylonitrile- based resin containing the diene rubber as the component (A) of the present invention will be described. Styrene -acrylo containing diene rubber as component (A)
The nitrile resin is composed of a diene rubber component and a resin component. First, as the diene rubber component, conjugated diene monomers such as butadiene, isoprene, dimethylbutadiene, chloroprene and cyclopentadiene, and non-conjugated diene such as 2,5-norbornadiene, 4-ethylidene norbornene and 1,4-cyclohexadiene. Homopolymers such as monomers, or conjugated diene monomers or non-conjugated diene monomers and aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, and cyanation Acrylic ester monomers such as vinyl monomer, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl Methacrylate, 2-ethylhexyl methacrylate, methacrylic acid ester monomers such as octyl methacrylate, ethylene, propylene, 1
-Olefin monomers such as butene, isobutylene and 2-butene, maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide and N-phenylmaleimide, acid anhydride monomers such as maleic anhydride , Vinyl vinyl monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and glycidyl vinyl ether, and copolymers of vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone. You can

Further, as the diene rubber component, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can be used as a crosslinking monomer. As the polyfunctional vinyl monomer, 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 polymerization method using 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 -acrylonitrile resin of the component (A) of the present invention is an aromatic compound such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene. Vinyl cyanide and 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- Acrylic ester monomers such as ethylhexyl acrylate and octyl acrylate, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and octyl methacrylate, acetic acid Amide-based monomers such as lamide and methacrylamide, 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-
Maleimide-based monomers such as ethyl maleimide, N-propyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, acid anhydride monomers such as maleic anhydride, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl. Vinyl ether monomers such as vinyl ether, phenyl vinyl ether and glycidyl vinyl ether, and vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone may be used alone or in combination for copolymerization.

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. If it is less than 20% by weight, the CFC resistance of the synthetic resin composite will not be sufficient, and if it exceeds 50% by weight, it will turn yellow due to the thermal history during molding.

The component (A) used in the present invention is composed of the diene rubber component and the resin component as described above, and the interface between the diene rubber component having a particulate structure and the resin component which is the continuous phase is It is necessary to interpose a graft structure. It is known that such a structure can be achieved by a so-called graft polymerization method in which a part or all of the monomers constituting the resin component are polymerized in the presence of the diene rubber component. The component) 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 may be separately acrylonitrile, styrene and α-methylstyrene. It is also possible to mix an acrylonitrile-styrene-α-methylstyrene copolymer obtained by polymerizing.

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

Specific examples of the diene rubber-containing styrene -acrylonitrile- based resin (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 -acrylonitrile- butadiene-styrene) resin, etc. are mentioned.

Next, the acrylic rubber polymer as the component (B) used in the present invention will be described. Examples of the component (B) include methyl acrylate, ethyl acrylate,
Homopolymers or copolymers of acrylic acid ester monomers such as butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethoxyethyl acrylate, and 2-hydroxyethyl acrylate. , And hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hexadecyl methacrylate, dodecyl methacrylate, decyl methacrylate, octadecyl methacrylate, stearyl methacrylate and homopolymers or copolymers of methacrylic acid ester monomers selected from pentyl methacrylate, Also, acrylic acid ester monomers and methyl methacrylate, ethyl methacrylate Propyl methacrylate,
It is 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.

The component (B) of the present invention has a glass transition temperature of 2
It is necessary to be 0 ° C or lower, and more preferably 10 ° C or lower. If the glass transition temperature exceeds 20 ° C,
Freon resistance and impact resistance deteriorate.

The component (B) of the present invention is required to have a gel content of 70% or less, more preferably a gel content of 50% or less. When the gel content of the component (B) 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 component (B) is precisely weighed (S ₀ g) and placed in a basket made of 400 mesh stainless steel wire netting to obtain 100 C.
After being immersed in toluene of C and left at 5 ° C. for 24 hours, the basket was pulled up and air-dried at room temperature, the insoluble content weight S ₁ g was measured, and the value was calculated according to the general formula (I). (S ₁ / S ₀ ) × 100 (%) (I)

The component (B) of the present invention contains 8.4 to 9.8.
It is necessary to have a solubility parameter in the range of (cal / cc) ^1/2 . More preferably, it is 8.6 to 9.6.
The range is (cal / cc) ^1/2 . The solubility parameter of the component (B) is less than 8.4 (cal / cc) ^1/2 or 9.
When it exceeds 8 (cal / cc) ^1/2 , the CFC resistance of the synthetic resin composite comprising the molded product of the thermoplastic resin composition and the urethane foam is poor, which is not preferable.

