JP3150638B2 - Vinyl chloride resin composition in which blocking during storage is prevented - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a general film
The present invention relates to a vinyl chloride resin composition for a sheet, and more particularly to a vinyl chloride resin composition for a general film / sheet which prevents blocking during storage.

More specifically, the present invention comprises a combination of a low-toxic or non-toxic metal salt compound containing no lead or cadmium, a heat stabilizing aid, an anti-blocking agent and a transparency improving agent. The present invention relates to a novel vinyl chloride-based resin composition for a general film or sheet which prevents blocking.

[0003]

2. Description of the Related Art Vinyl chloride resin has been widely used as an alternative material such as metal, wood, cloth and paper because of its various excellent properties. Above all, a so-called soft vinyl chloride resin composition in which the flexibility of a product can be adjusted by increasing or decreasing the amount of a plasticizer is used as a film or sheet for sundries, raincoat (kappa, umbrella, boots, etc.), toy, stationery, furniture decoration, bag. It is applied to various other uses. But,
The vinyl chloride resin has a drawback in that, when subjected to thermoforming, the resin is decomposed with dehydrochlorination to color the molded product, thereby lowering the commercial value. Therefore, conventionally, various stabilizers have been added thereto to stabilize the heat.

The components of such stabilizers include, for example, Ba-Z
n-type or Ca-Zn-type metal soap combined with an organic phosphite compound, a hindered phenol-based antioxidant or an epoxy compound, etc. Although the method of stabilizing the system resin composition has no problem in terms of toxicity, it is still insufficient in the performance of preventing coloring due to deterioration during thermoforming, and further improvement in performance has been demanded. For this reason, many methods have been proposed by the United States to further improve the performance by further adding various stabilizing aids to the above-mentioned stabilizer component.

The present applicant also discloses a method using a β-diketone compound in Japanese Patent Publication Nos. 52-47948 and 57-9386, and a method using a metal salt compound of β-diketone in Japanese Patent Publication No. 57-39260. In Japanese Patent Publication Nos. 1-58213 and 1-58214, a method using cyclopentanone and cyclohexanone-based compounds was proposed.

Although these methods are currently widely recognized to exhibit a remarkable effect in terms of preventing coloration, however, in order to expand recent vinyl chloride resin products and improve productivity, more advanced methods are used. There is a demand for a new molding technology.
New developments have also been made for stabilizers and auxiliaries used in the above, and stabilization auxiliaries with new formulations have been disclosed one after another.

For example, in the product catalog of Kyowa Chemical Industry, hydrotalcites, which are double salts of inorganic metals, are introduced as heat stabilizers for polyvinyl chloride.
No. 6012 discloses a method using a combination of a β-diketone compound and a hydrotalcite compound.

[0008] These methods can prevent zinc burning, which is a rapid degradation and decomposition, even when processed under severe heat conditions because an inorganic metal salt compound having excellent thermal stability is used. Zinc burning, as used herein, is a non-toxic or low-toxicity stabilizer that does not use lead at present, and zinc carboxylate, which is used as an essential component, captures hydrochloric acid gas released from vinyl chloride resin during high-temperature processing. Zinc chloride is generated, and this is used as a decomposition catalyst to break the bonds between the carbons that form the skeleton of the vinyl chloride resin one after another, eventually causing carbonization. Is the one most feared.

Although such zinc burning can be prevented by using the above-mentioned inorganic metal salt compound, if the amount required to achieve the effect is added, on the other hand, the coloring becomes intense and the color becomes transparent. There was a drawback that the properties deteriorated.

In recent years, vinyl chloride resins have begun to be used for applications in which products are exposed to high temperatures for a long period of time. Therefore, performance that can withstand such conditions has been required. Therefore, the present applicant has developed and proposed a new compound in response to the above-mentioned requirements.

For example, Japanese Patent Publication No. 62-16220 discloses a method using a complex compound comprising magnesium perchlorate and a polyhydric alcohol, and Japanese Patent Publication No. 63-462 discloses a method using sodium, barium, calcium perchlorate and a polyhydric alcohol. A method using a complex compound consisting of alcohols was proposed.

