JP2000119467A - Expandable vinyl chloride based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide expandable vinyl chloride based resin compositions which prevent a plastisol from thickening to enhance workability and prevent the plate-out upon embossing and furthermore, improve processability by possessing heat stability without impeding the kick-off of expansion and, in addition, can remarkably heighten the commercial value of the products. SOLUTION: Expandable vinyl chloride based resin compositions comprises 100 pts.wt. vinyl chloride based resin, (a) 30-120 pts.wt. plasticizer, (b) 30-200 pts.wt. filler, (c) 0.1-10 pts.wt. thermal decomposition type chemical blowing agent, (d) 0.05-5 pts.wt. at least one of alkaline earth metal perbasic carboxylate or alkylphenolate, and (e) 0.01-2 pts.wt. at least one compound represented by the formula: R-O(CH2CH2O)nH (wherein R is 4-18C alkyl or alkylaryl; and n is a number of 1-15).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamable vinyl chloride resin composition used for producing a foam. Furthermore, foamable vinyl chloride-based resin compositions that can significantly improve the commercial value by stabilizing the cells of the foam and imparting properties such as texture, surface smoothness, and rebound resilience to the foam product It is about things.

[0002]

2. Description of the Related Art As is well known, a vinyl chloride resin foam has excellent physical properties. In other words, it is excellent in tensile strength, elongation, tear strength, compression resistance, water resistance, chemical resistance, solvent resistance, etc., and is easily flame-retardant. It is very useful for such purposes.

[0003] As a method of obtaining these vinyl chloride resin foams, generally, a plasticizer, a filler, a foaming agent,
Using a stabilizer, plastisol blended with pigments of each color according to the application, apply it evenly on flame-retardant paper, perform gelation and melting treatment, and print as necessary,
Next, a foaming agent, for example, azodicarbonamide, contained in the plastisol is thermally decomposed at a high temperature of 200 to 300 ° C. to generate a gas, and a method for forming a gas bubble structure is widely and industrially practiced.

However, when producing a foam molded article by the above-mentioned method, when a large amount of a filler is blended, and depending on the type of the vinyl chloride resin, the bubbles of the foam do not become uniform and fine. In some cases, roughening occurred, and the surface smoothness was also impaired. In addition, the plate-out becomes intense and the viscosity of the plastisol becomes high, so that the workability may be remarkably reduced.

[0005] For example, the plate-out described above will be described in detail. When a foam is subjected to secondary processing to produce a product, embossing is performed in which an uneven pattern is formed on the surface of the foam to enhance texture. In the recesses on the surface of the embossing roll, the foaming agent, pigment, filler, other additives or their decomposition products transferred from the foam adhere and cause clogging of the recesses of the roll, which is called plate-out. is there. When plate-out occurs on the embossing roll, this causes the product's uneven pattern to become thin,
Insufficiency in appearance due to lack of three-dimensional appearance is conspicuous, which significantly reduces commercial value. In order to avoid such troubles, at the time when the plate-out occurs, the processing machine must be stopped and wiped off the plate-out material each time.
As a result, the efficiency of machining operations was greatly reduced,
Improvements in this regard have long been strongly sought in the market.

[0006] In the production of foams, the cells of the obtained foams are adjusted so that the cells of the products are fine and uniform, and the problem in the production process is the suitability of using plastisol as a raw material. High viscosity, prevention of plate-out during the above-mentioned production, early rise of foaming (to reach a required foaming ratio quickly), and the like. In addition to these, various performances are required as appropriate according to the application.

In order to improve these, various improvement methods have been proposed. For example, the method of adding a cell conditioner of acrylic acid or methacrylic acid-based polymer certainly makes the foam cells relatively uniform, but the effect is insufficient when a large amount of calcium carbonate or other filler is blended. Met. In addition, fine foam cells were not obtained by this method, and the thickening and plate-out of the plastisol could not be prevented.

On the other hand, as a method of obtaining fine foam cells,
It has been proposed to add a surfactant based on a metal salt of alkylbenzene sulfonic acid. Although this method is relatively effective in terms of the fineness of the foam cells, the uniformity is insufficient and the use of the above-mentioned polymer-based cell conditioner was required. Of course,
This method has a drawback that the discoloration of the foam and the plate-out are deteriorated due to the use of the metal salt of alkylbenzenesulfonic acid.

[0009] Regarding the rise of foaming, a technique using a zinc compound, urea or another rising accelerator (which accelerates the generation of decomposition gas of the foaming agent and promotes foaming) or a foaming agent which decomposes gas in a short time is used. It has been disclosed. However, each of these methods has a disadvantage that thermal stability is deteriorated.

