JPH04258619A - Molding material - Google Patents

Abstract

PURPOSE:To provide a molding material for a molding which does not cause stress-cracking even in contact with a new fluorocarbon gas such as Flon 141b or Flon 123, does not decrease in hardness and modulus even when swollen and is used in contact with a heat-insulating material prepared by using a fluorocarbon gas as a blowing agent. CONSTITUTION:A molding material for a molding used in contact with a heat- insulating material prepared by using a fluorocarbon gas as a blowing agent, said molding comprising a rubber-modified aromatic vinyl resin comprising 5-40 pts.wt. rubbery polymer (I) and 95-60 pts.wt. monomer component (II) comprising 9.5-94.5wt.% aromatic vinyl compound, 5-90wt.% vinyl cyanide compound, 0.5-30wt.% unsaturated carboxylic acid amide and 0-74.5wt.% another copolymerizable monomer and having a grafting ratio of the graft component upon the rubbery polymer (I) of 5wt.%.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material made of a rubber-modified aromatic vinyl resin that has excellent stress crack resistance against fluorocarbons and the like used as foaming agents for heat insulating materials.

0002

2. Description of the Related Art Conventionally, ABS resin has been widely used as the inner box material and frame material of electric refrigerators and the like. usually,
The inner box of an electric refrigerator is made by extruding ABS resin into a sheet and vacuum-forming it, and the frame material is molded by injection molding, and is characterized by its excellent appearance and excellent mechanical strength. The inner box and frame of an electric refrigerator come into contact with the insulation material,
This heat insulating material is generally urethane foam, and Freon 11 is used as the foaming agent. However, this CFC-11 will no longer be usable in 2000 AD due to the Conference of Parties to the Montreal Protocol. Freon 141b, Freon 123 to replace Freon 11
have been proposed as candidates, but at present, rubber-modified styrenic resins such as ABS resins suitable for these fluorocarbons have not yet been developed.

[0003] Freon 11 is Freon 141b, Freon 12
When substituted with No. 3, the expected problem is that it is highly soluble in ABS resin and the like. Current general ABS resins are hardly affected by Freon 11 and can withstand use sufficiently, but Freon 1
41b, Freon 123 has a strong ability to dissolve ABS resin, and swells due to stress cracks or absorption of Freon, resulting in a decrease in hardness and modulus and becoming easily deformed. Therefore, it is currently difficult for current ABS resins to be compatible with the new CFCs.

0004

[Problems to be Solved by the Invention] The present invention aims to provide a molding material for molded products that is brought into contact with a heat insulating material using fluorocarbon gas as a foaming agent, which does not cause stress cracks and does not cause a decrease in hardness and modulus due to swelling. Our goal is to provide the following.

[0005]

[Means for Solving the Problems] The present invention comprises 5 to 40 parts by weight of rubbery polymer (I), (a) 9.5 to 94.5% by weight of an aromatic vinyl compound, and (b) vinyl cyanide. Compound 5-90% by weight, (c) unsaturated carboxylic acid amide 0
．． Monomer component (II) consisting of 5 to 30% by weight, and (d) 0 to 74.5% by weight of other copolymerizable monomers.
95 to 60 parts by weight [where (I) + (II) = 1
00 parts by weight] and a rubbery polymer (
Foaming of a fluorocarbon gas characterized by comprising a rubber-modified aromatic vinyl resin (hereinafter referred to as "rubber-modified aromatic vinyl resin") in which the grafting ratio of the graft component grafted to I) is 5% by weight or more. The present invention provides a molding material for a molded article that is brought into contact with a heat insulating material.

The rubber-modified aromatic vinyl resin of the present invention is
Even if it is a graft copolymer resin obtained by graft polymerizing the monomer component (II) in the presence of the rubbery polymer (I), the rubbery polymer (I) and the monomer It may be a blended graft copolymer resin obtained by blending with the copolymer of component (II), or a blend of these graft and blended graft copolymer resins.

