JP2000344985A - Stabilized vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, being thermally stable, and improving weather resistance without damaging the transparency of its molded article by incorporating a specific metal salt compound, a β-diketone compound, etc., into a vinyl chloride-based resin. SOLUTION: This stabilized vinyl chloride-based resin composition is obtained by incorporating (B) 0.1-5 pt.wt. at least 1 kind of a metal salt compound of a carboxylic acid or an alkylphenol, (C) 0.0005-3 pt.wt. at least 1 kind of a β-diketone compound, (D) 0.0005-2 pt.wt. at least 1 kind of a heat-melted substance obtained by adding phosphoric acid or phosphorous acid to a compound of formula I [R is an alkyl or the like; (n) is 4-55; (x) is 1, 2] and heating, and (E) 0.001-3 pt.wt. at least 1 kind of a compound of formula II or III (M is Ca or the like) into as a combination to (A) 100 pts.wt. vinyl chloride-based resin. The metal in the component B is preferably any of the combination of barium-zinc, calcium-zinc or calcium-magnesium-zinc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized vinyl chloride resin composition, and more particularly to a stabilized vinyl chloride resin composition containing a low-toxic or non-toxic metal salt compound in combination with a heat stabilizing aid and a weather resistance improver. And a stabilized vinyl chloride resin composition.

[0002]

2. Description of the Related Art A vinyl chloride resin composition has various excellent properties. However, when it is subjected to thermoforming, it decomposes with dehydrochlorination, thereby coloring a molded article and deteriorating its commercial value. is there. For this reason, conventionally, it has been widely performed to add various stabilizers to stabilize the heat.

[0003] Components of such stabilizers include, for example, Ba-Z
It is obtained by combining an n-based or Ca-Zn-based metal soap with an organic phosphite compound, a hindered phenol-based antioxidant or an epoxy compound.

The method of heat stabilization by adding the above-mentioned stabilizer component has no problem in terms of toxicity, but it is still insufficient in prevention of coloring due to deterioration during thermoforming, and further improvement in performance is required. Was required. For this reason, conventionally, there have been proposed many methods for further improving the performance by further adding various stabilizing aids to the above-mentioned stabilizer.

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. , Tokiko Sho 61-44899
For example, a method using a ketoacetonitrile compound was proposed, and Japanese Patent Publication Nos. 1-58213 and 1-58214 proposed a method using cyclopentanone and cyclohexanone compounds.

[0006] When the above methods are used, the performance of preventing coloring due to deterioration during thermoforming processing is greatly improved. However, these methods prevent deterioration due to ultraviolet rays or acid rain when a processed product is exposed outdoors. It did not improve the so-called weather resistance.

In order to improve the weather resistance, the present applicant has the following general formula (2) or (3):

[0008]

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[0009]

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Wherein R represents alkyl, aryl, alkylaryl, arylalkyl, alkenyl or cycloalkyl, and M represents metal calcium, barium, magnesium or zinc. This object was achieved by adding at least one metal salt. There has been an example in which the weather resistance is improved by adding a metal salt of these organic phosphates. However, simply adding this compound to the conventional compounding recipe can certainly improve the weather resistance, but has the drawback of causing initial coloring during thermal processing and deteriorating the transparency of the product. .

[0011]

SUMMARY OF THE INVENTION The present invention relates to a method of adding a low-toxic or non-toxic metal salt compound to a vinyl chloride resin in combination with a novel heat stabilizing aid and a weather resistance improver. Thermal stability of the vinyl chloride resin composition,
In particular, it is intended to prevent initial coloring and black decomposition (carbonization) and to improve weather resistance without impairing the transparency of a molded article.

[0012]

According to the present invention, at least one kind of (a) a metal salt compound of a carboxylic acid or an alkyl phenol is added to 100 parts by weight of a vinyl chloride resin.
Parts by weight, (b) 0.0005 to 3 parts by weight of at least one kind of β-diketone compound, and (c) the following general formula (1)

[0013]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group;
~ 55, x represents the number of 1 or 2. ), At least one of 0.0005 to 2 parts by weight of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphoric acid ester and heating; General formula (2) or (3)

[0015]

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[0016]