The solubility parameter as used in this specification refers to John. Published by Wiley End Sons, Inc. in 1989, edited by Brand Wrap and Inmargut, Polymer Handbook, 3rd edition, VII519-559
Using the solubility parameter values described on the page, the solubility parameter δ _T of the copolymer is calculated by measuring the individual (meth) acrylic acid ester monomer amount constituting the copolymer composed of m kinds of (meth) acrylic acid ester monomers. From the solubility parameter δ _n of the homopolymer of the polymer and its weight fraction W _n.
It is calculated according to I).

[0025]

[Equation 1]

For example, normal butyl acrylate 80
The solubility parameter of the acrylic rubber-like polymer composed of 20% by weight of methyl methacrylate and 20% by weight of methyl methacrylate is as follows.
/ Cc) ^1/2 and the solubility parameter of methylmethacrylate of 9.5 (cal / cc) ^1/2 , substituting into general formula (II) gives 8.9 (cal / cc) ^1/2 .

The method for producing the acrylic rubber-like polymer of the component (B) of the present invention is not particularly limited, and known techniques such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used. Production by the emulsion polymerization method is industrially most advantageous. Because, in the present invention, (A) component, (B)
A polymer obtained by mixing an emulsion of the component (B) polymer and an emulsion of the component (C) polymer when producing the thermoplastic resin composition containing the component and the component (C) This is because a preferable thermoplastic resin composition can be obtained by mixing the mixture with the component (A), which is convenient when mixing in the emulsion state.

In producing the component (B) polymer, the acrylic ester monomer or the copolymerizable monomer is selected such that the glass transition temperature and gel content of the obtained component (B) polymer are selected. It is optional as long as the rate and the solubility parameter satisfy the requirements of the present invention.

Next, the polymer of the vinyl monomer as the component (C) will be described. 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. Polymers, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-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-ethoxyethyl acrylate, 2-
Acrylic ester monomers such as hydroxyethyl acrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, ethylene, propylene, 1-
Olefin monomers such as butene, isobutylene, 2-butene, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, etc. Monomers, acid anhydride monomers such as maleic anhydride, conjugated diene monomers such as butadiene, isoprene and chloroprene, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether, methyl vinyl ketone, phenyl vinyl ketone However, the present invention is not limited to these.

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 known techniques such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used.
Production by the emulsion polymerization method is industrially most advantageous. This is because emulsion polymerization can industrially easily produce a high-molecular weight polymer. Secondly, in the present invention, an emulsion of component (B) polymer and (C)
Since a preferred thermoplastic resin composition can be obtained by mixing the polymer mixture obtained by mixing the emulsion of the component polymer with the component (A), it is convenient when mixing in the emulsion state. Is.

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, (A) component is 50 to 99.5% by weight, (B) component is 0.1 to 40% by weight, and (C) component is 0.1 to 40% by weight, and (B) component + A thermoplastic resin composition is manufactured by mixing the components (C) so that the total amount of the components is 0.5 to 50% by weight. More preferably (A)
60 to 98% by weight of component, 0.6 to 28% by weight of component (B),
Component (C) is 0.6 to 28% by weight, and component (B) +
The total amount of the component (C) is 2 to 40% by weight. When the total amount of the component (B) + the component (C) is less than 0.5% by weight, the molded product of the obtained thermoplastic resin composition is inferior in freon resistance, and the wall thickness becomes nonuniform during vacuum molding. If it exceeds 5% by weight, the rigidity, moldability and heat resistance are poor, which is not preferable.

The mixing method with the components (A), (B), and (C) is not particularly limited, and both components in powder or pellet form are mixed to produce the desired thermoplastic resin composition. can do. Examples of the mixing device include a Henschel mixer and a tumbler. Examples of the melt mixing device include a screw extruder, a Brabender, a Banbury mixer, a co-kneader, and a mixing roll.