[0010]

SUMMARY OF THE INVENTION In the production of a vinyl chloride resin foam, the present invention prevents the thickening of the plastisol, enhances the workability, prevents plate-out during embossing, and starts foaming. It also improves the workability by having thermal stability without hindering the foaming, and also prevents foam settling due to reheating during embossing, and makes the foam cells uniform and fine, making the foam surface smooth An object of the present invention is to provide a foamable vinyl chloride resin composition which imparts properties and can significantly increase the commercial value.

[0011]

Means for Solving the Problems The inventors of the present invention have proposed that (a) 30 to 120 parts by weight of a plasticizer, (b) 30 to 200 parts by weight of a filler, and (c) heat in 100 parts by weight of a vinyl chloride resin. 0.1 to 10 parts by weight of a decomposable chemical blowing agent, (d) 0.05 to 5 parts by weight of at least one kind of basic carboxylate or alkylphenolate of alkaline earth metal and (e)
A foamable vinyl chloride resin composition containing a combination of at least one compound represented by the following general formula (1) and 0.01 to 2 parts by weight.

R—O (CH ₂ CH ₂ O) _n H (1) (wherein, R represents an alkyl or alkylaryl group having 4 to 18 carbon atoms, and n represents a number of 1 to 15). Claim 1) and the alkaline earth metal basic carboxylate or alkylphenolate is any of barium or calcium overbased carboxylate carbonate complex or barium or calcium overbased alkylphenolate carbonate complex. Item 1
The foamable vinyl chloride resin composition described in (2) (Claim 2).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described below.

The first aspect of the present invention is a vinyl chloride resin
0 parts by weight, 30 to 120 parts by weight of a plasticizer and 30 parts by weight of a filler 30
To 200 parts by weight, 0.1 to 10 parts by weight of a thermal decomposition type chemical blowing agent, and at least one of basic carboxylate or alkyl phenolate of alkaline earth metal.
5 parts by weight and the following general formula (1) R—O (CH ₂ CH ₂ O) _n H (1) (wherein R represents an alkyl or alkylaryl group having 4 to 18 carbon atoms, and n represents 1 With at least one compound represented by the formula (1):
An expandable vinyl chloride resin composition containing a combination of components.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, and the like. Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer Polymerization stop, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-male Acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride Acrylonitrile copolymer, vinyl chloride - various vinyl ether copolymers, vinyl chloride - styrene - maleic anhydride ternary copolymer, a vinyl chloride - styrene - acrylonitrile terpolymer, vinyl chloride -
Chlorine-containing resins such as vinylidene chloride-vinyl acetate terpolymer, and blends thereof or other chlorine-free synthetic resins such as acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene- Ethyl (meth) acrylate copolymers, blends with polyesters and the like, block copolymers, graft copolymers and the like can be mentioned. In particular, a vinyl chloride homopolymer is preferable, and the average degree of polymerization obtained by an emulsion polymerization method or a microsuspension (suspension polymerization) method is in the range of 700 to 1700 and the average particle diameter is 0.1.
Polyvinyl chloride having a fine particle size of about 5 μm and for processing at a cost is more preferable.

The plasticizer used in the present invention is not particularly limited as long as it is generally used for vinyl chloride resins. For example, di-2-ethylhexyl phthalate, di-n-octyl phthalate, phthalate Aromatic carboxylic esters such as diisooctyl acid, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, C _9-11 mixed alkyl butyl phthalate, diisooctyl isophthalate, diisooctyl adipate, diisodecyl adipate, sebacic acid Aliphatic carboxylic acid esters such as di-2-ethylhexyl, tricresyl phosphate, and phosphate esters such as trixylyl phosphate;
Halogen-containing plasticizers such as chlorinated paraffins and chlorinated fatty acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized castor oil, and other plasticizers such as polyesters. Can be used alone or in combination of two or more.

The amount of the plasticizer to be added is in the range of 30 to 120 parts by weight based on 100 parts by weight of the vinyl chloride resin, and is determined depending on the use of the foam to be obtained from relatively hard to soft. Is done.

The filler used in the present invention includes calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate, calcium sulfite, calcium borate, calcium silicate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium oxide, magnesium hydroxide. , Barium sulfate, aluminum hydroxide, titanium oxide, antimony oxide, silica, zinc borate, zinc stannate, zinc hydroxystannate, alum, talc, kaolin, clay, asbestos, synthetic zeolite and synthetic hydrotalcite, and the like. These can be used alone or in combination of two or more.