[0012] These methods are excellent in preventing the coloring of the product against long-term high-temperature heat storage. However, when a necessary amount for sufficiently exhibiting this effect is added, zinc burning is promoted and the transparency is improved. It could not be applied to general films and sheets, for example, and deteriorated printability. Neither is it considered for blocking. The term "blocking" as used herein refers to a phenomenon in which, while plastic films or sheets are superposed on each other and kept in contact for a long time, the plastic films or sheets are in close contact with each other and are not easily peeled off. By the way, usually, the processing company winds the produced film / sheet into a piece of cloth and saves it, and then performs secondary processing such as printing and squeezing. Let it. In addition, there are many cases where the raw material is wholesaled to a secondary processing specialist, and there is a problem that a film or sheet that causes blocking causes stains on the rewound film or when it is severely damaged, thereby lowering the commercial value. there were. .

As a method for preventing this blocking, a method in which a lubricant, an anti-adhesive agent, a dropping agent and the like are mixed into a raw material polymer is disclosed in Japanese Patent Publication No. 54-30698 and Japanese Patent Application Laid-Open No. Sho 62-270644. However, these proposals cause so-called bleeding, in which the kneaded compound is jetted to the surface of the product, resulting in poor ink sticking during printing. Also, the transparency is reduced.

As another method, a method of spraying a powdery substance such as talc silicate on the surface of a film or sheet is known to those skilled in the art. Similarly, JP-A-4-63840
Has proposed a method of spraying powder such as starch having a specified particle size on one surface of a film or the like before winding. Since these are not kneading methods during thermal processing,
It does not adversely affect the performance of the film / sheet, but must be sprayed on this side before winding the primary product, and the secondary material must be wiped off during spreading. However, this method has been a major problem for the industry in which the production efficiency has to be reduced and mass production has to provide a cost advantage.

[0015]

SUMMARY OF THE INVENTION According to the present invention, by selecting and combining the specified low-toxicity stabilizer and stabilizing aid, coloring and zinc burning are prevented and printability and transparency are not deteriorated. Moreover, it is an object of the present invention to obtain a vinyl chloride-based resin composition in which the high-temperature heat storage property is improved and the blocking during storage is prevented without lowering the production efficiency.

The present invention relates to a vinyl chloride resin 100 weight
In part, (a) a metal salt compound 0.1-5 parts by weight of a carboxylic acid or alkylphenols, and at least one 1-10 wt selected from among (b) mono alkylbenzene and di-alkylbenzene, (c) Β-diketone compound of either diaroylmethane or alkanoylaroylmethane and at least one of these metal salts
And 0.001 parts by weight, the storage time of the blocking, characterized in that comprising a combination of the (d) 2,5-dihydro-1,1-dioxide 0.001 parts by weight Prevented vinyl chloride resin composition (Claim 1), 100 parts by weight of vinyl chloride resin, (a) 0.1 to 5 metal salt compounds of carboxylic acid or alkylphenol
And parts by weight, of at least one 1 to 10 selected from among (b) mono alkylbenzene and di-alkylbenzene
Parts by weight , and (c) 0.001 to 1 weight of at least one of β-diketone compounds of either dialoylmethane or alkanoylaroylmethane and metal salts thereof
Parts and, (d) 2,5-dihydro-1,1-di <br/> oxide and 0.001 parts by _{weight, (e) Mg 1-x} Al x (OH) 2 (CO 3) x _{/ 2} · mH ₂ O (1) (where X is 0.3 ≦ X ≦ 0.33 and m is 0 <m
≦ 0.7. Magnesium represented by)
Aluminum composite hydroxide salt and Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) _{1 -x / 2} (ClO ₄ ) _x · mH ₂ O (2) where x is 0.5 ≦ x ≦ 2, and m represents 0 <m ≦ 6.) At least one selected from two inorganic salt compounds of magnesium-aluminum hydroxide perchloric carbonate hydrate 0.01 to 3 parts by weight of a vinyl chloride resin composition in which blocking during storage is prevented (Claim 2), wherein 100 parts by weight of the vinyl chloride resin is (A) 0.1 to 5 parts by weight of a metal salt compound of a carboxylic acid or an alkylphenol;
(B) at least 1 to 10 parts by weight selected from mono-alkylbenzene and di-alkylbenzene,
(C) at least one 0.001 to 1 part by weight of a β-diketone compound of either dialoylmethane or alkanoylaroylmethane and a metal salt thereof;
(D) 0.001 to 1 part by weight of 2,5-dihydrothiophene-1,1-dioxide, and (f) any one of sodium, magnesium, calcium and barium salts of perchloric acid Or a combination of any one of these metal salts and 0.01 to 0.5 parts by weight of a complex compound selected from a polyhydric alcohol or a derivative thereof. A vinyl chloride resin composition wherein blocking during storage is prevented (Claim 3), wherein the metal of the metal salt compound of carboxylic acid or alkylphenol is any combination of barium-zinc or calcium-zinc. The vinyl chloride resin composition according to any one of claims 1 to 3, wherein blocking during storage is prevented (claim 4), and the metal salt compound is barium or calcium. Blocking during storage according to any one of claims 1 to 3, which is a combination of any of an overbased carboxylate carbonate complex or an overbased alkyl phenate carbonate complex and zinc carboxylate. The prevented vinyl chloride resin composition (Claim 5), the β-diketone compound of dialoylmethane or alkanoylaroylmethane, and the metal salt thereof are either dibenzoylmethane or stearoylbenzoylmethane or a metal salt thereof. Claim 1
4. The vinyl chloride resin composition (claim 6) and the complex compound, wherein the blocking during storage according to any one of (1) to (3) is prevented, comprises sodium perchlorate or magnesium perchlorate, diethylene glycol monomethyl ether, diethylene glycol The vinyl chloride resin composition according to any one of claims 1 to 3 , which is a complex compound with any one of monobutyl ether and triethylene glycol monomethyl ether. . According to the present invention, the synergistic action of the above-mentioned novel combination components prevents coloring and zinc burning, does not deteriorate printability and transparency, and furthermore, improves high-temperature heat storage properties and does not lower production efficiency. To prevent blocking during storage.