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(Wherein R represents alkyl, aryl, alkylaryl, arylalkyl, alkenyl or cycloalkyl, and M represents metal calcium, barium, magnesium or zinc). A stabilized vinyl chloride resin composition (Claim 1) comprising a combination of 0.001 to 3 parts by weight of at least one metal salt of an ester or a metal salt of an organic phosphoric diester (claim 1). 100 parts by weight,
(A) 0.1 to 5 parts by weight of at least one metal salt compound of a carboxylic acid or an alkylphenol, and (b) β-
0.0005 to 3 parts by weight of at least one diketone compound, and (c) the following general formula (1)

[0018]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group, and n represents 4
~ 55, x represents the number of 1 or 2. ) At least one kind of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphate represented by the formula (1) and heating, and (d) the following: General formula (2) or (3)

[0020]

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[0021]

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Wherein R represents alkyl, aryl, alkylaryl, arylalkyl, alkenyl or cycloalkyl, and M represents metal calcium, barium, magnesium or zinc. 0.001 to 3 parts by weight of at least one kind of a metal salt of an ester or a metal salt of an organic phosphoric diester;
(E) the following general formula _{(4) Mg x Zn y Al} 2 · (OH) 2x + 2y + 4 · (CO 3) in _{1-z / 2 (ClO 4} ) z · mH 2 O (4) ( wherein, x, y And z represent a number that satisfies the condition represented by the following formula, and m represents 0 or an arbitrary number: 0 <x <
10, 0 ≦ y <10, 2 ≦ x + y <20, 0 ≦ z <2)
A stabilized vinyl chloride resin composition (Claim 2) containing at least one compound represented by the formula (1) in combination with 0.001 to 10 parts by weight, and a metal of a metal salt compound of a carboxylic acid or an alkylphenol. Is a combination of barium-zinc, calcium-zinc or calcium-magnesium-zinc, the stabilized vinyl chloride resin composition according to claim 1 or 2, and a metal salt compound. Is a combination of a barium or calcium overbased carboxylate carbonate complex or an overbased alkylphenolate carbonate complex with zinc carboxylate.
Or the stabilized vinyl chloride resin composition according to claim 2 or claim 4, wherein the β-diketone compound is any one of dibenzoylmethane, palmitoylbenzoylmethane and stearoylbenzoylmethane.
The stabilized vinyl chloride resin composition according to claim 5 (claim 5) and the general formula (1)

[0023]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group;
~ 55, x represents the number of 1 or 2. The polyoxyethylene organic group ether phosphate represented by the formula (1) is either tridecyl polyoxyethylene (4 to 10) phosphoric acid or nonylphenyl polyoxyethylene (5 to 55) phosphoric acid. The stabilized vinyl chloride resin composition according to claim 2 (claim 6). Hereinafter, these inventions are further described.

The invention of claim 1 is to provide at least one kind of metal salt compound of carboxylic acid or alkylphenol.
To 5 parts by weight, 0.0005 to 3 parts by weight of at least one kind of β-diketone compound, and the following general formula (1)

[0026]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group;
~ 55, x represents the number of 1 or 2. ), At least one kind of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphate represented by the formula (1), and 0.0005 to 2 parts by weight of the above general formula ( 2) or (3)

[0028]

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[0029]

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Wherein R represents alkyl, aryl, alkylaryl, arylalkyl, alkenyl or cycloalkyl, and M represents metal calcium, barium, magnesium or zinc. A stabilized vinyl chloride resin composition comprising a combination of four components of at least one metal salt of an ester or a metal salt of an organic phosphoric acid diester in an amount of 0.001 to 3 parts by weight.

The metal of the metal salt compound used in the present invention is
It is sodium, potassium, magnesium, calcium, barium or zinc, and is used in two or more of these. In this case, the combination of metals is preferably barium-zinc or calcium-zinc. The organic residue bonded to the metal is a carboxylic acid or an alkylphenol.

The carboxylic acid may be 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 or alkoxy acid having 2 to 10 carbon atoms, An aminocarboxylic acid having 2 to 9 carbon atoms, 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, trialkylacetic acid having 15 to 16 carbon atoms, Oleic acid, linoleic acid, ricinoleic acid, adipic acid, sebacic acid, benzoic acid, toluic acid, xylic acid, pt-butylbenzoic acid, phthalic acid, phthalic acid monoester, salicylic acid, aminoacetic acid, N-methylaminoacetic acid 2-aminopropionic acid, 3-aminopropionic acid, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminovaleric acid, 2-aminoisovaleric acid, 2-amino-2-methylbutyric acid, 2 -Aminohexanoic acid, 2-amino-3-hydroxypropionic acid, aminosuccinic acid,
2-amino-3-carbamoylpropionic acid, 2-aminoglutaric acid, N-acetylaminoacetic acid, N-glycylaminoacetic acid, N-benzoylaminoacetic acid, or a mixed carboxylic acid thereof.