Examples of the rubbery polymer (I) used in the rubber-modified aromatic vinyl resin of the present invention include polybutadiene, polyisoprene, styrene-butadiene random copolymer, acrylonitrile-butadiene copolymer,
Diene-based rubbery polymers such as styrene-butadiene block copolymers, hydrogenated products of the diene-based rubbery polymers,
Examples include ethylene-propylene-(diene) rubber and acrylic rubber, and these may be used alone or in combination of two or more. The amount of rubbery polymer (I) used is (I) to (II).
) The amount is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, based on 100 parts by weight of the total amount of components.If it is less than 5 parts by weight, sufficient impact resistance cannot be obtained, while if it exceeds 40 parts by weight, molding Poor workability and fluorocarbon resistance.

Next, monomer component (II) is composed of (
a) Aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N
, N-diethyl-p-aminoethylstyrene, N,N-
Examples include diethyl-p-aminoethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and styrene and α-methylstyrene are particularly preferred. These (a)
Aromatic vinyl compounds may be used alone or in combination of two or more. (a) The amount of the aromatic vinyl compound used is the monomer component (I
I) 9.5-94.5% by weight, preferably 15-94.5% by weight in I)
It is 80% by weight, more preferably 20 to 70% by weight, and if it is less than 9.5% by weight, sufficient moldability cannot be obtained.
On the other hand, if it exceeds 94.5% by weight, impact resistance and fluorocarbon resistance will be poor.

[0009] Furthermore, monomer component (II) is composed of (
b) Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, which may be used alone or in combination of two or more. Acrylonitrile is particularly preferred as the vinyl cyanide compound (b). (
b) The amount of vinyl cyanide compound used is the monomer component (I
I) is 5 to 90% by weight, preferably 15 to 80% by weight, more preferably 25 to 70% by weight; if it is less than 5% by weight, sufficient fluorocarbon resistance and impact resistance cannot be obtained; If it exceeds % by weight, moldability and impact resistance will be poor.

Furthermore, the unsaturated carboxylic acid amide (c) in the monomer component (II) includes acrylamide, methacrylamide, etc., and these may be used alone or in combination of two or more. In particular, this (c) unsaturated carboxylic acid amide is an essential component for the rubber-modified aromatic vinyl resin of the present invention to prevent stress cracks and a decrease in hardness and modulus due to swelling from Freon 141b and Freon 123. be. (c) The amount of unsaturated carboxylic acid amide to be used in monomer component (II) is from 0.5 to
The amount is 30% by weight, preferably 1 to 25% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, the desired fluorocarbon resistance cannot be obtained, while if it exceeds 30% by weight, the resistance will not be achieved. The fluorocarbon properties do not improve any further.

Furthermore, (d) other copolymerizable monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl Acrylic acid esters such as acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate , methacrylic acid esters such as phenyl methacrylate and benzyl methacrylate; maleic anhydride,
Unsaturated acid anhydrides such as itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide,
α- such as N-(p-methylphenyl)maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc.
or imide compounds of β-unsaturated dicarboxylic acids; epoxy compounds such as glycidyl methacrylate; and the like. These (d) other copolymerizable monomers are:
One type can be used alone or two or more types can be used in combination. (d) The amount of other copolymerizable monomers used is 0 to 74.5% by weight, preferably 0 to 74.5% by weight in monomer component (II).
~59% by weight, and if it exceeds 74.5% by weight, impact resistance will decrease.

Specific examples of the rubber-modified aromatic vinyl resin of the present invention are listed below. ■Rubber-modified aromatic vinyl resin consisting of the following (A-1) ■Rubber-modified aromatic vinyl resin consisting of the following (A-1)/the following (B-1) ■The following (A-2)/the following (B) -1) A rubber-modified aromatic vinyl resin consisting of the following (A-1)/the following (B-2) ■A rubber-modified aromatic vinyl resin consisting of the following (A-1)/the following (B-2) B-2
) rubber-modified aromatic vinyl resin above ■~
Among the rubber-modified aromatic vinyl resins described in (■), preferably ■
~■, ■, more preferably ■~■, ■.