That is, by replacing a part of the plasticizer represented by dioctyl phthalate or the like with at least one selected from mono-alkylbenzene and dialkylbenzene as the component (b), blocking can be achieved without impairing flexibility. In addition to preventing coloration, the addition of a β-diketone compound or a metal salt thereof as a component (c) prevents coloring, and a 2,5-dihydrothiophene-1,1 component as a component (d).
By adding-ヂ oxide, the transparency deteriorated by the addition of the component (b) is improved, the initial coloring is prevented, and the component (e), which is represented by the formulas (1) and (2), is specified. While preventing zinc burning by at least one addition selected from the two inorganic salt compounds described above,
It is intended to improve the high-temperature heat storage property by adding a metal salt of perchloric acid as the component (d) or a complex compound of these and a polyhydric alcohol in addition to the component (d). The present invention has solved various difficult problems which are contradictory when trying to prevent blocking by the synergistic effect of the above-mentioned components.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin composition according to claim 1 of the present invention, in which blocking during storage is prevented,
(A) a metal salt compound of a carboxylic acid or an alkylphenol, (b) at least one of mono-alkylbenzene and di-alkylbenzene, and (c) a β-diketone compound of dialoylmethane or alkanoylaroylmethane on a vinyl chloride resin. And at least one of these metal salts and (d) 2,5-dihydrothiophene-1,1-dioxide in combination.

The metal of the metal salt compound as the stabilizer component (a) used in claim 1 is calcium, barium, strontium, magnesium, zirconium, aluminum, zinc or tin, and is used in two or more of these. . In this case, the combination of metals is preferably barium-zinc or calcium-zinc. If the metal salt compound is a combination of barium or calcium overbased carboxylate carbonate complex or overbased alkyl phenate carbonate complex and zinc carboxylate, the effect is reduced even if the amount used is reduced. Have.

The organic residue bonded to the metal is a carboxylic acid or an alkylphenol. The carboxylic acid is a carboxylic acid of a saturated or unsaturated fatty acid having 2 to 22 carbon atoms, an alicyclic, heterocyclic or aromatic carboxylic acid having 7 to 16 carbon atoms, for example, octanoic acid, 2-ethyl Hexanoic acid, decanoic acid, isodecanoic acid, lauric acid,
Myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, behenic acid,
Tris alkyl (C ₁₅ ~C ₁₆₎ acetic acid, oleic acid, linoleic acid, ricinoleic acid, adipic acid, sebacic acid, benzoic acid, m- toluic acid, xylyl acid, p-t-butylbenzoic acid, phthalic acid, salicylic acid or These are mixed carboxylic acids.

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

These carboxylic acid metal salt compounds and alkylphenol metal salt compounds may be acidic salts or neutral salts, and may be basic salts or overbased salts. The amount of the metal salt compound is preferably 0.1 to 5 parts by weight, particularly preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. In the case of the compounding amount in this range, the releasability from the metal surface of the processing machine and the heat stabilizing effect are preferable. When the amount exceeds 5 parts by weight, not only the increased effect is not obtained but also a so-called bloom (bleed) in which an excessive amount of a metal salt compound or a decomposition product thereof and a plasticizer or other compounding agent oozes on the surface of a molded product. A phenomenon may occur.