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 0.1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.3 to 3 parts by weight. If the amount is less than 0.1 part by weight, the thermal stability is not sufficient. If the amount exceeds 5 parts by weight, plateout, bloom or bleeding occurs, and the transparency is also deteriorated.

The β-diketone compound of the stabilizer component (b) of claim 1 is, for example, dehydroacetic acid, cyclohexane-
1,3-dione, 2-acetylcyclopentanone, 2-
Benzoylcyclopentanone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, acetylstearoylmethane, acetylacetone, benzoylacetone, palmitoylbenzoylmethane, stearoylbenzoylmethane, dibenzoylmethane, tribenzoylmethane, 4-methoxybenzoyl-benzoylmethane,
Bis (4-methoxybenzoylmethane), 4-chlorobenzoyl-benzoylmethane, benzoyltrifluoroacetone, thenoyltrifluoroacetone, palmitoyltetralone, stearoyltetralone, and benzoyltetralone.

The β-diketone compound may be a metal complex salt, and the metal constituting the complex salt is sodium,
Calcium, barium or zinc. These β-
The addition amount of the diketone compound is 0.0005 to 3 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
005 to 1 part by weight. If the amount is less than 0.0005 parts by weight, the anti-coloring property is not sufficient, and if it exceeds 3 parts by weight, black decomposition (carbonization) is promoted.

The stabilizer component (c) according to the first aspect is obtained by adding phosphoric acid or phosphorous acid to the following general formula (1):

[0038]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group;
~ 55, x represents the number of 1 or 2. ), And dissolved by heating with addition of a polyoxyethylene organic group ether phosphate. Polyoxyethylene organic ether phosphate ethers originally have poor reactivity with metal salts, but they are converted to highly reactive compounds by heating and dissolving them with phosphoric acid or phosphorous acid. When added and subjected to thermoforming, it reacts with the zinc salt mixed in the vinyl chloride resin composition to form a complex compound, which prevents plate-out and improves transparency and thermal stability. Work in a typical way. The component (c) is used in an amount of 0.000 parts per 100 parts by weight of the vinyl chloride resin.
5 to 2 parts by weight, preferably 0.001 to 1 part by weight is added. If the added amount is less than 0.0005 parts by weight, transparency, heat stability, initial coloring prevention properties and plate-out prevention properties are not sufficient, and if it exceeds 2 parts by weight, the color of the latter stage is deteriorated,
It causes adhesion to the molding machine.

The stabilizer component (d) of the first aspect is represented by the following general formula (2) or (3):

[0041]

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[0042]

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Wherein R represents alkyl, aryl, alkylaryl, arylalkyl, alkenyl or cycloalkyl, and M represents metal calcium, barium, magnesium or zinc. It is a metal salt of an ester or a metal salt of an organic phosphoric acid diester. These include, for example, calcium, barium, magnesium or zinc salts of mono (2-ethylhexyl) acid phosphate, calcium, barium, magnesium or zinc salts of di (2-ethylhexyl) acid phosphate, calcium, barium, magnesium monolauryl acid phosphate Or calcium zinc salt, dilauryl acid phosphate,
Barium, magnesium or zinc salt, calcium monooleyl acid phosphate, barium, magnesium or zinc salt, calcium, barium, magnesium or zinc salt of dioleyl acid phosphate, calcium, barium, magnesium or zinc salt of monostearyl acid phosphate, di Calcium, barium, magnesium or zinc salts of stearyl acid phosphate, calcium, barium, magnesium or zinc salts of monotetracosyl acid phosphate,
Calcium, barium, magnesium or zinc salts of ditetracosyl acid phosphate, calcium, barium, magnesium or zinc salts of mono (2,4-di-t-butylphenyl) acid phosphate, di (2,
And calcium, barium, magnesium or zinc salts of 4-di-t-butylphenyl) acid phosphate. Among them, particularly preferred are a magnesium salt of mono (2-ethylhexyl) acid phosphate, a magnesium salt of di (2-ethylhexyl) acid phosphate, a zinc salt of monooleyl acid phosphate, a zinc salt of dioleyl acid phosphate, These are zinc salts of stearyl acid phosphate and zinc salts of distearyl acid phosphate. The amount of these compounds is 0.001 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.001 part by weight, it is not sufficient to improve the weather resistance. If the amount exceeds 3 parts by weight, initial coloring and pre-out occur during thermal processing, resulting in deterioration of the transparency of the product.

