JP3155320B2 - Chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a chlorine-containing resin composition having improved processability, and more particularly, to a process stability obtained by adding an organic phosphorus-containing metal salt and a hydrotalcite compound to a chlorine-containing resin in combination. The present invention relates to a hard chlorine-containing resin composition having improved properties.

[0002]

2. Description of the Related Art Hard chlorine-containing resin has a high heat deformation temperature, and is excellent in heat resistance and weather resistance, so that it is widely used for building materials such as window frames and pipes for water and sewage. Have been.

However, a hard chlorine-containing resin containing little plasticizer has a lower gelation rate, a higher melting temperature, and a lower fluidity than a soft resin composition containing a large amount of plasticizer. However, there is a drawback that thermal degradation is apt to occur during processing, and the thermal stability, light stability, mechanical properties, and the like of the resulting product are deteriorated due to the thermal degradation.

In order to compensate for these drawbacks, an acrylic processing aid is added to a chlorine-containing resin or is directly copolymerized with a resin to increase the gelation rate.
Attempts have been made to lower the melting temperature, but the effect is still inadequate. Conventionally, lead-based stabilizers, which are particularly excellent in heat resistance, have been widely used in hard vinyl chloride-based resin compositions, but recently, due to the problem of toxicity, a formulation containing no lead-based stabilizer has been used. It was strongly desired to be established.

For such a purpose, Japanese Patent Application Laid-Open No. 57-20994
No. 3, JP-A-60-199043, etc., it has been proposed to add a specific organotin compound and a hydrotalcite compound in combination, but they have not been practically satisfactory. JP-A-60-219246 proposes adding perchloric acid-treated hydrotalcite and an organic metal phosphate to a halogen-containing resin. In this case, too, a hard chlorine-containing resin composition is used. However, it was not sufficient in terms of improving the heat resistance during processing.

Japanese Patent Application Laid-Open No. 1-255653 discloses that a hydrotalcite compound, a metal salt of a higher alcohol phosphate and a fluorine-containing compound are added in combination, which contains a large amount of a plasticizer. The purpose is to improve the weather resistance of soft agricultural films, and there is no suggestion about the effect of improving the processability of hard chlorine-containing resins.

[0007] The hard chlorine-containing resin composition and the soft composition have completely different characteristics required for the stabilizer with the difference in the characteristics. Therefore, development of a stabilizer system suitable for a hard chlorine-containing resin composition has been demanded.

[0008]

Means for Solving the Problems In view of the above situation, the present inventors have made various studies and found that a specific organic phosphorus-containing metal salt and a hydrotalcite compound are added to a chlorine-containing resin in combination. As a result, a chlorine-containing resin composition having improved processing stability was obtained, and the present invention was completed.

That is, the present inventors have the following [formula 3]
(Same as [Chemical Formula 1]) and at least one kind of the organic phosphorus-containing metal salt represented by the general formula (I) or (II); The present invention provides a chlorine-containing resin composition having improved processing stability by adding at least one hydrotalcite compound represented by the formula (1).

[0010]

Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 18 carbon atoms, M ₁ represents an alkali metal, an alkaline earth metal, a zinc atom or an aluminum atom. A represents 1 to 3,
b represents 0 or 1, and a + b represents the valence of the metal. M ₂ represents an alkali metal, an alkaline earth metal, a zinc atom or an aluminum atom. c is 、 １, 1, 3/2, d
Represents 0 or 1, and 2c + d represents the valence of the metal. )

[0011]

Embedded image Mg _X1 Zn _X2 Al ₂ (OH) _{2 (X1 + X2) + 4} · CO ₃ · mH ₂ O (III) (where x1 and x2 satisfy the conditions represented by the following formulas, respectively) And m represents a real number: 0 ≦ x2 / x1 <10,
2 ≦ x1 + x2 <20)

Hereinafter, the chlorine-containing resin composition of the present invention will be described in detail.