Further, preferred component (A), component (B),
As the method of mixing the component (C), the polymer mixture obtained by mixing the emulsion of the component (B) polymer and the emulsion of the component (C) polymer and separating the mixture (A) ) The method of mixing with the component is preferable. That is, the emulsion 20 of the component (B)
-80% by weight (as solid content of polymer) and 20-80% by weight (as solid content of polymer) of component (C) in an emulsion state, respectively, and then separated to obtain a polymer mixture Is obtained and mixed with the component (A) by the mixing method described above. The more preferable emulsion liquid of the component (B) is 30 to 70% by weight.
(As solid content of polymer), emulsion of component (C) 30-
70% by weight (as polymer solids). If the amount of the component (B) is less than 20% by weight, the CFC resistance is insufficient and the fluidity is significantly reduced, which is not preferable. If the amount of the component (B) exceeds 80% by weight, the compatibility with the component (A) becomes poor, and a layered peeling phenomenon and surface defects such as flow marks are likely to appear in the molded product, and the wall thickness is insufficient during vacuum molding. It is not preferable because it tends to be uniform.

When the emulsion of the component (B) and the emulsion of the component (C) are mixed in an emulsion state, the polymer of the component (B) or the polymer of the component (C) is produced by emulsion polymerization. In this case, the emulsion polymerization liquid 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 known techniques can be arbitrarily applied. 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 emulsifier and water to prepare an emulsion, but the method is not limited to these.

There are no particular restrictions on the type of emulsifier used for emulsion polymerization of the (B) component polymer or (C) component polymer, or for the emulsification of the polymer. Anionic surfactants, cationic surfactants and amphoteric interfaces are used. The surfactant can be arbitrarily selected from the nonionic surfactants, but the anionic surfactant can be most advantageously used.

The mixing method of the emulsion of the component (B) polymer and the emulsion of the component (C) polymer is not particularly limited, and a fixed container type mixing device, a rotary container type mixing device, a static mixer,
The mixing can be performed using a device such as a pipeline mixer.

Mixing of Emulsion of Component (B) Polymer and Emulsion of Component (C) Polymer The method of separating the polymer mixture from the emulsion is not particularly limited, and the emulsion may be hydrochloric acid, sulfuric acid or phosphoric acid. , Acid such as acetic acid, electrolyte such as sodium chloride, calcium chloride, aluminum chloride, sodium sulfate, magnesium sulfate, polyvinyl alcohol, polyethylene glycol, polyethylene glycol-polypropylene glycol block copolymer, water-soluble polymer depositing agent such as carboxymethyl cellulose And the like, a method of freezing the emulsion and destroying the emulsion, a method of spraying the emulsion in a high temperature gas, and the like.

The polymer mixture separated from the mixed liquid of the emulsion of the component (B) polymer and the emulsion of the component (C) polymer can be further fed to a melt kneader to be melt-kneaded. The melt-kneading device that can be used, for example, Banbury mixer, intensive mixer, co-kneader,
There are extruders and rolls. 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 synthetic resin composite of the present invention is prepared by using the thermoplastic resin composition in the presence of a molded article which has been preformed.
It is produced by reacting a mixture containing a polyisocyanate, a polyol, and a foaming agent as main components, but the composition and production 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, Freon 11 and Freon 1 were used.
2, CFC 113, CFC 123, CFC 141b, methylene chloride and the like.

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

[0049]

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 which is the material of the molded body will be described. (1) Component (A) An ABS resin powder consisting of 50% polybutadiene, 15% acrylonitrile, and 35% styrene and an AS resin having a different component ratio of styrene and acrylonitrile are blended at a ratio shown in Table 1, and a component (A) is blended. A-1, A-2 and A-4 were obtained. Further, ABS resin powder consisting of 50% polybutadiene, 20% acrylonitrile and 30% styrene and AS resin consisting of 60% styrene and 40% acrylonitrile were blended at a ratio shown in Table 1 to obtain component (A) A-3. It was The AS resin used as the component (A) had a weight average molecular weight by GPC of less than 200,000.

(2) Component (B) Production of component (B) 120 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate are charged into an autoclave and stirred at 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 (B) -1 to (B) -6. The properties of the obtained component (B) are also shown in Table 2.

