JPH0873687A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE: To obtain a colorless composition having excellent heat stability and slight change of physical properties with time, by blending a halogen- containing resin with specific two kinds of phenolic antioxidants, a hydrotalcite and a zinc compound. CONSTITUTION: This composition is obtained by blending (A) 100 pts.wt. of a halogen-containing resin with (B) preferably 0.005-5 pts.wt. of phenolic antioxidants of formula I and formula II [R is a group of formula III (R<1> to R<3> are each H, methyl or t-butyl); R' is a group of formula IV], (C) preferably 0.05-10 pts.wt. of a preferably synthetic hydrotalcite [preferable example; Mgx Al2 (OH)2x+4 CO3 .nH2 O (X is 4-6; (n) is 0-20)] and (D) preferably 0.001-3 pts.wt. of a zinc compound such as an organic acid zinc salt, zinc oxide or zinc carbonate. The weight ratio of the compound of formula I to the compound of formula II of the component B is preferably 0.05-20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-containing resin composition, and more specifically, it is characterized in that two kinds of specific phenolic antioxidants, hydrotalcites and zinc compounds are added to a halogen-containing resin in combination. And a halogen-containing resin composition.

[0002]

2. Description of the Related Art Halogen-containing resins are resins having excellent flame retardancy and chemical resistance,
It is used for various purposes. However, the halogen-containing resin is thermally unstable and desorbs hydrogen halide,
It has a defect that it is colored and mechanical strength is deteriorated, and its commercialability is impaired. Therefore, various stabilizers have been developed, and it is known that a lead compound or a mixture of a cadmium compound and a barium compound has an excellent stabilizing effect. However, in recent years, the use of lead compounds and cadmium compounds has tended to be restricted from the viewpoint of safety, and zinc compounds with high safety and organic acid salts of alkaline earth metals, hydrotalcites, inorganic materials such as zeolites, etc. It is being changed to stabilization by combined use with compounds.

A method for stabilizing a halogen-containing resin with the above-mentioned zinc compound and hydrotalcites is disclosed in JP-A-55 / 55.
No. -80445 is proposed.

However, the stabilization with a zinc compound and hydrotalcites does not provide satisfactory stabilizing effects such as thermal stability and colorability, and therefore JP-A-57-14755.
JP-A-57-8 discloses that a polyhydric alcohol is used in combination.
In JP-A-0444, a combined use of β-diketone is disclosed in JP-A-58 / 58.
No. 122951 proposes the combined use of perchlorates, JP-A-4-359945 proposes the combined use of phosphoric acid ester metal salts, and JP-A-3-126746 discloses the use of hindered amine light stabilizers. A combination is proposed, a combination of an ultraviolet absorber is proposed in JP-A-4-202254, and a combination of a phenol-based antioxidant and a thioether-based antioxidant is proposed in JP-A-4-359947. It worked, but it was still unsatisfactory.

Therefore, an object of the present invention is to provide a halogen-containing resin composition using a zinc compound and hydrotalcites, which has no coloring property, is excellent in thermal stability, and has little change in physical properties over time. .

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, as a halogen-containing resin stabilized with a zinc compound and hydrotalcites, two kinds It was found that the halogen-containing resin excellent in thermal stability, colorability, and retention of physical properties over time, which cannot be obtained by using the phenol-based antioxidant alone, can be obtained by adding the phenol-based antioxidant of 1.

The present invention has been made based on the above findings, and a halogen-containing resin can be prepared by adding the following [Chemical formula 2] (the above-mentioned [Chemical formula 1]
And a phenolic antioxidant represented by the general formulas (I) and (II), hydrotalcites, and a zinc compound are added. .

[0008]

Embedded image

The halogen-containing resin composition of the present invention will be described in detail below.

The halogen-containing resin used in the present invention includes polyvinyl chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, and chloride. Vinyl
Butadiene copolymer, vinyl chloride-styrene copolymer,
Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, chlorinated polyethylene, chlorinated polypropylene, and a copolymer of the above halogen-containing resin and vinyl chloride, vinyl chloride-styrene-maleic anhydride ternary copolymer Examples thereof include polymers.