[0013]

Accordingly, the organic phosphorus-containing metal salt used in the chlorine-containing resin composition of the present invention includes, for example, the following:
Compounds of Chemical Formulas 7 to 11, Chemical Formula 14, Chemical Formula 16 to Chemical Formula 18 (Compound Nos. 3 to 7, 10, 12 to 1)
4 ).

[0015]

[0016]

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

[0023]

[0024]

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[0025]

[0026]

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[0027]

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[0028]

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The amount of the organic phosphorus-containing metal salt is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the chlorine-containing resin.
Parts by weight, more preferably 0.05 to 3 parts by weight.

The hydrotalcite compound used in the chlorine-containing resin composition of the present invention is represented by the general formula (III):
Magnesium and aluminum, or zinc, represented by
It is a double salt compound having a layered structure composed of magnesium and aluminum, and may be a hydrate or an anhydride.

The above hydrotalcite compound may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280, JP-B-50-3
Known methods described in JP-A-0039, JP-B-51-29129, JP-A-61-174270 and the like can be exemplified. Further, in the present invention, it can be used without being limited by its crystal structure, crystal particle diameter and the like.

The surface of the above hydrotalcite compound may be made of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher fatty acid amide. And those coated with higher fatty acid esters or waxes.

The addition amount of the above hydrotalcite compound is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The organic phosphorus-containing metal salt and the hydrotalcite compound used as a stabilizer in the chlorine-containing resin composition of the present invention can be separately added to the chlorine-containing resin, respectively. They can be used as a mixture, and in this case, they can be used as so-called composite stabilizers containing other stabilizer components if necessary.

The following are examples of the chlorine-containing resin in the present invention. For example, polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer Copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl, cycloalkyl or arylmaleimide Copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , Vinyl chloride-acrylate Coalescence,
Chlorine-containing resins such as vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer and the above chlorine-containing resin and polyethylene, polypropylene, Polybutene, α-olefin polymers such as poly-3-methylbutene or ethylene-vinyl acetate copolymer, polyolefins such as ethylene-propylene copolymer and copolymers thereof, polystyrene,
Acrylic resin, copolymer of styrene with other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, methacrylate ester butadiene-styrene copolymer, polyurethane Blend products and the like can be mentioned.

The hard chlorine-containing resin composition of the present invention contains no plasticizer, or contains no chlorine-containing resin.
It contains only 10 parts by weight or less of a plasticizer with respect to 00 parts by weight.

The chlorine-containing resin composition of the present invention may further comprise L
The stabilizing effect is remarkably improved by using an organic acid salt of a metal such as i, K, Na, Mg, Sr, Ca, Ba, Zn, Cd, Sn, and Pb, an organic tin compound, or the like in combination.

As the organic acid residue of the above-mentioned organic acid salt of a metal, carboxylic acids, phenols and the like are useful.

As the carboxylic acid, for example, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexyl acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearin Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid Monohydric carboxylic acids such as ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid,
Divalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or monoesters or monoamide compounds thereof, butanetricarboxylic acid, butanetetracarboxylic acid, hemi-mellitic acid, trimellitic acid, melophanic acid, pyromellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids.

The above phenols include phenol, cresol, xylenol, methyl propyl phenol, methyl tertiary octyl phenol, ethyl phenol, isopropyl phenol, tertiary butyl phenol, n-butyl phenol, diisobutyl phenol,
Isoamylphenol, diamylphenol, isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenol, etc. No.

The amount of the metal salt of the organic acid is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the chlorine-containing resin.
Parts by weight, more preferably 0.1 to 5 parts by weight.