The invention according to claim 2 is characterized in that the vinyl chloride resin
(A) the same metal salt compound as the invention of claim 1 described above,
(B) β-diketone compound, (c) polyoxyethylene
Organic ether phosphate, phosphoric acid or phosphorous acid
(D) metal of organophosphate monoester
Salt or a metal salt of an organic phosphoric diester.
Furthermore, in order to improve thermal stability, a synthetic high
Add Drotarsite compound and combine 5 ingredients
Stabilized vinyl chloride-based resin composition containing
It is. The stabilizers (a) to (d) of the invention according to claim 2
Is as described above. Combination of component (e)
The hydrotalcite compound is a compound represented by the general formula (4)_xZn_yAl₂・ (OH)_{2x + 2y + 4}・ (CO₃)_{1-z / 2}(ClO₄)_z・ MH₂O (4) wherein R is alkyl, aryl, alkylaryl,
Arylalkyl, alkenyl, cycloalkyl, al
Represents a kylene or an acyl group, and n is 4-55, x is
Represents a number of 1 or 2. ), But this
As the properties of these compounds, the onset temperature of decrystallization water is about 23.
So-called BET, which is an adsorption isotherm of 0 ° C. and multilayer adsorption
Specific surface area is 20m^Two/ G or less, and the particle size distribution is 1 μm
It is preferable that less than 92%. Typical compound
The object is, for example, Mg₄Al₂(OH) ₁₂CO₃・ 3H₂
O [hereinafter referred to as (HT-1). ], Mg4Mg₄Al₂
(OH)₁₂CO₃・ 0-2H₂O [hereinafter (HT-2)
That. ], Mg₃ZnAl ₂(OH)₁₂CO₃・ 3
H₂O [hereinafter referred to as (HT-3). ], Mg₃ZnAl
₂(OH)₁₂CO₃・ 0-1H₂O [hereinafter (HT-
4). ], Mg₄Al₂(OH)₁₂(CO₃)
_{1-x / 2}(ClO₄)_x・ 0-6H₂O [wherein (x
= 0.5 to 2.0). [Hereinafter referred to as (HT-5)
U. ], Mg₃ZnAl₂(OH)₁₂(CO₃)
_{1-x / 2}(ClO₄)_x・ 0-6H₂O [wherein (x
= 0.5 to 2.0). ] [Hereafter referred to as (HT-6)
U. ]. Conversion of these synthetic hydrotalcites
The compound is used in an amount of 0.0
01 to 10 parts by weight, preferably 0.01 to 5 parts by weight
Is done. If the amount added is less than 0.001 part by weight, black during processing
Prevention of color separation (carbonization) and long-term heat resistance of the resulting molded product
(Heat storage) property is not enough, and if it exceeds 10 parts by weight, coloring
The transparency becomes extremely bad.

Claim 3 specifies the metal of the metal salt compound as any combination of barium-zinc, calcium-zinc or calcium-magnesium-zinc. Claim 4 specifies an organic residue that binds to the metal of the metal salt compound. Claim 5 specifies a β-diketone compound. Further, claim 6
Is the following general formula (1)

[0046]

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Wherein R represents an alkyl, aryl, alkylaryl, arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group, and n represents 4
~ 55, x represents the number of 1 or 2. ) Is specified.

In the present invention, various stabilizing aids and other additives can be used in addition to the above-mentioned stabilizer components. Antioxidants such as organic phosphites, hindered phenol-based or sulfur-containing alkyl esters, epoxy compounds, perchlorates, polyhydric alcohols or esters thereof, ultraviolet absorbers, light stabilizers, inorganic oxides or inorganics It is an additive such as a metal salt compound, a surfactant and a lubricant, and these can be appropriately used according to the purpose.