(A-1); In the presence of the rubbery polymer (I), (a) an aromatic vinyl compound, (b) a vinyl cyanide compound, (c) an unsaturated carboxylic acid amide and, if necessary, Graft copolymer (A-2) obtained by polymerizing other copolymerizable monomers (d) used; in (A-1), (c) without using an unsaturated carboxylic acid amide; The resulting graft copolymer (B
-1); (a) aromatic vinyl compound, (b) vinyl cyanide compound, (c) unsaturated carboxylic acid, and (d) other copolymerizable monomers used as necessary. copolymer (B-2) obtained without using (c) unsaturated carboxylic acid amide in (B-1);

[0014]
The composition ratios of the graft copolymers (A-1) to (A-2) and the copolymers (B-1) to (B-2) above are as follows:
It is appropriately set so that the rubber-modified aromatic vinyl resin targeted by the present invention can be obtained. For example, (A-1) above
Rubbery polymer (I) in the graft copolymer of (A-2)
The amount used is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, while monomer component (II)
The amount used is preferably 95 to 20 parts by weight, more preferably 90 to 30 parts by weight [however, (I) + (II)
= 100 parts by weight]. In addition, the above (A-1) to (
A-2) graft copolymer, or (B-1) to (
Monomer component (II) used in the copolymer of B-2)
The preferred amount of (a) aromatic vinyl compound used is 9
~95% by weight, more preferably 15-80% by weight, (
b) The preferred amount of vinyl cyanide compound used is 5 to 90
% by weight, more preferably 15 to 80% by weight, (c) the unsaturated carboxylic acid amide is preferably used in an amount of 0 to 50% by weight, more preferably 0 to 40% by weight, (d) other copolymerizable units. The preferred amount of the polymer used is 0 to 86% by weight, more preferably 0 to 80% by weight. In addition,(
A-1) to (A-2) graft copolymers and the above (
The amounts used of each component in the copolymers B-1) and (B-2) are based on the assumption that the polymerization conversion rate is 100%, and therefore the composition ratio of the graft copolymer and the copolymer. This applies to

The grafting ratio of the rubber-modified aromatic vinyl resin of the present invention as described above is 5% by weight or more, preferably 1% by weight or more.
The content is 0 to 150% by weight, more preferably 30 to 120% by weight, and if it is less than 5% by weight, impact resistance, moldability, and fluorocarbon resistance will be poor. Here, the graft rate is
It refers to the proportion of the copolymer component directly graft-bonded to the rubber-like polymer relative to the amount of rubber in the graft copolymer. This grafting rate can be controlled by the amount of polymerization initiator, polymerization temperature, etc. To specifically determine the graft ratio, first, 2 g of the rubber-modified aromatic vinyl resin is added to acetone at room temperature, thoroughly stirred, and the insoluble content (w) is determined. On the other hand, the amount of rubbery polymer in the insoluble matter (w) can be calculated based on the polymerization recipe. The calculated amount of rubbery polymer is set as R, and the grafting rate is determined from the following formula. Grafting rate (wt%) = [(w-R)/R] x 100

[
The method for producing the rubber-modified aromatic vinyl resin of the present invention includes emulsion polymerization, suspension polymerization, and solution polymerization when polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc. are used as the rubbery polymer. In addition, when ethylene-propylene rubber, ethylene-propylene-nonconjugated diene rubber, styrene-butadiene block bodies and their hydrogenated products are used as rubber-like polymers, solution polymerization and bulk polymerization are performed. It is common to use These may be carried out by a commonly known graft polymerization method. In addition, the monomer component (
II) In order to obtain a copolymer composed only of (II), a conventional and well-known polymerization method may be used. That is, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization are used. The polymerized polymer [graft copolymer consisting of components (I) to (II), copolymer consisting only of component (II)] is dried through a recovery process such as coagulation, washing, and dissolution, and then turned into powder. Or make it into granules. When these polymers are blended, heat stabilizers, lubricants, etc. are added and the resulting pellets are used for injection molding and extrusion molding. The inner box of the electric refrigerator is obtained by further vacuum forming the extruded sheet.