The amount of the filler to be added is 30 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin, and is in the above range depending on the purpose of use such as a bulking agent, a processing aid, a reinforcing agent, a flame retardant or a pigment. It is determined appropriately within.

Examples of the thermal decomposition type chemical foaming agent used in the present invention include azo foaming agents, nitroso foaming agents, hydrazide foaming agents, carbazide foaming agents, and triazine foaming agents. More than one species can be used in combination. In particular, azo-based azodicarbonamide, hydrazide-based p, p'-oxybis (benzenesulfonyl hydrazide) or a combination thereof is preferred.

Examples of the azo foaming agent include azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate, and azobis (hexahydrobenzonitrile).

Examples of the nitroso foaming agent include N,
N'-dimethyl-N, N'-dinitroterephthalamine, N, N'-dinitropentamethylenetetramine and the like.

Examples of the hydrazide-based blowing agent include benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 3,3'-disulfonehydrazidephenylsulfone, toluenedisulfonylhydrazone, thiobis (benzenesulfonylhydrazide), p, p'-oxybis ( Benzenesulfonyl hydrazide) and the like.

As the carbazide foaming agent, for example, p-
Toluenesulfonyl semicarbazide, 4,4′-oxybis (benzenesulfonyl semicarbazide) and the like.

Examples of the triazine-based blowing agent include trihydrazinotriazine and 1,3-bis (o-biphenyltriazine).

The amount of the thermal decomposition type chemical foaming agent to be added is in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin, and is determined according to the use of the foam to be obtained.

The alkaline earth metal basic carboxylate or alkylphenolate metal used in the present invention is beryllium, magnesium, calcium, strontium or barium.

The carboxylic acid is a saturated or unsaturated aliphatic carboxylic acid having 2 to 22 carbon atoms, a cyclic or heterocyclic carboxylic acid having 7 to 16 carbon atoms, a hydroxy acid or an alkoxy acid having 2 to 10 carbon atoms. Yes, for example, acetic acid, propionic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
12-hydroxystearic acid, behenic acid, carbon number 15
~ 16 trialkylacetic acids, oleic acids, linoleic acids,
Ricinoleic acid, adipic acid, sebacic acid, benzoic acid,
o, m or p-toluic acid, xylic acid, pt-butylbenzoic acid, phthalic acid, phthalic acid monoester, salicylic acid or a mixed carboxylic acid thereof.

Examples of the alkylphenol include pt-butylphenol, pt-octylphenol, nonylphenol, dinonylphenol, decylphenol and dodecylphenol.

The basic carboxylate or alkylphenolate of the alkaline earth metal is added in an amount of 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin. . If the amount is less than 0.05 part by weight, thermal stability is not good, and if it exceeds 5 parts by weight, foaming is suppressed.

The following general formula (1) RO (CH ₂ CH ₂ O) _n H (1) (wherein R represents an alkyl or alkylaryl group having 4 to 18 carbon atoms) n represents a number of 1 to 15.) are compounds generally referred to by the chemical name of polyoxyalkylene alkyl ether, such as polyoxyethylene butyl ether, polyoxyethylene hexyl ether, and polyoxyethylene nonyl. Ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene butyl Fe Ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl phenyl ether, and the like. The degree of polymerization of these polymers is preferably 15 or less, more preferably 3 to 5.

The amount of the above compound is 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.01 part by weight, the cell adjusting effect is not sufficient, and if it exceeds 2 parts by weight, the foam is colored.

Claim 2 specifies the basic carboxylate or alkylphenolate of the alkyl earth metal as an overbased carboxylate carbonate complex of barium or calcium or an overbased alkylphenolate carbonate complex of barium or calcium. Things.

The composition of the present invention may optionally contain a foaming accelerator, a cell conditioner, a stabilizing aid and the like.

Examples of the foaming accelerator used herein include organic zinc compounds such as urea, zinc oxide and zinc carboxylate, sodium carboxylate, potassium carboxylate, oxalic acid, tartaric acid, sodium and calcium perchlorates, and the like.
Examples thereof include magnesium, barium or zinc salts, glycol complexes thereof, and copper compounds. In particular, organic zinc compounds such as zinc carboxylate are preferable, and these can be used alone or in combination of two or more.