(3) Component (C) 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 ethylenediamine tetraacetic acid tetrasodium salt 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 monomer mixture having the composition shown in Table 3 was continuously added over 4 hours. At the same time, potassium persulfate 0.05
An aqueous solution prepared by dissolving 25 parts of pure water in 25 parts of pure water was continuously added over 6 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., stirring was continued for 2 hours to complete the polymerization, and (C) -1 to (C) -3 was obtained. The properties of the obtained component (C) are shown in Table 3 together.

(4) Polymer mixture based on component (B) emulsion and component (C) emulsion Polymer mixture (D) obtained by mixing component (B) emulsion and component (C) emulsion ), The emulsion of the component (B) polymer and the emulsion of the component (C) polymer are mixed in the emulsion state in the proportions shown in Table 4 (as the solid content of the polymer), and calcium chloride / 2 water is added. 80 parts of an aqueous solution prepared by dissolving 5 parts of salt in 400 parts of pure water
The mixture was heated to ˜95 ° C., and the above mixed emulsion was added thereto with stirring to deposit. The obtained slurry is filtered, washed with water, and dried in an atmosphere at 70 ° C. to obtain a polymer mixture D-1 to D-D.
-15 was obtained.

Each physical property value was determined by the following methods. (1) Glass transition temperature (B) component or (C) component Emulsion is added dropwise to methanol to obtain a solid, which is then dried and used as a DuPont measuring instrument.
It was measured using a 10 differential scanning calorimeter and a 990 thermal analyzer. (2) Weight-average molecular weight Tosoh Co., Ltd. HLC-802A type gel permeation chromatography was measured by serially connecting two GMH-6 type columns manufactured by the same company. A refractometer was used as the detector, and tetrahydrofuran was used as the solvent. The sample is (C)
A solid obtained by precipitating the component emulsion with methanol was used. (3) Gel content (B) component or (C) component emulsion was dropped into methanol to obtain a solid. About 1.0 g thereof was precisely weighed and measured and calculated by the method described above. However, the solvent used was different between the component (B) and the component (C), methyl ethyl ketone was used for the component (B), and toluene was used for the component (C). (4) Solubility parameter The solubility parameter value of the acrylic rubber polymer as the component (B) was measured and calculated by the method described above.

Example 1 As shown in Table 5, 60% of A-1 shown in Table 1 and 60% of the polymer mixture D-2 << (B) -1 shown in Table 4 and (C) -1 Was obtained by mixing a mixture of 40% of the polymer in an emulsified state with 40% of the polymer in a twin-screw extruder at 230 ° C. to obtain a thermoplastic resin composition. The resin composition was supplied to a single-screw extruder 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 molded by a plug-assist type compressed air vacuum molding machine while controlling the surface temperature of the flat plate to about 160 ° C. to obtain a box-shaped thermoplastic resin molded body without a lid shown in FIG. As a result, the wall thickness was uniform.

This molded product was combined with the uncovered box-shaped steel molded product shown in FIG. 1, and 110 parts of tolylene diisocyanate, an adduct of methylglycoside and propylene oxide (hydroxyl group) were provided in the space surrounded by both molded products. Equivalent 110) 1
00 parts, Freon 141b 30 parts, water 3.5 parts, di-n-
A mixture of 0.4 parts of octyltin laurate and 0.2 parts of tetramethylguanidine was injected and reacted at 50 ° C. for 30 minutes to obtain a synthetic resin composite. The obtained synthetic resin composite is placed in a constant temperature bath, -10 ° C / 3 hours to 40 ° C /
The 3 hour cooling / heating cycle was repeated twice. When 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, no crack was observed in the molded body of any thermoplastic resin composition.

The synthetic resin composite shown in FIG. 1 has a width of 1
It is 75 mm × length 256 mm × height 30 mm, and the thickness of the urethane foam is 5 mm. The evaluation results are shown in Table 5 together with the composition ratio of the resin composition.

Examples 2 to 14 Component (A) and polymer mixture (D) in the composition ratios shown in Table 5
And were melt-mixed with a twin-screw extruder at 230 ° C. to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 1. Table 5 shows each evaluation result.
Is also shown together with the composition ratio of the resin composition.