[0017]

[Examples] The present invention will be explained in more detail below with reference to Examples. In the examples, parts and percentages are based on weight unless otherwise specified. Moreover, various evaluations in Examples are values measured as follows. Press the swelling degree blend powder at 220℃ to a thickness of 2mm,
After making a test sheet of 0x30mm, Freon 123
The sample was placed in a desiccator containing water and left in steam for 24 hours at 23°C, and then the amount of Freon 123 absorbed was determined and defined as the degree of swelling. The sheet extruded to a critical strain of 1.1 mm thick was attached to a 1/4" oval jig, placed in a desiccator containing Freon 123, and
After being left in steam for 16 hours at 5°C, it was broken by hand and the amount of strain that caused cracks was defined as the critical strain. Change in hardness: The initial hardness of a sheet extruded to a thickness of 1.1 mm and the hardness of the sheet after being placed in a desiccator containing Freon 123 and left in steam at 35°C for 16 hours were measured using Shore D hardness, and the changes were measured. Examined.

Reference Example 1 (Preparation of Graft Copolymer A-1) In a reactor, 40 parts of polybutadiene rubber [manufactured by Japan Synthetic Rubber Co., Ltd., JSR #700] (in terms of solid content) and 10 parts of styrene (ST) were placed. 8 parts, acrylonitrile (AN)7.
2 parts, 0.1 part of t-dodecyl mercaptan, 0.5 part of potassium oleate, and 150 parts of ion-exchanged water.
After raising the temperature to 0°C, 0.3 part of sodium pyrophosphate, 0.35 part of dextrose, 0.01 part of ferrous sulfate, and 0.1 part of cumene hydroperoxide were added to initiate polymerization. 1 hour after the start of polymerization, ST21.8 parts, AN2
0.2 parts of t-dodecyl mercaptan, 0.3 parts of cumene hydroperoxide were added continuously over 3 hours, and then an additional 0.2 parts of sodium pyrophosphate was added.
．． 1 part, dextrose 0.11 parts, ferrous sulfate 0.0
0.3 parts of cumene hydroperoxide and 0.1 part of cumene hydroperoxide were added, and the polymerization was continued for 1 hour. The polymerization conversion rate was 96%. After adding an antiaging agent to the obtained latex, it was coagulated with calcium chloride, separated, washed with water, and dried to obtain a graft copolymer A-1 with a graft ratio of 70%.

Reference Example 2 (Preparation of Graft Copolymer A-2) In a reactor, 40 parts of polybutadiene rubber [manufactured by Japan Synthetic Rubber Co., Ltd., JSR #700] (in terms of solid content) and 9 parts of styrene (ST) were added. , 7.2 parts of acrylonitrile (AN), 1.8 parts of acrylamide (AAm), 0.1 part of t-dodecylmercaptan, 0.5 parts of potassium oleate, and 150 parts of ion-exchanged water, and after raising the temperature to 40°C, pyrroline was added. 0.3 parts of sodium chloride, 0.35 parts of dextrose, 0.01 parts of ferrous sulfate, and 0 parts of cumene hydroperoxide.
．． 1 part was added to initiate polymerization. One hour after the start of polymerization, 17.6 parts of ST, 20.2 parts of AN, 4.2 parts of AAm, 0.2 parts of t-dodecyl mercaptan, and 0.3 parts of cumene hydroperoxide were added continuously over 3 hours, and then, Furthermore, sodium pyrophosphate 0.1
parts, dextrose 0.11 parts, ferrous sulfate 0.003 parts
1 part and 0.1 part of cumene hydroperoxide were added, and the polymerization was continued for 1 hour. The polymerization conversion rate was 96%. After adding an antiaging agent to the obtained latex, it was coagulated with calcium chloride, separated, washed with water, and dried to obtain a graft copolymer A-2 with a graft ratio of 73%.