The above-mentioned organic zinc compounds such as zinc carboxylate include, for example, zinc acetate, zinc propionate, zinc 2-ethylpentanoate, zinc 2-ethyl-4-methylpentanoate, zinc 2-methylhexanoate, 2-ethylhexanoate. Zinc hexanoate, zinc isooctylate, zinc n-octylate, zinc neodecanoate, zinc isodecanoate, zinc n-decanoate,
Zinc laurate, zinc myristate, zinc palmitate, zinc stearate, zinc isostearate, 12-
Zinc hydroxystearate, zinc behenate, zinc oleate, zinc linoleate, zinc linoleate, zinc ricinoleate, zinc benzoate, o, m or zinc p-toluate, zinc pt-butyl benzoate, Zinc salicylate,
Zinc phthalate, zinc salt of monoalkyl phthalate (C _4-18 ) ester, zinc naphthenate, zinc dehydroacetate, zinc dibutyldithiocarbamate, zinc aminocrotonate, zinc salt of 2-mercaptobenzothiazole, zinc pyrithione, urea or And zinc complex of diphenylurea.

The organic zinc compound such as zinc carboxylate may be an acidic salt, a neutral salt or a basic salt, and the amount of these added is 0.05 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. Parts, preferably 0.2 to 2 parts by weight.

As the cell conditioner used here, there may be mentioned the following surfactants and acrylic polymers.

Examples of the surfactant include sodium, barium, calcium or zinc salts of lauryl alcohol sulfonate, sodium, potassium, barium or zinc n-dodecylbenzenesulfonate, sodium dodecylphenoxypolyoxyethylene sulfonate and the like. Can be given.

Examples of the acrylic polymer include butyl methacrylate polymer, isobutyl methacrylate polymer, tert-butyl methacrylate polymer, and isooctyl methacrylate having a polymerization degree in the range of 100 to 2,000. Examples include ester polymers, 2-ethylhexyl methacrylate polymer, isodecyl methacrylate polymer, lauryl methacrylate polymer, and the like.

Examples of the stabilizing aid used here include organic phosphites, organic phosphates and metal salts thereof.

Examples of the organic phosphite include triphenyl phosphite, triisooctyl phosphite, tristridecyl phosphite, diphenyl monooctyl phosphite, diphenyl monodecyl phosphite, and 4,4'-isopropylidene diphenyl alkyl. (C ₁₂ ~C ₁₅₎ diphosphite, and the like.

Examples of the organic phosphate and the metal salt thereof include diisooctyl acid phosphate, bistridecyl acid phosphate, zinc or potassium salt of diisooctyl acid phosphate, and zinc or potassium salt of bistridecyl acid phosphate. can give.

As other various additives, there may be mentioned those usually used for vinyl chloride resins, for example, partial esters of dipentaerythritol and adipic acid,
Heat-resistant assistants such as polyols and tris (2-hydroxyethyl) isocyanurate, epoxy compounds such as epoxidized resins, coloring inhibitors such as sulfolene and β-diketone compounds, phenol-based or sulfur-based antioxidants, hindered amines System light stabilizer, UV absorber, pigment, flame retardant, flame retardant, lubricant, antistatic agent, plate-out inhibitor, fungicide, antibacterial agent, anti-aging agent, vulcanization accelerator, cross-linking agent, matting Agents, rebound resilience improvers, sol viscosity lowering agents, silicon, titanium and aluminum coupling agents, phosphorus surfactants, metal deactivators, release agents, surface treatment agents and the like.

[0045]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples, but the scope of the present invention is not limited to only the following examples.

(Examples 1 to 4, Comparative Examples 1 to 3) The expandable vinyl chloride resin composition to which the components of the present invention and the comparative examples were added was prepared as follows, and then a foam was molded. .

In this example, the polyvinyl chloride (average degree of polymerization: 800) obtained by emulsion polymerization was used for (a) of the present invention.
A component (e) and a comparative example of the component (e), a cell conditioner (an air bubble stabilizer), a foaming accelerator, and a diluent are added and blended, and the mixture is sufficiently mixed with a mixer to obtain a uniform plastisol compound. did.