Organic phosphites include trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, bisphenol-A-phosphites, polyhydric alcohol phosphites, salicyl phosphites, and organic groups of ester residues. One or more of which are represented by an acid phosphite substituted by a hydrogen atom, such as triphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite, triisotridecyl phosphite, triisodecyl Thiophosphite, tribenzyl phosphite, trisnonylphenyl phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite,
Diisodecyl pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite,
Poly (dipropylene glycol) phenyl phosphite, trilauryl trithio phosphite, distearyl pentaerythritol diphosphite, tri-2,4-
Di-t-butylphenyl phosphite, 2,4-di-t
- butylphenyl diisodecyl phosphite, tributoxyethyl phosphite, 4,4'-isopropylidene diphenyl alkyl _(C l2 _{-C 15)} diphosphite, 4,4'-isopropylidene dicyclohexyl alkyl _(C l2 _{-C 15)} diphosphite, to Ptakis (dipropylene glycol) triphosphite, salicyloctyl phosphite and the like.

Acid phosphites in which one or more of the organic residues in the above phosphite are substituted by hydrogen atoms are also effective, for example, diphenyl acid phosphite, monophenyl acid phosphite, diisooctyl. Acid phosphite, monoisooctyl acid phosphite, ditridecyl acid phosphite, dibenzyl acid phosphite, dinonylphenyl 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, such as epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, and epoxidized linseed oil. Safflower oil, epoxidized linseed oil fatty acid butyl, epoxy butyl stearate, alkyl esters such as isooctyl, 2-ethylhexyl, 3- (xenoxy) -1,2-epoxypropane, di-2-ethylhexyl epoxyhexahydrophthalate , Epoxy polybutadiene, bisphenol-A
-Diglycidyl ether and the like.

The perchlorate is a sodium salt of perchloric acid,
Magnesium salt, calcium salt, barium salt or alkyl ammonium salt. Further, a complex compound composed of these perchlorates and a polyhydric alcohol or a derivative thereof may be used. These compounds are useful as long-term heat (heat storage) aids.

Other stabilizing aids are polyhydric alcohols such as mono- and dipentaerythritol, mannitol, sorbitol and trehalose, and ester compounds of the polyhydric alcohol with carboxylic acids, amino acids or rosins, such as stearic acid Pentaerythritol, pentaerythritol adipate, dipentaerythritol adipate, dipentaerythritol pyrrolidonecarboxylate, dipentaerythritol glutamate, wood rosin pentaerythritol, maleic anhydride-modified wood rosin pentaerythritol, and wood rosin glycerol ester. In addition, these ester compounds may be partial ester compounds. Further, an ester compound of β-aminocrotonic acid, which is a nitrogen-containing compound, with 1,3 or 1,4-butanediol, 1,2-dipropylene glycol, thiodiethylene glycol lauryl alcohol, and the like, and tris (2-hydroxyethyl) Isocyanurate compounds such as isocyanurate. These improve the thermal stability during processing and the long-term heat resistance (heat storage) of the molded product.

The thing used as an ultraviolet absorber may be a known one represented by a benzotriazole type, a hindered amine type or the like, and the known light stabilizer is a known hindered amine type such as a piperidine compound. May be something. These are added when it is desired to further prevent deterioration and discoloration or chalking (chalking) of the molded article due to sunlight, rainwater and the like.

The inorganic oxide or inorganic metal salt compound may be, for example, a metal whose sodium, potassium, magnesium, calcium, barium, zinc, aluminum or tin is used, and an oxide, hydroxide or silicate of these metals. , Borate, sulfate, phosphite, phosphate, basic carbonate, basic phosphate, stannate, hydroxystannate. 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 examples of these compounds include, for example, calcium oxide, magnesium oxide, zinc oxide, silicon oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, sodium silicate, and silica. Calcium silicate, zinc silicate, aluminum silicate, potassium-aluminum silicate (mica), sodium borate, potassium borate, aluminum borate, aluminum sulfate, aluminum sulfate 18 hydrate, aluminum sulfate-potassium 12 hydrate, aluminum sulfate -Sodium dodecahydrate, sodium phosphate, sodium pyrophosphate, magnesium phosphate, calcium phosphate, calcium orthophosphate, zinc orthophosphate, zinc stannate, zinc hydroxystannate, sodium, calcium, magnesium A zeolite substituted with arm or zinc, wollastonite, tobermorite such and the like. These additions, besides improving thermal stability and weather resistance,
It is suitable for preventing plate-out, bloom and bleed, imparting printability and flame retardancy, and the like.

