JPH0764945B2 - Expandable vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a highly filler-containing expandable vinyl chloride resin composition, more specifically, a vinyl chloride resin derived from a filler, a plasticizer, and a hydroxycarboxylic acid. To a highly expandable vinyl chloride resin composition having good workability and processability, having uniform foam cells, and having improved plate-out property, which is obtained by blending the polyester and the heat-decomposable organic foaming agent.

[Prior art and its problems]

Since vinyl chloride resin has good physical and chemical properties, it is a suitable material for application to leather, wallpaper, cushioning material, etc. as a foamed molded product. When a foam molded article is produced by adding a large amount of a filler to a vinyl chloride resin, the viscosity becomes high and the workability is significantly reduced. In addition, the foamed cells become rough and the plate-out is large, so that practical improvement has been required.

For example, although a method of adding a large amount of a plasticizer has been proposed, it has the effect of lowering the viscosity, but it does not improve the foamed cells and the plate-out property. Further, a method of adding a cell adjusting agent such as an acrylic acid resin or a methacrylic acid ester resin has been proposed. By this method, relatively uniform foam cells can be obtained, but when a large amount of the filler is mixed, the effect is small, and the effect of lowering the viscosity and the effect of preventing plate-out are not exhibited. The effect of using a combination of a plasticizer and a cell adjuster is small, and plate-out cannot be prevented.

[Means for solving problems]

The present inventors, in view of the above-mentioned current situation, as a result of repeated earnest studies, when a large amount of a filler is blended, workability and workability are good, a uniform foam cell is provided, and plate-out property is improved. A highly expandable vinyl chloride resin composition was found.

That is, the present invention, with respect to 100 parts by weight of vinyl chloride resin,
(A) 50 to 250 parts by weight of a filler, (b) 30 to 100 parts by weight of a plasticizer, (c) 0.01 to 5 parts by weight of a polyester compound derived from a hydroxycarboxylic acid, and (d) a pyrolytic organic foaming agent 0.05. The present invention provides a foamable vinyl chloride resin composition characterized by being mixed in an amount of 10 to 10 parts by weight.

Hereinafter, the expandable vinyl chloride resin composition of the present invention will be described in detail. As the vinyl chloride resin used in the present invention,
Vinyl chloride homopolymer; vinyl chloride vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-ethylene-vinyl acetate copolymers and other vinyl chloride-based copolymers; ethylene-vinyl acetate copolymers or ethylene Examples thereof include a vinyl chloride-based graft copolymer obtained by graft-polymerizing vinyl chloride on a propylene-based copolymer and the like. The average degree of polymerization (JIS K-6721) is preferably in the range of 600 to 1800.

The filler used in the present invention includes calcium carbonate,
Examples thereof include aluminum hydroxide, titanium oxide, talc, asbestos and silica.

The plasticizer used in the present invention is not particularly limited as long as it is a vinyl chloride type, and examples thereof include di-n-butyl phthalate, di-n-octyl phthalate and di-phthalate. 2-ethylhexyl, diisooctyl phthalate, octyl decyl, diisodecyl phthalate, di C ₇ ~ ₉ alkyl, butyl benzyl phthalate, phthalate plasticizers such as isophthalic acid di-2-ethylhexyl adipate, di - Fatty acid ester plasticizers such as 2-ethylhexyl, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate , Phosphate ester plasticizers such as trixylyl phosphate, chlorinated parasite Fin, chlorine plasticizers such as chlorinated fatty acid esters, polyester plasticizers and the like, can be used as a mixture alone or in combination.

The polyester compound derived from the hydroxycarboxylic acid used in the present invention has the formula: HO-R-COOH (wherein R represents a divalent saturated or unsaturated aliphatic group having at least 8 carbon atoms, One or more polyesters derived from a hydroxycarboxylic acid having at least 4 carbon atoms between the hydroxy group and the carboxylic acid, or from a mixture of such hydroxycarboxylic acid and a carboxylic acid having no hydroxy group. Or the salt is included. The group represented by R in the hydroxycarboxylic acid preferably has 12 to 20 carbon atoms, and further preferably has 8 to 14 carbon atoms between the carboxylic acid and the hydroxy group. Further, the hydroxy group is preferably a secondary hydroxy group. Examples of such hydroxycarboxylic acids are ricinoleic acid, a mixture of 9- and 10-hydroxystearic acid (obtained by sulfating oleic acid and subsequent hydrolysis), 12-hydroxystearic acid and also 12-hydroxystearic acid. Commercially available hydrogenated castor oil fatty acids containing small amounts of stearic acid and palmitic acid in addition to stearic acid are mentioned.

Carboxylic acids which can be used together with hydroxycarboxylic acids to obtain polyesters are preferably saturated or unsaturated aliphatic carboxylic acids, especially alkyl and alkenyl carboxylic acids having 8 to 20 carbon atoms. Examples of such acids include lauric acid, palmitic acid, stearic acid and oleic acid.

Next, specific examples of the polyester compound used in the present invention are shown.

(Polyester A) 12-hydroxystearic acid in xylene (acid value 178,
The hydroxyl value of 155) was stirred at 190 to 200 ° C for 24 hours. Next, a polyester (acid value 31) obtained by distilling off water of reaction and xylene.

(Polyester B) A polyester (acid value 85) obtained from 72 parts of 12-hydroxystearic acid and 28 parts of stearic acid in the same manner.

(Polyester C) A polyester obtained similarly from ricinoleic acid (acid value 18).

(Polyester D) Similarly, a polyester obtained from 15 parts of oleic acid and 85 parts of ricinoleic acid (acid value 39).