The following stabilizer component (b), mono-alkylbenzene and di-alkylbenzene, is, for example, dodecyl.
Benzene, m-hexyl dodecyl benzene and p-
Hexyl dodecyl benzene.

The alkylbenzene compound may be a mixture thereof. In addition, the compounding amount is 1 to 10 parts by weight, especially 2 to 100 parts by weight of the vinyl chloride resin.
-5 parts by weight is preferred. Since this compound has a drawback of significantly deteriorating the transparency of the product, if it exceeds 10 parts by weight, the deteriorating transparency cannot be completely prevented even with the specific composition in the present invention.

The β-diketone compound of the stabilizer component (c) is, for example, acetylacetone, benzoylacetone, palmitoylbenzoylmethane, stearoylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoylmethane) And 4-chlorobenzoyl-benzoylmethane and the like.

The β-diketone compound may be a metal salt, and the metal constituting the metal salt is sodium, calcium, barium or zinc. These β
-The compounding amount of the diketone compound is 100 vinyl chloride resin.
0.001 to 1 part by weight, preferably 0.1 to 1 part by weight, per part by weight.
005 to 0.5 parts by weight. If the proportion of β-diketone is too large, zinc burning is promoted.

The amount of the stabilizer component (d), 2,5-dihydrothiophene-1,1-dioxide, is preferably 0.001 to 1 part by weight based on 100 parts by weight of the vinyl chloride resin. More preferably, it is 0.01 to 0.5 part by weight. 2,5-dihydrothiophene-1,1-dioxide is effective in preventing initial coloring, but in the present invention, further, in the present invention, extreme deterioration of transparency due to the addition of the component (b) important for preventing blocking. Is the only substance that can prevent However, if it is added in an excessively large amount, it causes a bloom phenomenon and promotes zinc burning.

According to a second aspect of the present invention, the components (a) to (d) of the first aspect of the present invention are blended, and the components (e) and (e) of the second aspect of the present invention are further added. (2) vinyl chloride which is prevented from blocking during storage, characterized by comprising at least one selected from the two kinds of inorganic salt compounds specified in (2) and containing five components in combination. It is a system resin composition.

(A) to (d) of the invention of claim 2
The component is as described in the first aspect of the present invention. With respect to (e), when these are added, an effect of preventing zinc burning can be obtained. The mixing ratio is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

In a third aspect of the present invention, the components (a) to (d) of the first aspect of the present invention are blended, and the component (f) according to the third aspect is sodium perchlorate, magnesium, or perchlorate. It is one to which one selected from complex compounds composed of any one of calcium and barium salts or any one of these metal salts and a polyhydric alcohol or a derivative thereof is added. In this case, the high-temperature heat storage property is remarkably improved, but when added in a large amount, the transparency is deteriorated and the phenomenon of seepage onto the surface of the product, so-called bleeding, is caused. Therefore, when used for general films and sheets, the compounding ratio is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the vinyl chloride resin. .

Claim 4 describes that the metal of the metal salt compound is most commonly barium-zinc, calcium-free without toxicity.
It is specified for the combination of zinc. Claim 5
Specifies an organic residue that binds to the metal of the metal salt compound. By using such a composition, the desired effect can be obtained even if the amount of the stabilizer used is reduced.
Further, claim 6 specifies the β-diketone compound as commonly used dibenzoylmethane, stearoylbenzoylmethane or a metal salt thereof. Claim 7 specifies the metal of the metal salt of perchlorate that forms the complex compound, and further specifies the polyhydric alcohol that forms a coordinate bond with the metal salt.

In the present invention, various stabilizing aids and other additives can be used in addition to the above-mentioned stabilizer components. For example, antioxidants such as organic phosphites, hindered phenol-based or sulfur-containing alkyl esters, epoxy compounds, polyhydric alcohols or esters thereof, ultraviolet absorbers, light stabilizers, inorganic or inorganic metal salt compounds, and antibacterial agents And additives such as an antifungal agent, which can be appropriately used according to the purpose.