Reference Example 3 (Preparation of Graft Copolymer A-3) Graft copolymer A-3 with a graft ratio of 71% was obtained by replacing acrylamide with methacrylamide in Reference Example 2. Reference Example 4 (Preparation of Graft Copolymer A-4) In the reactor,
Polybutadiene rubber [manufactured by Japan Synthetic Rubber Co., Ltd., JSR
#700] 26 parts (solid content equivalent), 0.5 part of potassium oleate, and 150 parts of ion-exchanged water were heated to 40°C, then 0.3 part of sodium pyrophosphate, 0.35 part of dextrose, and sulfuric acid were added. 0.01 part of ferrous iron, 0.1 part of cumene hydroperoxide, 31 parts of ST, 35.6 parts of AN, 7.4 parts of AAm, 0.45 parts of t-dodecyl mercaptan
part, 0.25 part of cumene hydroperoxide were added continuously over 5 hours, and then further added 0.1 part of sodium pyrophosphate, 0.11 part of dextrose,
0.003 part of ferrous sulfate and 0.1 part of cumene hydroperoxide were added and polymerization was continued for 1 hour. The polymerization conversion rate was 95%. After adding an antiaging agent to the obtained latex, it was coagulated with calcium chloride, separated, washed with water, and dried to obtain a graft copolymer A-4 with a graft ratio of 87%.

Reference Example 5 (Preparation of Graft Copolymer A-5) In Reference Example 4, the monomer components were 37.4 parts ST and 37.4 parts AN.
The same polymerization was carried out except that 36.0 parts of AAm and 0.6 parts of AAm were used to obtain a graft copolymer A-5 with a graft ratio of 83%. Reference Example 6 (Preparation of Graft Copolymer A-6) In Reference Example 4, the monomer components were 30 parts of ST, 33 parts of AN, and AAm.
A graft copolymer A-6 with a graft ratio of 85% was obtained by carrying out the same polymerization except that 7 parts and 4 parts of ethyl acrylate were used.
I got it. Reference Example 7 (Preparation of Graft Copolymer A-7) In the reactor,
EPDM [manufactured by Japan Synthetic Rubber Co., Ltd., JSR EP24
]26 copies, ST37 copies, AN33.3 copies, AAm3.7
After adding 100 parts of toluene and completely dissolving the rubber, add 0.1 part of t-dodecyl mercaptan, 0.2 part of dibenzoyl peroxide, and 1-butyl peroxide.
0.2 part of propyl carbonate and 0.1 part of dicumyl peroxide were added, and polymerization was carried out at 1000°C for 7 hours. The polymerization conversion rate was 96%. After removing unreacted monomers by steam distillation, the grafting rate is 53 by crushing and drying.
% of graft copolymer A-7 was obtained.

Reference Example 8 (Preparation of Copolymer B-1) A reactor was charged with 2.5 parts of sodium dodecylbenzenesulfonate and 300 parts of ion-exchanged water, and after heating to 60°C, potassium persulfate was added to 0. .3 parts, acidic sodium sulfite 0.1 part, S
50 parts of T, 45 parts of AN, 5 parts of AAm, and 0.45 parts of t-dodecylmercaptan were added continuously over 5 hours, and then the polymerization was continued for an additional hour. The polymerization conversion rate was 98%. The obtained latex was coagulated with calcium chloride, separated, washed with water, and dried to form copolymer B-1.
I got it. Reference Example 9 (Preparation of Copolymer B-2) In Reference Example 8, the monomer components were 45 parts ST and 45 parts AN45.
Copolymer B-2 was obtained in the same manner except that 10 parts and 10 parts of AAm were used. Reference Example 10 (Preparation of Copolymer B-3) In Reference Example 8, the monomer components were 45 parts of ST, 40 parts of AN, and AA.
Copolymer B-3 was obtained in the same manner except that 5 parts of m and 5 parts of ethyl acrylate were used. Reference Example 11 (Preparation of Copolymer B-4) In Reference Example 8 (Copolymer B-1), the monomer component was ST45
parts, 40 parts of AN, 5 parts of AAm, 5 parts of methyl methacrylate
Copolymer B-4 was obtained in the same manner as above.