(Polyester E) A polyester (acid value 35) obtained from a mixture of 9- and 10-hydroxystearic acid in the same manner.

(Polyester F) Similarly, a polyester obtained from 12-hydroxystearic acid (acid value 40).

Examples of the heat-decomposable organic blowing agent used in the present invention include N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalamide and other nitroso compounds, and azodicarbonate. Amides, azo compounds such as azobisisobutyronitrile, benzenesulfonyl hydrazides, sulfonylhydrazides such as P, P'-oxybis (benzenesulfonylhydrazide), toluenesulfonylhydrazide and their derivatives, and those containing these as the main components Is mentioned.

A metal salt stabilizer is generally used in the composition of the present invention.
Examples of these metal salts include one or more organic acid salts selected from barium, calcium, magnesium, strontium, sodium, potassium, zinc, tin or organic tin. Examples of the organic acid constituting the organic acid salt include acetic acid, hexanoic acid, octanoic acid, 2-ethylhexoic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and myrilic acid. Strain acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, arachidic acid, erucic acid and animal fatty acids, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid , Cottonseed oil fatty acid, tall oil fatty acid, and benzoic acid,
Toluic acid, chlorobenzoic acid, p-t-butylbenzoic acid, xylyl acid, ethylbenzoic acid, isopropylbenzoic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, hydroatorobaic acid, atorobaic acid, fulic acid, tenic acid,
Nicotinic acid, isonicotinic acid, glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, acetoacetic acid, levulinic acid, salicylic acid, anisic acid, cyclohexanoic acid, β-mercaptopropionic acid, isooctylthioglycolate, 2 -Ethylhexyl β-mercaptopropyroic acid and the like can be mentioned.

The composition of the present invention further comprises an organic phosphite compound and / or
Alternatively, when used together with an epoxy compound, an excellent synergistic effect is exhibited.

Examples of the organic phosphite compound include diphenyldecyl phosphite, triphenyl phosphite, and tris-
Nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite,
Dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethylphosphite, distearyl pentaerythritol diphosphite, diisodecyl Pentaerythritol diphosphite, diphenyl acid phosphite, tris (lauryl-2-thioethyl) phosphite, tetotatridecyl-
1,1,3-tris (2'-methyl-5'-tert-butyl-
4'-oxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tris (4-oxy-2,5
-Di-tert-butylphenyl) phosphite, tris (4
-Oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite Phyto, diphenyl bis [4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl)
-Bis [4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol di Phosphite,
Phenyldiisodecyl osphite, tetratridecyl-4,4'-n-butylidene bis (2-tert-butyl-5-
Examples include methylphenol) diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, and the like.

The addition amount of these organic phosphite compounds is preferably 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the resin.

As the epoxy compound, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized polybutadiene, epoxidized methyl stearate, -butyl, -2 ethylhexyl, -Stearyl, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol A diglycidyl ether, Vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6
-Methylepoxycyclohexanecarboxylate and the like.

The addition amount of these epoxy compounds is preferably 0.01 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the resin.

A colorant, a flame retardant, an antioxidant, an antistatic agent, a light stabilizer, an antifungal agent and the like may be appropriately added to the composition of the present invention as long as the physical properties of the molded article are not impaired.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 The following formulations were mixed using a muller for 20 minutes to make a uniform paste sol. The viscosity of this paste sol immediately after mixing and after standing for 2 days was measured with a B-type viscometer. Further, the paste sol was applied onto flame-retardant paper to a thickness of 0.18 mm, and semi-cured in an oven at 140 ° C. for 1 minute. 220 ° C
The mixture was heated for 30 to 90 seconds to form a foam. The cell state of the obtained foam was observed. In addition, a semi-cured sample
Put the coated surface on the chrome-plated plate several times in an oven at 150 ° C, and plate out the chrome-plated plate (cloudy state).
Was observed. The results are shown in Table 1 below.

The foam cell state and the plate-out property were evaluated on a scale of five.

Example 2 A paste sol and a test piece were prepared in the same manner as in Example 1 with the following formulation, and the performance was evaluated. The results are shown in the table below.
2 shows.

(Compound) Parts by weight PVC (P-455K made by Mitsubishi Kasei Vinyl) 100 Dioctyl phthalate 50 Calcium carbonate (H) 100 Aluminum hydroxide 50 Titanium oxide (R) 20 MARK FL-30 (Adeka Argus K / Zn liquid stable) Agent) 3 Chlorinated paraffin 15 Epochized soybean oil 2 Azodicarbonamide 1 P, P′-oxybis (benzenesulfonylhydrazide) 1 Mineral spirit 10 Additives (Table-2) 0.5 Example 3 A paste sol and a test piece were prepared in the same manner as in Example 1 with the following formulation, and the performance was evaluated. The results are shown in the table below.
3 shows.

(Compounding) Parts by weight PVC (PSL-31 manufactured by Kanebuchi Kagaku) 100 Dioctyl phthalate 60 Calcium carbonate (H) 200 Titanium oxide (R) 20 Zn-based liquid stabilizer 3 Azodicarbonamide 3 Tricresyl phosphate 15 Mineral spirit 10 Additive (Table-3) 0.5 EFFECT OF THE INVENTION The expandable vinyl chloride resin composition of the present invention has good workability and processability, has uniform foam cells, and has improved plate-out properties.

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 50 to 250 parts by weight of a filler, (b) 30 to 100 parts by weight of a plasticizer, (c) 0.01 to 5 parts by weight of a polyester compound derived from a hydroxycarboxylic acid, and (d) a pyrolytic organic foaming agent 0.05. A foamable vinyl chloride resin composition containing about 10 parts by weight.