In addition to the above stabilizing aids, the processability is further improved, and the antifogging property, antistatic property, printability,
For the purpose of imparting antibacterial properties and the like, a lubricant, a gelling accelerator, a boundary activator, an antibacterial and antifungal agent and the like can be appropriately used.

The stabilized vinyl chloride resin composition of the present invention can be used in a wide range from hard to soft by increasing or decreasing the amount of a plasticizer, for example, adipate or phthalate, depending on the use of the molded article. Moldings can be obtained. If necessary, a filler, a pigment, a rust inhibitor, a cross-linking agent, a matting agent, a foaming agent, and other processing aids can be appropriately used in combination.

The vinyl chloride resin in the present invention is not particularly limited to a polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.
Chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride- Vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-maleic acid ester copolymer, Vinyl chloride
Methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer , Vinyl chloride-based resins such as vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, and their mutual blended products or other chlorine-free synthetic resins,
For example, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester, etc.
Examples include block copolymers and graft copolymers.

[0061]

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.

(Synthesis Examples 1 to 4)
Although the component (c) of the present invention is synthesized, it is needless to say that the present invention is not limited to these examples.

Synthesis Example 1 Tridecyl polyoxyethylene (4 to 10) phosphoric acid 80
g and 20 g of phosphoric acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid.

Synthesis Example 2 Tridecyl polyoxyethylene (4-10) phosphoric acid 80
g and 20 g of phosphorous acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid.

Synthesis Example 3 80 g of nonylphenylpolyoxyethylene (5-55) phosphoric acid and 20 g of phosphoric acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid.

Synthesis Example 4 80 g of nonylphenylpolyoxyethylene (5-55) phosphoric acid and 20 g of phosphorous acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid.

(Examples 1 to 3, Comparative Examples 1 to 4) A stabilized vinyl chloride resin composition obtained by combining and adding the components (a) to (e) used in the present invention was obtained. The behavior of this product, such as thermal stability, plate-out prevention, transparency, and peeling lubricity, was examined. The composition and test method are as follows.

Formulation Polyvinyl chloride (degree of polymerization: 1300) 100 parts by weight Diisononyl adipate 40 エ ポ キ シ Epoxidized soybean oil 10 イ ソ Isostearic acid 0.3 ポ リ Polyglycerin oleate 1.0 〃 Sorbitan monolaurate 2.0 安 Benzo Calcium acid salt 0.1 亜 鉛 Zinc oleate 0.1 亜 鉛 Zinc ricinoleate 0.1 〃 * Components (a) to (d) Described in Table 1 〃 * Components of the above (a) to (d) are as follows The compound shown in FIG. (A-1): overbased oleate carbonate complex of calcium (b-1): stearoylbenzoylmethane (c-1): component of Synthesis Example 1 (c-2): component of Synthesis Example 2 (d-1) : Zinc salt of distearyl acid phosphate (e-1): HT-2 (trade name: Alkamizer-2 manufactured by Kyowa Chemical Industry Co., Ltd.)

Test 1 The above composition was kneaded with a kneading roll heated to 185 ° C. for 5 minutes to form a uniform sheet having a thickness of 0.5 mm, and a part of this sheet was collected. This was used as the original sheet. The sheet on the roll surface was continuously kneaded for another 15 minutes. In this rolling test, the coloring of the sheet due to thermal aging, plate-out (corresponding to eye rejection during extrusion molding), lubricity, and the like were examined. The results are shown in Table 1.

The determination of coloring was shown in the table by the following numerical values. 5 is uncolored, 4 is slightly yellow, 3 is yellow, 2 is tan,
1 is reddish brown. Next, the plate out judgment was indicated by the following numerical values. 5 is not dirty at all, 4 is slightly dirty, 3 is slightly dirty, 2 is dirty, and 1 is severely dirty. The determination of lubricity was indicated by the following numerical values. 5 is very good, 4 is good, 3 is slightly bad, 2 is bad, and 1 is very bad. In addition, if these numerical values are 4 or more, there is no problem in industrial implementation.

Test 2 Using the above-mentioned original sheet at 185 ° C. in a press molding machine for 5 minutes
The plate was pressed for 3 minutes (150 kg / cm ² ) to produce a plate having a thickness of 3 mm. The transparency of this plate was examined. The results are shown in Table 1. The judgment of transparency was indicated by the following numerical values. 5 is very good, 4 is good, 3 is slightly bad, 2 is bad, and 1 is very bad. In addition, if this numerical value is 4 or more, there is no problem in industrial implementation.