The organic phosphite is a triaryl phosphite, a trialkyl phosphite, an alkyl aryl phosphite, a bisphenol-A-phosphite, a polyhydric alcohol phosphite, or an organic group of an ester residue. The above is represented by an acid phosphite substituted by a hydrogen atom, and the phosphite compound is, for example, triphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite, triisotridecyl phosphite, triisodecyl thiophyte. Phosphite, tribenzyl phosphite, trinonyl phenyl phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, diisodecyl pentaerythritol Sulfite, tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, trilauryl trithiophosphite, distearyl pentaerythritol diphosphite, tri-2,4-di-t-butylphenyl phosphite, 2,4-di-t-butylphenyl diisodecyl phosphite, tributoxyethyl phosphite, 4,4'-isopropylidene diphenylalkyl (C ₁₂ -C ₁₅ ) diphosphite, heptakis (dipropylene glycol) triphosphite and the like. .

Acid phosphites in which one or more of the organic residues in the above-mentioned phosphite are substituted by a hydrogen atom are also effective. For example, diphenyl acid phosphite, monophenyl acid phosphite, diisooctyl Acid phosphite, monoisooctyl acid phosphite, diisodecyl acid phosphite, monoisodecyl acid phosphite, ditridecyl acid phosphite, monotridecyl acid phosphite, dinonyl phenyl acid phosphite, monononyl phenyl acid phosphite , Dibenzyl acid phosphite, monobenzyl acid phosphite and the like.

Antioxidants include hindered phenols, such as alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenol esters, such as butylated hydroxytoluene, 4-hydroxymethyl. -2,6-di-t-butylphenol, 4,
4'-dihydroxy-2,2'-diphenylpropane,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-
3-methylphenol), tetrakis [methylene-3-
(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane. Examples of the sulfur-containing alkyl alkanoate include dilauryl thiopropionate and distearyl thiodipropionate.

The epoxy compound is an epoxidized unsaturated oil, an epoxidized unsaturated fatty acid ester, an epoxycyclohexane derivative or an epichlorohydrin derivative,
For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, butyl epoxystearate,
Alkyl esters such as isooctyl and 2-ethylhexyl, 3- (2-xenoxy) -1,2-epoxypropane, di-2-ethylhexyl epoxyhexahydrophthalate, epoxy polybutadiene, bisphenol-A
-Diglycidyl ether and the like.

Other stabilizers include polyhydric alcohols such as mono- and dipentaerythritol, mannitol and sorbitol, and ester compounds of the polyhydric alcohol with carboxylic acids, amino acids or rosins, such as pentaerythritol stearate. Pentaerythritol adipate, dipentaerythritol pyrrolidonecarboxylate, dipentaerythritol glutamate, wood rosin pentaerythritol, maleic anhydride-modified wood rosin pentaerythritol, and wood rosin glycerol ester. In addition, the nitrogen-containing compound β
Ester compounds of aminocrotonic acid with 1,3 or 1,4-butanediol, 1,2-dipropylene glycol, thiodiethylene glycol, lauryl alcohol, etc., and tris (hydroxyethyl) isocyanurate, tris (mercaptoethyl) isocyanate Isocyanurate compounds such as nurate.

When weather resistance is particularly required depending on the use, an ultraviolet absorber or a light stabilizer can be added.
First, those used as ultraviolet absorbers are represented by benzophenone type, salicylate type, benzotriazole type, hydroxybenzoate type, cyanoacrylate type and oxalic acid anilide type, for example, 2-hydroxy-4-n-octoxybenzophenone, p -T-butylphenyl salicylate, 2- (5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3-t
-Butyl-5-methyl-2-hydroxyphenyl) -5
-Chlorobenzotriazole, 2- (3,5-di-t-
Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, ethyl-2-cyano-3,3-diphenylacrylate, ethanediamide-N- (2-ethoxyphenyl) -N'-(2-ethylphenyl 1) (oxalic anilide) and the like.

Those used as light stabilizers are represented by hindered amines such as bis (2,2)
2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) succinate
-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl) imino].

The inorganic substance or the inorganic metal salt compound is described in claim 2
In addition to the component (e) (1) and (2), various compounds can be used in combination. For example, the metal is calcium, barium, magnesium, zinc, aluminum or tin, and oxides, hydroxides, borates, sulfates, phosphites, phosphates, basic carbonates, basics of these metals It is a phosphate. These compounds may be double salts, anhydrates or hydrates having water of crystallization, or may be in the form of a mixture or the like.
Representative of these compounds are, for example, calcium oxide, magnesium oxide, zinc oxide, aluminum oxide,
Tin oxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, tin hydroxide, aluminum borate, aluminum sulfate, aluminum sulfate 18 hydrate, aluminum sulfate-sodium 1
Dihydrate, zinc phosphite, zinc acid phosphite, calcium phosphate, calcium orthophosphate, magnesium phosphate, magnesium acid phosphate, zinc orthophosphate, zinc acid phosphate, hydroxyapatite, synthetic zeolite,
Calcium partially modified synthetic zeolite, ion activated synthetic zeolite, zinc partially modified synthetic hydrotalcite, sulfuric acid partially modified synthetic hydrotalcite, wollastonite,
Tobermorites, silica and silicon compounds.