Reference Example 12 (Preparation of Copolymer C-1) A reactor was charged with 2.5 parts of sodium dodecylbenzenesulfonate and 300 parts of ion-exchanged water, and the temperature was raised to 60°C.
0.3 parts of potassium persulfate, 0.1 part of acidic sodium sulfite,
74 parts ST, 26 parts AN, 0 t-dodecylmercaptan
．． 45 parts were added continuously over 5 hours, after which polymerization was continued for an additional hour. The polymerization conversion rate was 98%. The obtained latex was coagulated with calcium chloride, separated, washed with water, and dried to obtain copolymer C-1. Reference Example 13 (Preparation of Copolymer C-2) Copolymer C was prepared in the same manner as in Reference Example 12 (Copolymer C-1) except that the monomer components were 45 parts ST and 55 parts AN.
-2 was obtained.

Examples 1 to 5, Comparative Example 1 Graft copolymers and copolymers prepared in reference examples are shown in Tables 1 to 5.
Pellets were produced by mixing according to the formulation shown in 2, melt-mixing at a resin temperature of 230° C. using a vented extruder, and extruding. Using this pellet, the cylinder temperature was 220℃ and the mold temperature was 210℃ using a 30φ extruder.
A sheet was prepared at ℃ and each physical property was evaluated. The results are shown in Table 1~
Shown in 2. As is clear from Tables 1 and 2, Examples 1 to 4
Although graft copolymer A-1 does not contain unsaturated carboxylic acid amide, copolymers B-1 to B-4 do contain it, so the degree of swelling is significantly lower than that of Comparative Example 1. , critical strain and hardness change are greatly improved. In particular, as in Example 2, when the amount of unsaturated carboxylic acid amide increases, the effect becomes even greater. Examples 6-11 Experiments were conducted in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1-2. The results are shown in Tables 1 and 2. Examples 6-1
1, graft copolymers A-2 to 5, copolymer B-2
When both contain unsaturated carboxylic acid amide, the degree of swelling becomes even smaller. However, as in Example 9,
When Copolymer C-1, which does not contain unsaturated carboxylic acid amide, is also added, the degree of swelling tends to increase, but compared to Comparative Example 1, it is extremely superior.

Examples 12-14 Experiments were carried out in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1-2. The results are shown in Tables 1 and 2. Even in the case of a single graft copolymer using 26 parts of a rubbery polymer, the same tendency as in the blend system is shown. Even if the rubbery polymer is changed as in Example 14, if unsaturated carboxylic acid amide is copolymerized, changes in swelling degree and hardness will be small. Comparative Example 2 An experiment was carried out in the same manner as in Example 1, except that the formulation was changed to Table 2. The results are shown in Table 2. When the amount of acrylonitrile copolymerized was increased, Comparative Example 2 had a higher degree of swelling than Comparative Example 1.
Although the change in hardness is reduced, the appearance becomes extremely poor and the color changes to brown. Comparative Examples 3 and 4 Experiments were conducted in the same manner as in Example 1, except that the formulation was changed to Table 2. The results are shown in Table 2. If the amount of unsaturated carboxylic acid amide in the resin is less than 0.5%, the swelling degree and hardness change will be large and the fluorocarbon resistance will be poor.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

Effects of the Invention The molding material made of the rubber-modified aromatic vinyl resin of the present invention is particularly effective against Freon 141b and Freon 123.
On the other hand, it does not cause stress cracks or a decrease in hardness or modulus due to swelling, and therefore exhibits extremely high performance as a molding material for molded products that come into contact with heat insulating materials using these CFC gases as foaming agents. Examples of molded products that come into contact with the above-mentioned heat insulating material include electric refrigerators, freezers,
Examples include iceboxes, ice makers, thermal storage, housings, etc.

Claims (1)

[Claims] Claim 1: 5 to 40 parts by weight of rubbery polymer (I),
and (a) 9.5 to 94.5% by weight of an aromatic vinyl compound, (b) 5 to 90% by weight of a vinyl cyanide compound, (
c) 95 to 60 parts by weight of monomer component (II) consisting of 0.5 to 30% by weight of unsaturated carboxylic acid amide, and (d) 0 to 74.5% by weight of other copolymerizable monomers [ (I) + (II) = 100 parts by weight], and the grafting rate of the graft component grafted onto the rubbery polymer (I) is 5% by weight or more. A molding material for a molded product that is made of a resin based on a resin and is brought into contact with a heat insulating material using fluorocarbon gas as a foaming agent.