Test 3 Further, a strip-shaped test piece was prepared from the original sheet, and
The film was placed in a gear oven aging tester heated to 90 ° C., and the time until coloring and black decomposition due to thermal deterioration were examined. The results are shown in Table 1. The determination of coloring was shown in the table by the following numerical values. 5 is uncolored, 4 is slightly yellow, 3 is yellow, 2 is yellow-brown, and 1 is red-brown. If this value is 4 or more after 30 minutes, there is no problem in industrial practice. In addition, the time until black separation was expressed in minutes. In addition, if this numerical value is 80 minutes or more, there is no problem in industrial practice.

[0073]

[Table 1]

As is clear from Table 1, the comparative example
According to the present invention, excellent results are obtained in all respects of coloring, plate-out (in the case of extrusion molding, it is equivalent to eye filing deposited on a die or a screw portion), lubricity, transparency, and black decomposition time. Is shown.

(Examples 4 and 6, Comparative Examples 5 and 8) The stabilized vinyl chloride resin composition for hard extruded gutters obtained by combining and adding the components (a) to (e) used in the present invention was prepared. Obtained. About this, thermal stability, plate-out prevention,
Behavior such as weather resistance (prevention of so-called chalking) was examined. The composition, test method and test conditions were as follows, and the results are shown in Table 2.

Formulation Polyvinyl chloride (degree of polymerization: 1000) 100 parts by weight Light calcium carbonate 7.0 {Bengara 0.6} Carbon black 0.01 {Polyhydric alcohol fatty acid ester (lubricant) 1.0} Zinc stearate 6 マ グ ネ シ ウ ム magnesium oxide 0.3 〃 silicon oxide 0.2 合成 synthetic zeolite 3.0 部分 partial ester of dipentaerythritol and adipic acid 0.2 ２ ， 2,2′-methylenebis (4-methyl-6-t-butyl) Phenol 0.1 * (a) to (e) component described in Table 2 * Each component of the above (a) to (e) is a compound shown below: (a-2): Basic calcium stearate (b- 2): dibenzoylmethane (c-3): Component of Synthesis Example 3 (c-4): Component of Synthesis Example 4 (d-2): Monostearyl acid phosphate Lead salt (e-2): HT-5 (manufactured by Kyowa Chemical Industry Co., Ltd. under the trade name: Arukamaiza -5)

Test 4 The above composition was mixed with a mixing roll having a surface temperature of 200 ° C. (electric induction heating type variable speed test roll machine, 15
5φ × 380 mm (roll interval = 0.2 mm, front roll rotation speed = 22 rpm, rear roll rotation speed = 20 rpm)
m. ) And kneading for 10 minutes, during which the plate was judged to be out by observing the degree to which the surface of the roll was stained with deposits. The results are shown in Table 2. The determination of the plate-out is shown in the table by the following numerical values. 5 is not dirty at all, 4 is slightly dirty, 3 is slightly dirty, 2 is dirty, and 1 is severely dirty. If this value is 4 or more, there is no problem in industrial implementation.

Test 5 Using the same mixing roll as above, a surface temperature of 200 ° C.
For 5 minutes to prepare a uniform original sheet having a thickness of 0.3 mm. A strip-shaped test piece was prepared from this original sheet, and the strip was placed in a gear oven aging tester heated to 200 ° C., and the time required for thermal degradation was measured to evaluate the thermal stability during high-temperature processing. The results are shown in Table 2. Incidentally, if the measurement time is 70 minutes or more, there is no problem in industrial practice.

Test 6 Further, the original sheet was used at 195.degree.
Min (200 kg / cm ² ) to prepare a plate (plate), and apply the plate to an accelerated weathering tester (I-Super UV tester W-13, manufactured by Dainippon Plastics Co., Ltd .; 50 mW / cm ² ,
Black panel temperature = 45 ° C, cycle mode = 2 (L
→ D), shower mode = 3 (showing 10 seconds before and after D), L = 45 ° C. × 70%, D = 30 ° C. × 90% or more,
One cycle is 8 hrs and L / D = 4 hr / 4 hr. ), The time of occurrence of chalking was measured, and the results are shown in Table 2.
It was shown to. In addition, 160 hours of this test correspond to 8 months when actually exposed outdoors. In markets such as outdoor building materials, the measurement time is required to be 600 hours or more. Incidentally, the current situation is 160 to 240 hours.