Basic Compound Polyvinyl chloride 100 parts by weight Diisooctyl phthalate [component (a)] 48 parts by weight 45% chlorinated paraffin [component (a)] 8 parts by weight Heavy calcium carbonate [(b) component] 100 parts by weight Part Rutile-type titanium oxide [component (b)] 15 parts by weight Azodicarbonamide [component (c)] 4 parts by weight Overbased carboxylate carbonate complex of barium [component (d)] 0.6 parts by weight methacrylic acid Isobutyl ester polymer (cell regulator) 0.3 parts by weight Zinc propionate (foaming accelerator) 0.5 parts by weight Basic zinc neodecanoate (foaming accelerator) 1.0 parts by weight White kerosene (diluent) 10 parts by weight Component (e) of the present invention and components of comparative examples Table 1 Test 1 Viscosity immediately after preparation of the above plastisol compound and after standing for 7 days Was measured with a B-type viscometer, the results first
It is shown in the table. If this measured value is less than 4000 cps immediately after, and less than 5000 cps after 7 days, there is no problem in industrial practice.

Test 2 The above plastisol compound was uniformly applied on a flame-retardant paper as a base material so as to have a thickness of 0.2 mm with a doctor knife. This was placed horizontally in a heating furnace heated to 150 ° C. and left standing for 60 seconds to gel to form a sheet, which was used as an original sheet.

A part of the original sheet was sampled to prepare a test piece, which was placed in a foaming furnace heated to 240 ° C. for a predetermined time to foam. At this time, the state of foaming, particularly the rise of foaming (foaming speed), thermal stability (degree of burning due to thermal degradation), uniformity and fineness of bubbles, surface smoothness, etc. were examined. In addition, about the size of the bubble which shows the uniformity and fineness of the bubble, the cut surface of the foamed sheet was observed using a microscope of 40 times.

Test 3 The plate-out test was performed as follows. Three pieces of 30 × 30 mm sheets were collected from the above-mentioned original sheet, and one piece was placed on a ferro board so that the application surface was in contact therewith.
It was placed in a heating furnace at 110 ° C., taken out 5 minutes later, immediately pressed by a roller, and then the sheet was removed. Next, a new sheet piece was placed on the ferro-plate at the same position as the previous crimping surface, and the same operation was performed. This operation was repeated three times in total. By repeating this operation, the amount of contaminants (degree of contamination) adhering to the mirror surface on the ferro-plate, that is, the plate-out, was observed.

The results of Tests 2 and 3 are shown in Table 1 below.

The rising of foaming, thermal stability, surface smoothness, and plate-out are indicated by 5 levels, which are indicated as 5, excellent, 4, excellent, normal, 3, slightly poor, and 2 bad. Expressed by evaluation. The diameter of the bubble was measured with a microscope. Bubble diameter 200
5,200 to 250 in case of extremely excellent at less than μm
Less than μm is 4,250-350 μm is less than 3,350
It was expressed by a five-point scale of 2 below 500 μm and 1 when it was worse than 500 μm. If these five-step numerical values are 4 or more, there is no problem in industrial implementation.

Test 4 Next, the foamed sheet foamed as described above was placed in a foaming furnace heated to 225 ° C. for a predetermined time, and the degree of settling due to reheating during embossing was examined. The results are shown in Table 1. In addition, the judgment of the result was expressed by giving a percentage by the following formula.

(Thickness of reheated foam sheet / thickness of foam sheet) × 100 = degree of settling% If this percentage value is 80 or more, there is no problem in industrial practice.

[0056]

[Table 1]

As is clear from Table 1, the sol viscosity, the rise of foaming, the thermal stability, the uniformity of the bubbles, the size of the bubbles indicating the uniformity and the fineness, and the surface smoothness of the comparative example are different from those of the comparative example. The results show excellent results in all aspects of prevention of settling due to plate-out and reheating.

(Examples 5 to 9 and Comparative Examples 4 and 5) The foamable vinyl chloride resin compositions of Examples and Comparative Examples were added in combination with low-toxicity compounding agents.

Basic blend Polyvinyl chloride 100 parts by weight Diisononyl adipate [component (a)] 50 parts by weight Heavy calcium carbonate [component (b)] 50 parts by weight Rutile-type titanium oxide [component (b)] 15 parts by weight azodicarbon Amide [(c) component] 3 parts by weight p, p'-oxybis (benzenesulfonylhydrazide) [(c) component] 1.5 parts by weight Calcium overbased carboxylate carbonate complex [(d) component] 0.6 Parts by weight isobutyl methacrylate polymer [cell adjuster] 0.2 parts by weight sodium n-dodecylbenzenesulfonate [cell adjuster] 0.2 parts by weight zinc 2-ethylhexanoate [foaming accelerator] 0.8 parts by weight Part zinc oleate [foaming accelerator] 1 part by weight n-dodecylbenzene [diluent] 10 parts by weight ) Ingredients and Ingredients of Comparative Examples Table 2 shows a test using the above plastisol compound under the same method and conditions as in Examples 1 to 4 and Comparative Examples 1 to 3 described above. Was. The results are shown in Table 2.