In recent years, antimicrobial agents that have been spotlighted in various fields include metal ions (in particular, silver, copper, and zinc have strong antibacterial activity) that are adsorbed or ionized on a carrier used as an additive for a vinyl chloride resin. Generally, the carrier is retained by exchanging, but in order to further enhance the stability, a carrier in which metal ions are incorporated into the crystal lattice of the carrier by calcination may be used. The carrier here is represented by phosphates, silicates and the like, and these are, for example, zirconia phosphate, aluminum phosphate, hydroxyapatite, calcium phosphate, zeolite, clay mineral, silica gel, glass, activated carbon, carbon fiber, silica, Alumina, calcium silicate and the like. Many organic antibacterial and fungicides are also known, but they are organic iodine, benzimidazole, isothiazoline, nitrile, pyridine, triazine, N-haloalkylthio, pyrithione, and organic copper. These compounds are represented by, for example, 3-iodo-2-propylbutylcarbamate, 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolecarbamate,
2-n-octyl-4-isothiazolin-3-one,
2,4,5,6-tetrachloroisophthalonitrile,
2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, N, N ', N "-trishydroxyethylhexahydro-s-triazine, N- (fluorodichloromethylthio) phthalimide, N-trichloromethylthio Tetrahydrophthalimide, bis (pyridine-2-
Thiol-1-oxide) zinc salt, 2-pyridinethiol-1-oxide sodium salt, 2,2'-dithiobispyridine-1-oxide, 8-oxyquinoline copper, copper naphthenate, amino acid metal salt, 10,10 '-Oxybisphenoxaarsine.

Examples of the vinyl chloride resin in the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-propylene copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-urethane copolymer. ,
Chlorinated polyvinyl chloride, and polyvinyl chloride and the following elastomers, for example, polybutene, poly-3-methylbutene, polyurethane rubber, polyisoprene, polychloroprene, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, styrene-isoprene Copolymers, styrene-ethylene-butadiene copolymers, and blends of methacrylate-butadiene-styrene copolymers and acrylate-butadiene-styrene copolymers can be given.

The vinyl chloride resin composition of the present invention, in which blocking during storage is prevented, can be used in accordance with the degree of flexibility required for molded articles, for example, dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dioctyl adipate. By increasing or decreasing the amount of a general-purpose plasticizer such as diisooctyl adipate, diisononyl adipate, or trioctyl trimellitate, or a polyester plasticizer, it is possible to meet a wide range of applications. If necessary, a filler, a pigment, a cross-linking agent, a flame retardant and other processing aids can be appropriately used in combination.

[0044]

The present invention will be further described below with reference to examples and comparative examples. (Examples 1 to 9, Comparative Examples 1 to 13) [Formulation 1] below
Is a mixing roll having a surface temperature of 180 ° C. (electric induction heating type variable speed type test roll machine, 155φ × 380 mm, roll interval = 0.3 mm, front roll rotation speed = 22 rpm.
m. , Rear roll rotation speed = 20 r. p. m. ) And kneaded for 3 minutes to prepare a uniform original sheet having a thickness of 0.3 mm.

A strip-shaped test piece was prepared from the original sheet, and the test piece was placed in a gear oven aging tester heated to 180 ° C., and the time until black decomposition was measured to evaluate the thermal stability. Tables 1 to 3 (Examples) and Tables 4 to
5 (Comparative Example) (the same display method was used in each of the following tests). Note that if the measurement time is 80 minutes or longer, there is no problem in industrial practice.

Further, the original sheet was pressed (190 kg / cm ² ) at 190 ° C. for 2 minutes using a press molding machine to prepare a sheet having a thickness of 3 mm, and the transparency and coloring degree of this sheet were examined. Further, the same sheet was pressed for 15 minutes and 30 minutes to examine the change in the degree of coloring. These results are shown in Tables 1 to 3 (Examples) and Tables 4 and 5 (Comparative Examples).