[0080]

[Table 2]

As is clear from Table 2, for the comparative example,
According to the present invention, excellent results are shown in all respects such as chalking, plate-out, and thermal degradation decomposition time during processing. In particular, it turns out that chalking is excellent.

[0082]

As shown in the examples, the stabilized vinyl chloride resin composition of the present invention has an excellent plate-out prevention effect without impairing the thermal stability required during thermoforming. Therefore, the workability is remarkably improved, and the obtained molded product can be prevented from deteriorating in transparency and can be prevented from causing chalking when used outdoors, and the commercial value can be significantly increased.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/52 C08K 5/52 (72) Inventor Junichi Ishii 521 No.56, Miyazawa-cho, Akishima-shi, Akishima-shi, Tokyo Victoria K305 F term (reference) 4J002 BD041 BD051 BD061 BD071 BD081 BD181 BN121 BP031 CH052 DE289 EE047 EG026 EG027 EG036 EG037 EG046 EG047 EJ076 EJ077 EW048 EW049 FD030 FD032 FD050 FD070

Claims (6)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 0.1 to 5 parts by weight of at least one metal salt compound of a carboxylic acid or an alkylphenol, and (b) β-
0.0005 to 3 parts by weight of at least one diketone compound, and (c) the following general formula (1): (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), At least one of 0.0005 to 2 parts by weight of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphoric acid ester and heating; General formula (2)
Or (3) Embedded image (Wherein R is alkyl, aryl, alkylaryl,
M represents arylalkyl, alkenyl or cycloalkyl, and M represents the metal calcium, barium, magnesium or zinc. A stabilized vinyl chloride resin composition comprising a combination of at least one metal salt of an organic phosphoric acid monoester or a metal salt of an organic phosphoric acid diester represented by the formula (1) in an amount of 0.001 to 3 parts by weight. 2. 100 parts by weight of a vinyl chloride resin,
(A) 0.1 to 5 parts by weight of at least one metal salt compound of a carboxylic acid or an alkylphenol, and (b) β-
0.0005 to 3 parts by weight of at least one diketone compound and (c) the following general formula (1) (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), At least one of 0.0005 to 2 parts by weight of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphoric acid ester and heating; General formula (2)
Or (3) Embedded image (Wherein R is alkyl, aryl, alkylaryl,
M represents arylalkyl, alkenyl or cycloalkyl, and M represents the metal calcium, barium, magnesium or zinc. (E) at least one kind of a metal salt of an organic phosphoric acid monoester or a metal salt of an organic phosphoric acid diester represented by the following general formula (4): Mg _x Zn _y Al _2. (OH) _{2x + 2y + 4} · (CO ₃ ) _{1−z / 2} (ClO ₄ ) _z · mH ₂ O (4) (where x, y and z are numbers satisfying the condition represented by the following formula, m represents 0 or an arbitrary number: 0 <x <
10, 0 ≦ y <10, 2 ≦ x + y <20, 0 ≦ z <2)
A stabilized vinyl chloride resin composition comprising a combination of at least one compound represented by the formula (1) and 0.001 to 10 parts by weight. 3. The method according to claim 1, wherein the metal of the metal salt compound of carboxylic acid or alkylphenol is barium-zinc, calcium-
3. The stabilized vinyl chloride resin composition according to claim 1, which is a combination of zinc or calcium-magnesium-zinc. 4. The metal salt compound according to claim 1, wherein the metal salt compound is a combination of a barium or calcium overbased carboxylate carbonate complex or an overbased alkyl phenolate carbonate complex with zinc carboxylate. A stabilized vinyl chloride resin composition. 5. The method according to claim 1, wherein the β-diketone compound is any one of dibenzoylmethane, palmitoylbenzoylmethane, and stearoylbenzoylmethane.
4. The stabilized vinyl chloride resin composition according to item 1. 6. General formula (1) (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; The polyoxyethylene organic group ether phosphate represented by the formula (1) is either tridecyl polyoxyethylene (4 to 10) phosphoric acid or nonylphenyl polyoxyethylene (5 to 55) phosphoric acid. 3. The stabilized vinyl chloride resin composition according to item 2.