Among the phenolic antioxidants represented by the above general formulas (I) and (II) used in the present invention, more specific examples of the phenolic antioxidants represented by the above general formula (I) are given. Examples of the compound include compound No. 1 and compound No. 2 of the following [Chemical Formula 3] and [Chemical Formula 4].

[0012]

[Chemical 3]

[0013]

[Chemical 4]

The amount of the above-mentioned phenolic antioxidant added is
The total amount of the two kinds is preferably 0.005 to 5 parts by weight with respect to 100 parts by weight of the halogen-containing resin. If the addition amount is less than 0.005 parts by weight, a sufficient stabilizing effect cannot be obtained, and if it exceeds 5 parts by weight, the stabilizing effect is not improved so much, which is economically disadvantageous. The weight ratio of the phenolic antioxidant represented by the general formula (I) and the phenolic antioxidant represented by the general formula (II) (the latter / the latter) is preferably 0.05 to Twenty.
If the weight ratio is out of the above range, the synergistic effect becomes difficult to be recognized.

The zinc compound used in the present invention is used as a stabilizer for the halogen-containing resin composition of the present invention. Examples of the zinc compound include aliphatic carboxylic acids such as zinc stearate, zinc laurate and zinc oleate. Zinc salt of
Examples thereof include zinc salts of aromatic carboxylic acids such as zinc benzoate and zinc p-tert-butylbenzoate, zinc salts of organic acids such as zinc phosphate salts, and inorganic zinc salts such as zinc oxide and zinc carbonate. The amount of the zinc compound added is preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the halogen-containing resin. If the addition amount is less than 0.001 part by weight, a sufficient stabilizing effect cannot be obtained, and if it exceeds 3 parts by weight, thermal stability becomes insufficient due to zinc burning.

The hydrotalcites used in the present invention are used as a stabilizer for the halogen-containing resin composition of the present invention, and the hydrotalcites include compounds represented by the following general formula (III): preferable.

Mg _X Al ₂ (OH) _{2X + 4} CO ₃ · nH ₂ O (III) (in the formula, 4 ≦ X ≦ 6 and 0 ≦ n ≦ 20 are shown.)

The above-mentioned hydrotalcite may be a natural product or a synthetic product, but a synthetic product in which the resin is less contaminated by impurities is preferable. The composition of the hydrotalcites may be one obtained by substituting part or all of magnesium in the general formula (III) with zinc or another alkaline earth metal, and part or all of the carbonate anion being perchloric acid. It may be substituted with an anion or the like. The hydrotalcites may be surface-treated with fatty acid or the like. The addition amount of the above hydrotalcites is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the halogen-containing resin.
5 parts by weight. If the addition amount is less than 0.05 parts by weight, the stabilizing effect is not recognized, and if it exceeds 10 parts by weight, the color tone and mechanical strength of the resin are impaired.

The halogenated resin composition of the present invention contains other stabilizers, plasticizers, other phenolic antioxidants, phosphorus antioxidants, light stabilizers, ultraviolet absorbers, etc. which are usually used.
Antifogging agent, antistatic agent, flame retardant, lubricant, modifier, strengthening agent,
You may use together with a pigment, a foaming agent, etc. Further, another resin may be mixed as long as it does not impair the mechanical properties of the halogenated resin.

As the above-mentioned other stabilizers, known ones can be used, and specifically, alkaline earth metal soaps such as calcium soap and barium soap, aluminum soaps, organic phosphate metal salts and the like organic compounds. Inorganic metal salts such as metal salts, metal oxides, metal hydroxides, metal carbonates, inorganic complex metal salts such as zeolite, barium chlorate, barium perchlorate, halogen oxyacid salts such as sodium perchlorate, β Non-metal stabilizers such as diketones, polyhydric alcohols, epoxy compounds and the like.

Examples of the plasticizer include ester plasticizers,
Examples include ether plasticizers, epoxy plasticizers, and phosphoric acid ester plasticizers. The plasticizer is preferably used in an amount of 0 to 300 parts by weight, based on 100 parts by weight of the halogen-containing resin, depending on the application of the halogenated resin composition.

Specific examples of the plasticizer include, as the ester plasticizer, acids such as phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid and azelaic acid, and n-propanol, isopropanol, n-butanol. , Isobutanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n -Ester or butanedio consisting of linear or branched alkyl alcohols such as nonanol, isononanol, n-decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol, alone or in a mixture. Polyester plasticizers such as esters of Le and adipic acid.