Also, an organotin compound (organotin stabilizer)
Examples thereof include mono- or dialkyltin compounds such as mono- or dimethyltin-, mono- or dibutyltin- or mono- or dioctyltin compounds, and more specifically, sulfides, oxides or sulfides of mono- or dialkyltin. Oxides; carboxylate such as octoate, laurate, malate-laurate, stearate, isostearate, crotonate, oleate, basic laurate; dialkyltin cyclic malate or malate polymer; dialkyltin butyl malate, octyl malate And ester malates such as malate-octyl malate, stearyl malate, oleyl malate, basic butyl malate; mono- or dialkyltin octyl mercaptide, lauryl mercaptide, stearyl mer Alkyl mercaptides such as peptide; thioglycolic acid ester salts such as isooctyl thioglycolate, 2-ethylhexyl thioglycolate, tetradecyl thioglycolate, isooctyl thioglycolate-sulfide of mono- or dialkyltin; mono- or dialkyl Thiopropionate salts such as isooctylthiopropionate, 2-ethylhexylthiopropionate and tetradecylthiopropionate of tin; and mercaptoethanol ester salts such as 2-mercaptoethyl oleate salt of mono- or dialkyltin. Among these organotin-based stabilizers, malate-based, ester malate-based, and thiocarboxylic acid ester-based stabilizers are particularly preferable.

The amount of the organotin-based stabilizer to be added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

An excellent synergistic effect is exhibited by using an organic phosphite compound and / or an epoxy compound in combination with the chlorine-containing resin composition of the present invention.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono and di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-didaisanbutylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite,
Bis (neopentyl glycol) / 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C ₁₂ -C
₁₅ mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis ( 2
-Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphite and the like.

The amount of the organic phosphite compound added is
Preferably, 0.0 parts by weight based on 100 parts by weight of the chlorine-containing resin.
It is 1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

The epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and epoxidized linseed oil. Fatty acid butyl, epoxy methyl stearate,
-Butyl, 2-ethylhexyl or -stearyl,
Tris (epoxypropyl) isocyanurate, 3-
(2-xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate and the like Is mentioned.

The amount of the epoxy compound to be added is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

If a light stabilizer is added to the chlorine-containing resin composition of the present invention, the light stability can be improved, and these can be appropriately selected and used according to the purpose of use. These light stabilizers include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, hindered amines, various metal salts or metal chelates, especially nickel or chromium salts or chelates.

The coloring property and the like can be improved by adding other organic stabilizing aids, metal perchlorates and the like to the chlorine-containing resin composition of the present invention.

Examples of the organic stabilizing aid include phenolic antioxidants, polyhydric alcohols, β-diketone compounds, and organic nitrogen-containing compounds.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butyl) Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid]
Glycol ester, 4,4'-butylidenebis (6-
Tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-
Ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tert-butyl-4-methyl-6- (2-hydroxy-3-
Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-
Hydroxylbenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-−２ (3-tert-butyl Butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) −5-
Methylphenyl) propionate].

The polyhydric alcohols include, for example,
Pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, sorbitol, trishydroxyether isocyanurate,
Examples thereof include trimethylolpropane, ditrimethylolpropane, and ester compounds or partial ester compounds thereof.

Examples of the β-diketone compound include β-diketone compounds such as dibenzoylmethane, benzoylacetone, stearylbenzoylmethane, dehydroacetic acid, and metal salts thereof.

As the organic nitrogen-containing compound, for example,
2,6-dimethyl-1,4-dihydropyridine-3,5
-Dicarboxylic acid didodecyl ester, 2-phenylindole, melamine and the like.

Examples of the metal component of the metal perchlorate include lithium, sodium, potassium, magnesium, magnesium, calcium, strontium, barium, zinc, cadmium, lead, aluminum and the like. Perchloric acid-treated metal salts may be used, and these metal salts of perchloric acid may be anhydrous or hydrated. It may be dissolved in a solvent such as alcohol or a dehydrated product thereof.

Further, in order to obtain a non-toxic or low-toxic chlorine-containing resin composition, if a non-toxic or low-toxic one of the above-mentioned commonly used organic acid metal salts is selected and used, it is non-toxic or low-toxic. A chlorine-containing resin composition having good heat stability can be obtained.

If necessary, the chlorine-containing resin composition of the present invention may contain, for example, a crosslinking agent, a filler, a modifier, a pigment,
Foaming agent, antistatic agent, anti-fog agent, plate-out inhibitor,
Surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, fungicides,
Light deteriorating agents, non-metallic stabilizers, processing aids, release agents and the like can be included.