[0060]

[Table 2]

As is clear from Table 2, according to the present invention, the sol viscosity, the rise of foaming, the thermal stability, the uniformity of the bubbles and the size of the bubbles exhibiting the fineness, and the surface smoothness of the comparative example are different from those of the comparative example. It shows excellent results in all aspects of preventing settling due to reheating during plate-out and embossing.

[0062]

As shown in the examples, the foamable vinyl chloride resin composition of the present invention has a low sol viscosity to enhance workability, prevent plate-out during embossing, and reduce foaming. It also improves workability by having thermal stability without disturbing the rise, and
Prevents settling of foaming due to reheating, and makes it possible to impart surface smoothness of foam by making foam cells uniform and fine,
Product value can be significantly increased.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] September 6, 1999 (September 9, 1999)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011]

According to the present invention , (a) 30 to 120 parts by weight of a plasticizer, (b) 30 to 200 parts by weight of a filler, and (c) a thermally decomposable resin are added to 100 parts by weight of a vinyl chloride resin. Chemical foaming agent 0.1 to 10 layers, (d ) barium, mug
Nebasium or calcium overbased carboxylates
Carbonate complex or barium, magnesium
Or calcium overbased alkylphenolate carb
At least one of a complex of 0.05 to 5 times
A foamable vinyl chloride-based resin composition comprising a combination of at least one part by mass and (e) 0.01 to 2 parts by weight of at least one compound represented by the following general formula (1). _{R-O (CH 2 CH 2} O) n H (1) ( wherein, R represents an alkyl or alkylaryl group having 4 to 18 carbon atoms, n is a number of 1 to 15.) It is.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Deleted

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

According to the present invention, 30 to 120 parts by weight of a plasticizer and 30 to 20 parts by weight of a filler are added to 100 parts by weight of a vinyl chloride resin.
0 parts by weight, 0.1 to 10 parts by weight of pyrolytic chemical blowing agent, and barium, magnesium or calcium oversalt
Basic carboxylate carbonate complex or barium
Overbased magnesium, magnesium or calcium
At least one of the rufenolate carbonate complexes
And 0.05 to 5 parts by weight of the following, and the following general formula (1): RO (CH ₂ CH ₂ O) _n H (1) (wherein R is alkyl or alkyl having 4 to 18 carbon atoms) Represents an aryl group, and n represents a number of 1 to 15.) A foamable vinyl chloride resin composition containing a combination of at least one compound represented by formula (1) and 0.01 to 2 parts by weight. .

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Deleted

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

The above barium, magnesium or potassium
Overbased carboxylate carbonate complex of lucium
Or excess of barium, magnesium or calcium
Any of the basic alkylphenolate carbonate complexes
The amount of the one kind is 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.05 part by weight, thermal stability is not good, and if it exceeds 5 parts by weight, foaming is suppressed.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Deleted

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/09 C08K 5/09 5/138 5/138 F term (Reference) 4F074 AA29 AA35 AA36 AA64 AA65 AC17 AC19 AC20 AC22 AC26 AC30 AC31 AC32. DE147 DE187 DE237 DE287 DG047 DG057 DH047 DJ007 DJ017 DJ037 DJ047 DK007 ED029 ED039 EG039 EG049 EG059 EG079 EH096 EH146 EJ069 EJ079 EQ018 EQ028 EQ038 ES008 ET008 EU188 EV268 EW046 FD017 FD030 FD017 FD022 FD022

Claims (2)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 30 to 120 parts by weight of a plasticizer, (b) filler 30 to
200 parts by weight, (c) thermal decomposition type chemical blowing agent 0.1 to 10
(D) at least one kind of basic carboxylate or alkylphenolate of alkaline earth metal;
A foamable vinyl chloride resin composition comprising a combination of 0.5 to 5 parts by weight and (e) at least one kind of a compound represented by the following general formula (1): 0.01 to 2 parts by weight. . _{R-O (CH 2 CH 2} O) n H (1) ( wherein, R represents an alkyl or alkylaryl group having 4 to 18 carbon atoms, n is a number of 1 to 15.) 2. The alkaline earth metal basic carboxylate or alkyl phenolate is either a barium or calcium overbased carboxylate carbonate complex or a barium or calcium overbased alkyl phenolate carbonate complex. Item 4. An expandable vinyl chloride resin composition according to Item 1.