As the epoxy plasticizer, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized linseed oil fatty acid butyl, octyl epoxy stearate, epoxy triglyceride, diisodecyl epoxyhexahydrophthalate, and Epoxy resins such as low molecular weight reaction product resins of epichlorohydrin and bisphenol A.

Examples of the phosphoric acid ester-based plasticizer include tricresyl phosphate, trixylenyl phosphate, monobutyldixylenyl phosphate, trioctyl phosphate and the like.

The above-mentioned other phenol-based antioxidant may be any of those usually used, for example,
2,6-di-tert-butyl-p-cresol, 2,6-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-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4 '-Thiobis (6
-Tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,
2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-)
Tert-Butylphenyl) butyric acid] glycol ester, 2,2′-ethylidene bis (4,6-di-tert-butylphenol), 2,2′-ethylidene bis (4-)
(Tert-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 (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-ditert-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-{(3-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) -5
Methylphenyl) propionate] and the like. The phenolic antioxidant is a halogen-containing resin 100
It is preferably used in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on parts by weight.

As the above-mentioned phosphorus-based antioxidant, any of those usually used may be used, and examples thereof include trisnonylphenylphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, and tris [2-tertiary]. Butyl-4-
(3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite,
Di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-
Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4 ′ -N-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl)
Butanetriphosphite, tetrakis (2,4-ditertiarybutylphenyl) biphenylene diphosphonite, 9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) -2-ethylhexylphosphite, and the like, and others. , JP-A-5
A high molecular weight phosphorus compound proposed in JP-A 7-192460 can be mentioned. The phosphorus antioxidant is preferably 0.001 with respect to 100 parts by weight of the halogen-containing resin.
To 5 parts by weight, more preferably 0.005 to 3 parts by weight.

Examples of the ultraviolet absorber include 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as (hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tertiary octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; Ethyl-α -Cyano-β, β-
Examples thereof include cyanoacrylates such as diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate. The ultraviolet absorber is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 100 parts by weight of the halogen-containing resin.
It is used to be up to 5 parts by weight.

Examples of the light stabilizer include 2,2,2
6,6-tetramethyl-4-piperidyl stearate,
1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, screw (1, 2,
2,6,6-Pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-)
Piperidyl) butanetetracarboxylate, tetrates (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2)
2,6,6-Pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2
-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate,
1,6-bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2) , 6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2
6,6-Tetramethyl-4-piperidyl) amino) -s
-Triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4
-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1 , 6,11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Examples thereof include hindered amine compounds such as piperidyl) amino) -s-triazin-6-ylamino] undecane. The light stabilizer is used in an amount of preferably 0.001 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the halogen-containing resin.

Examples of the method for processing the halogen-containing resin composition of the present invention include extrusion processing, calendar processing, blow molding, press processing, powder molding, injection molding and the like.

The halogen-containing resin composition of the present invention is used for packaging materials such as wrap films for food packaging, floor materials, ceiling materials,
Building materials such as wall materials, window frames, corrugated boards, rain gutters, automobile exterior materials, automobile interior materials, agricultural materials, wire coating materials, paints, adhesive tapes, label films, shrink films, hoses, tubes, packings, It can be used for any application as long as the usual halogen-containing resin composition is used for daily sundries such as gaskets, pipes, leather and toys.

[0031]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

Example 1 and Comparative Examples 1 to 4 To the composition of the following (basic formulation 1), the compound (stabilizer) of the following [Table 1] was added and blended in a Henschel mixer,
Roll kneading was performed under the conditions of 160 ° C. × 20 rpm × 0.3 mm × 7 minutes to obtain a sheet for thermal stability test.

Thermal stability test: The obtained sheet was heated at 210 ° C.
The time to blackening in the gear oven was evaluated at 10 minute intervals.

Colorability test: The obtained sheet was subjected to 180 ° C. ×
The yellowness of the sheet obtained by pressing for 5 minutes × 1 mm was measured to evaluate the colorability.