[0059]

Next, the stabilizing effect of the chlorine-containing resin composition of the present invention will be specifically described by way of examples. However, the present invention is not limited by the following examples.

Example 1 Using the following formulation, the temperature was 190 using a Labo Plastomill (torque rheometer manufactured by Toyo Seiki Seisaku-sho, Ltd.).
The decomposition time of each composition was measured under the conditions of ° C., the number of rotations of 40 rpm, and the input amount of 65 g / 60 cc.

The results are shown in the following [Table 1]. In addition, the compound Nos. 3 to 7, 10 , 12 to 14 in the table were each
[Chemical Formula 7] to [Chemical Formula 11], [Chemical Formula 14], and [Chemical Formula 16] to [Chemical Formula 18].

[Combination] Parts by weight Vinyl chloride resin (degree of polymerization 800) 100 Calcium carbonate 10 Titanium dioxide 5 Rice bran wax 0.7 Partially oxidized polyethylene wax 0.3 Calcium stearate 0.6 Zinc stearate 0.7 Alkamizer 4 ^{* 1} 1.0 Test compound (see [Table 1]) 0.3 * 1 Zinc-modified hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0063]

[Table 1]

Example 2 Using the following formulation, the temperature of 190 was measured using a Labo Plastomill (torque rheometer manufactured by Toyo Seiki Seisaku-sho, Ltd.).
The decomposition time of each composition was measured at a temperature of 40 ° C., a rotation speed of 40 rpm, and an input amount of 70 g / 60 cc.

The results are shown in Table 2 below. "Comparative compound 1" in the table is a compound represented by the following [Chemical Formula 19].

[Combination] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Calcium carbonate 3 Titanium dioxide 6 Acrylic modifier 5 Acrylic processing aid 0.5 Polyethylene wax 0.6 Stearic acid monoglyceride 0.4 Di Pentaerythritol 0.5 Calcium stearate 0.6 Zinc stearate 1.0 Alkamizer 1 ^{* 2} 1.0 Test compound (see [Table 2]) 0.4 * 2 Hydrotalcite manufactured by Kyowa Chemical Co., Ltd.

[0067]

[Table 2]

[0068]

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[0069]

[0070]

[0071]

[0072]

As is evident from the examples, the processing stability of the hard chlorine-containing resin was significantly improved even when only one of the phosphorus-containing metal salt or the hydrotalcite compound used in the chlorine-containing resin composition of the present invention was added. No significant improvement is observed. However, by containing both of them, a large effect is exhibited that cannot be predicted from the case where each is added alone. From this, it is clear that the chlorine-containing resin composition of the present invention is an excellent hard chlorine-containing resin composition.

[0074]

The chlorine-containing resin composition of the present invention has improved processing stability.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-98105 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/04 C08K 3/26 C08K 5 / 52

Claims (1)

(57) [Claims] An organic acid is added to 100 parts by weight of a chlorine-containing resin.
At least one of 0.01 to 10 parts by weight of the lead salt, (b) at least one 0.01-5 weight of the organic phosphorus-containing metal salt represented by the following formula [Formula 1] (I) or (II) at least one 0.01-10 weight parts and (b) hydrotalcite compound represented by the following general formula [formula 2] (III)
Part was processed stability improvement obtained by adding a plasticizer total
A hard chlorine-containing resin composition that does not contain any more or less than 10 parts by weight . Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 18 carbon atoms, M ₁ represents an alkali metal, an alkaline earth metal, a zinc atom or an aluminum atom. A represents 1 to 3,
b represents 0 or 1, and a + b represents the valence of the metal. M ₂ represents an alkali metal, an alkaline earth metal, a zinc atom or an aluminum atom. c is 、 １, 1, 3/2, d
Represents 0 or 1, and 2c + d represents the valence of the metal. Mg _x1 Zn _x2 Al ₂ (OH) _{2 (x1 + x2) + 4} · CO ₃ · mH ₂ O (III) (where x1 and x2 are conditions represented by the following formulas, respectively) M represents a real number, and 0 ≦ x1 / x2.
<10, 2 ≦ x1 + x2 <20)