The transparency by the press thermoforming is shown by the following numerical values. 10 is particularly good, 9 is good, 8 is particularly good, 7 is good, 6 is slightly good, 5 is normal, 4 is slightly bad, 3 is bad, 2 is particularly bad, and 1 is opaque.
The degree of coloring by press thermoforming was indicated by the following numerical values. 10 is non-colored, 9 is extremely yellow, 8 is slightly yellow, 7 is pale yellow, 6 is yellow, 5 is pale yellow brown, 4 is yellow brown, 3 is brown, 2 is black brown, and 1 is black. If the values of the transparency and the degree of coloring are 8 or more, there is no problem in industrial practice.

Next, the thermal stability is evaluated by a rolling test, which is a test method close to actual thermoforming processing (kneading for a long time at a high temperature in an atmosphere directly affected by oxygen) by a calender roll machine or the like. did. In this method, the surface temperature is adjusted to 18 using the mixing roll described above.
While keeping the temperature at 5 ° C, the following [Blend-1] was charged and kneaded. A piece of the sheet was sampled at regular intervals and the degree of coloring was examined. In addition, [Formulation-1] was colored and deteriorated with the lapse of time for a long period of kneading, the loss of peeling lubricity was lost, and the time required for the phenomenon of sticking to the roll surface to appear was shown. The results are shown in Tables 1 to 3 (Examples) and Tables 4 and 5 (Comparative Examples). The indication of the degree of coloring is the same as that of the press thermoforming described above, and a value of 8 or more is required for industrial implementation. In this rolling test, if kneading is possible for 40 minutes or more, there is no problem in industrial practice.

Next, printability (a phenomenon in which characters and patterns printed on the sheet surface are peeled off with the passage of time) was examined. This test was performed by the following method. First, 10 rectangular test pieces (3 cm × 10 cm) were prepared for each formulation example using the original sheet, and the test pieces were aged at 70 ° C. in a thermo-hygrostat set at 90% humidity for 30 days. During this time, each test piece was collected every three days, and a bar code (a stainless steel bar with a 1 mm wide and 0.5 mm deep groove was continuously engraved on its surface)
Then, the test ink (cyclohexanone-based vinyl ink diluted to 33% with ethyl acetate) was applied while spreading, and left for 2 hours to dry. Thereafter, a cellophane tape was adhered to the ink-coated surface, and the cellophane tape was pulled to determine the number of days when the ink printed on the test piece was peeled off. The number of days is shown in Tables 1 to 3 (Examples) and Tables 4 and 5 (Comparative Examples). In addition, if it does not peel off for 30 days by this test method, there will be no problem at the time of industrial implementation.

Next, the blocking property, which was the highest priority improvement task of the present invention, was examined. This test was performed by the following method. A stack of two original sheets is placed on each other, and a 5 kg weight is placed on the sheet so that the load is evenly applied. The sheets are aged at 70 ° C. in a thermo-hygrostat set at 90% humidity for 16 hours, and then peeled off with a strograph. G was measured, and the measured values are shown in Tables 1-3 and 4-5. If the measured value is less than 150, there is usually no problem in industrial practice, but if the measured value exceeds 100 under hot and humid conditions such as in summer, there is a risk of causing trouble.

Next, the following tests were conducted for high-temperature heat storage. First, a strip-shaped test piece was prepared from an original sheet, placed in a gear oven aging tester heated to 100 ° C. for a long time, and samples were collected at two points of 300 hours and 600 hours during the heat storage ( Coloring degree caused by prolonged heating)
And the results are shown in Tables 1-3 (Examples) and Tables 4-5.
(Comparative Example). The indication of the degree of coloring is the same as that of the press thermoforming described above, and even if the product is used in applications where the thermal conditions are severe in industrial practice, this indication value is 8 or more in 300 hours. If there are 7 or more in 600 hours, there is no problem. [Blend-1] Polyvinyl chloride (degree of polymerization 1100) 100 parts by weight Epoxidized soybean oil 1 {overbased barium oleate carbonate complex 0.5} barium oleate 0.5 {zinc oleate 0.1} p- Zinc t-butyl benzoate 0.2 {Diphenylisodecyl phosphite 0.6} Stabilizer components (b) to (f) Described in Tables 1 to 5 These are the components of the present invention described in Tables 1 to 5. (B) ~
The compound name or composition of (f) is as follows. [(B) component] Compound-A: dodecylbenzene / hexyldecylbenzene = 1/2 (weight ratio) [(c) component] Compound-B: dibenzoylmethane Compound-C: stearoylbenzoylmethane [(d) component] Compound-D: 2,5-dihydrothiophen-1,1-dioxide [component (e)] Compound-E: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5
H ₂ O [(f) component] Compound-F: Complex salt of sodium perchlorate-diethylene glycol monomethyl ether (45:55 weight ratio) Compound-G: Magnesium perchlorate-diethylene glycol monobutyl ether (42:58 weight ratio) complex salt