Heat Aging Test: 170 the roll sheet
The press sheet obtained by pressing at ℃ × 4 minutes × 0.4 mm was placed in an oven at 136 ° C, and a sample after 480 hours was subjected to a tensile test (JIS K 711302, tensile speed: 200 mm / m.
in.) was performed to measure the elongation rate, and the heat aging property was evaluated by the elongation residual rate of each sample with respect to the elongation of the sample before being placed in the oven.

The results are shown in the following [Table 1] together with the type and amount of the compound (stabilizer) used for the evaluation.

(Basic Mixture 1) [Basic Mixture for Evaluation of Vinyl Chloride Resin for Insulation Coating Material] Vinyl Chloride Resin 100 parts by weight Trioctyl trimellitate 50 〃 clay 15 〃 calcium carbonate 20 〃 synthetic calcium silicate 0.47 〃 Benzoylmethane 0.015〃 Sorbitol 0.03〃

[0038]

[Table 1]

* 1 to * 4 in the above [Table 1] are as follows (hereinafter the same). * 1: Kyowa Chemical Co., Ltd. hydrotalcite Mg _4.5 Al ₂ (O
H) ₁₃ CO ₃ · 3.5H ₂ O * 2: Compound shown in [Chemical Formula 3] * 3: Asahi Denka Kogyo Co., Ltd. phenolic antioxidant ADEKA STAB AO-404,4′-butylidene bis (6-third) Butyl-m-cresol) * 4: Deterioration is severe and measurement is not possible

Examples 2 to 4 and Comparative Examples 5 to 6 The compounds (stabilizers) shown in Table 2 below were added to the compositions shown below (basic formulation 2), and the same evaluations as in Example 1 were carried out.
The processing conditions and the evaluation method of the test piece used for the evaluation were the same as the vinyl chloride resin for insulating coating material except that the test temperature of the thermal stability test was changed to 190 ° C.
The colorability was evaluated. The results are shown in [Table 2] below.
Shown in

(Basic Mixture 2) [Basic Mixture for Evaluation in Semi-Hard Vinyl Chloride Resin] Vinyl chloride resin 100 parts by weight Dioctyl phthalate 5 〃 Epoxidized soybean oil 5 〃 Titanium dioxide 15 〃 DHT-4A ^{* 1} 0.8 〃 Stearin Zinc acid salt 0.5 〃 Barium oleate 0.7 〃 Barium benzoate 0.2 〃 Phosphorus antioxidant ^{* 5} 0.3 〃 Stearoylbenzoylmethane 0.3 〃

[0042]

[Chemical 5]

[0043]

[Table 2]

Examples 5 and 6 and Comparative Examples 7 to 9 The compounds (stabilizers) shown in Table 3 below were added to the compositions shown below (basic formulation 3), and the same evaluations as in Example 1 were carried out.
The processing conditions and the evaluation method of the test piece used for the evaluation were the same as the vinyl chloride resin for insulating coating material except that the test temperature of the thermal stability test was changed to 190 ° C.
The colorability was evaluated. The results are shown in [Table 3] below.
Shown in

(Basic mix 3) [Basic mix for evaluation of hard vinyl chloride resin] Vinyl chloride resin 100 parts by weight Titanium dioxide 0.3 〃 Zinc stearate 0.5 〃 Calcium stearate 0.4 〃 Dipentaerythritol 0.3 〃 Alkamizer 1 ^{* 6} 0.3 〃 AO-50 ^{* 7} 0.1 〃 Dibenzoylmethane 0.1 〃 Polyethylene wax 0.5 〃 Glycerin distearate 0.2 〃 * 6: Hydro by Kyowa Chemical Co., Ltd. Talcite Mg ₄ Al ₂ (O
_{H) 12 CO 3 · 3H 2} O * 7: Asahi Denka Co. phenolic antioxidant ADK STAB AO-50 stearyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

[0046]

[Table 3]

[0047]

EFFECTS OF THE INVENTION The halogen-containing resin composition of the present invention is free from coloration and is excellent in thermal stability by using a hydrotalcite compound, a zinc compound, and two specific types of phenolic antioxidants in combination. It has a small change in physical properties over time.

Claims (1)

[Claims] 1. A halogen-containing resin to which a phenolic antioxidant represented by the following general formulas (I) and (II), hydrotalcites, and a zinc compound are added. A halogen-containing resin composition. Embedded image