The vacuum formability was evaluated by visually observing the wall thickness after vacuum forming to determine if it was uniform. If it was uniform, it was evaluated as ○, and if it was not uniform, it was evaluated as ×. I passed. Further, the cooling / heating cycle test removes the molded body of the thermoplastic resin composition from the synthetic resin composite after the test,
The appearance was observed, and a good appearance with no cracks or whitening was marked with ◯, and a crack or whitening part was marked with x.

Example 15 80% of (A) -1 as the (A) component, 12% of (B) -1 as the (B) component, and (C)-as the (C) component.
The mixture in which 8% of 1 was mixed was melt-mixed at 230 ° C. in a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 1.
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 16 60% of (A) -1 as the component (A), 24% of (B) -2 as the component (B), and (C)-as the component (C).
A mixture in which 12% of 2 was mixed was melt-mixed at 230 ° C. in a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 1. 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 1 to 9 Component (A) and polymer mixture (D) in the composition ratios shown in Table 6
And were melt-mixed with a twin-screw extruder at 230 ° C. to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 6 together with the composition ratio of the resin composition.

Comparative Example 10 80% of (A) -1 as the component (A), 12% of (B) -1 as the component (B), and (C)-as the component (C)-
The mixture obtained by mixing 8% of 3 was melt-mixed at 230 ° C. in a twin-screw extruder to obtain a thermoplastic resin composition. Each of these thermoplastic resin compositions was evaluated in the same manner as in Example 1.
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.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

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.

[0071]

As described above, a styrene -acrylonitrile- based resin containing a diene rubber, an acrylic rubber-like polymer, and a unit amount of an aromatic vinyl having a weight average molecular weight of 200,000 or more .
The thermoplastic resin composition comprising a vinyl polymer having the total amount of the polymer and the vinyl cyanide monomer as a main component has good vacuum moldability, and a molded product of this thermoplastic resin composition The synthetic resin composite made of urethane foam is effective in applications such as a heat insulating material, a vibration damping material, and a sound insulating material, because the generation of cracks in a use environment such as a cold heat cycle is suppressed.

[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: Steel compact 3: Urethane foam

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B32B 27/40 B32B 27/40

Claims (3)

(57) [Claims] 1. The following component (A), component (B), and component (C) are contained, and the ratio of each component is (A) component 5:
0-99.5% by weight, component (B) 0.1-40% by weight,
And component (C) is 0.1 to 40% by weight, and (B)
A synthetic resin composite composed of a molded product of a thermoplastic resin composition in which the total amount of the component + (C) component is 0.5 to 50% by weight, and a urethane foam. Component (A): Styrene-acrylonitrile resin containing diene rubber (B) Component: Glass transition temperature selected from the following polymers is 20 ° C or lower, gel content is 70% or lower, and solubility parameter is 8. Acrylic rubbery polymer having 4 to 9.8 (cal / cc) ^1/2 . (1) Homopolymer or copolymer of acrylic acid ester monomer, (2) Hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hexadecyl methacrylate, dodecyl methacrylate, decyl methacrylate, octadecyl methacrylate, stearyl methacrylate and pentyl methacrylate. (3) Acrylic ester monomer and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, hydroxy methacrylate, and (2) (4) A copolymer obtained by copolymerizing one or more monomers of the methacrylic acid ester monomers of (4), (4) above (1) to (3) A polymer obtained by optionally using ethylene glycol dimethacrylate in the polymerization of 1). Component (C): glass transition point is higher than 20 ° C., weight average molecular weight is 200,000 or more, and total amount of aromatic vinyl monomer and vinyl cyanide monomer is 90% by weight to 100% by weight.
% Vinyl polymer. 2. A polymer mixture obtained by mixing an emulsion of an acrylic rubbery polymer as the component (B) with an emulsion of a polymer as the component (C), and then separating the thermoplastic resin composition. Styrene -acrylonit containing (A) component diene rubber
The synthetic resin composite according to claim 1, which is obtained by mixing a ril resin. 3. A heat insulating steel sheet-synthetic resin laminate comprising the synthetic resin composite according to claim 1 and a steel sheet.