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

Industrial Applicability The vinyl chloride resin composition of the present invention, in which blocking during storage is prevented, does not deteriorate heat stability, transparency and printability as shown in Examples, and has a high-temperature heat storage property. Since the anti-blocking, which is the technical concept of the present invention, is achieved while improving, an excellent sundries film / sheet can be obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-287147 (JP, A) JP-A-4-183735 (JP, A) JP-A 4-122757 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 27/06 C08K 5/03 C08K 5/07-5/08 C08K 5/098 C08K 5/41-5/42

Claims (7)

(57) [Claims] (1) 100 parts by weight of a vinyl chloride resin, (a)
Metal salt compound of carboxylic acid or alkylphenol 0.
1 to 5 parts by weight and (b) at least one selected from mono-alkylbenzene and di-alkylbenzene
10 and weight, (c) any of the β- diketone compound of Jiaroirumetan or alkanoyl aroyl methane and at least one of these metal salts 0.001
Parts by weight , and (d) 2,5-dihydrothiophene-1,1
-A vinyl chloride resin composition in which blocking during storage is prevented, comprising 0.001 to 1 part by weight of a dioxide. 2. 100 parts by weight of a vinyl chloride resin, (a)
Metal salt compound of carboxylic acid or alkylphenol 0.
1 to 5 parts by weight and (b) at least one selected from mono-alkylbenzene and di-alkylbenzene
And 10 parts by weight, either β- diketone compound of (c) Jiaroirumetan or alkanoyl aroyl methane and at least one 0.001 in these metal salts
1 part by weight , and (d) 2,5-dihydrothiophene-1,
0.001 to 1 part by weight of 1-dioxide and (e) Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (1) 3 ≦ X ≦ 0.33, m is 0 <m
≦ 0.7. Magnesium represented by)
Aluminum composite hydroxide salt and Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) _{1 -x / 2} (ClO ₄ ) _x · mH ₂ O (2) where x is 0.5 ≦ x ≦ 2, and m represents 0 <m ≦ 6.) At least one selected from two inorganic salt compounds of magnesium-aluminum hydroxide perchloric carbonate hydrate A vinyl chloride resin composition wherein blocking during storage is prevented, comprising 0.01 to 3 parts by weight in combination. 3. 100 parts by weight of a vinyl chloride resin, (a)
Metal salt compound of carboxylic acid or alkylphenol 0.
1 to 5 parts by weight and (b) at least one selected from mono-alkylbenzene and di-alkylbenzene
And 10 parts by weight, either β- diketone compound of (c) Jiaroirumetan or alkanoyl aroyl methane and at least one 0.001 in these metal salts
1 part by weight , and (d) 2,5-dihydrothiophene-1,
0.001 to 1 part by weight of 1-dioxide and (f) any one of sodium, magnesium, calcium and barium salts of perchloric acid, or any one of these metal salts and a polyhydric alcohol Or blocking during storage characterized by comprising a combination of 0.01 to 0.5 parts by weight of a complex compound selected from derivatives thereof. Vinyl chloride resin composition. 4. The blocking during storage according to claim 1, wherein the metal of the metal salt compound of the carboxylic acid or the alkylphenol is any combination of barium-zinc or calcium-zinc. A vinyl chloride-based resin composition in which odor is prevented. 5. The method according to claim 1, wherein the metal salt compound is a combination of any one of an overbased carboxylate carbonate complex or an overbased alkylphenate carbonate complex of barium or calcium and zinc carboxylate. The vinyl chloride resin composition according to any one of the above, wherein the blocking during storage is prevented. 6. The β-diketone compound of dialloylmethane or alkanoylaroylmethane and a metal salt thereof are either dibenzoylmethane or stearoylbenzoylmethane or a metal salt thereof.
4. The vinyl chloride resin composition according to any one of items 1 to 3, wherein blocking during storage is prevented. 7. A complex compound, either as sodium perchlorate or magnesium perchlorate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, claim 1 is a complex compound with any kind of triethylene glycol monomethyl ether The vinyl chloride resin composition according to any one of the above, wherein blocking during storage is prevented.