JP5192182B2 - Chlorine-containing polymer stabilizer and chlorine-containing polymer composition - Google Patents

Description

  The present invention relates to a stabilizer for a chlorine-containing polymer, and more specifically, a stabilizer for a non-metallic chlorine-containing polymer that does not contain a metal component, and the stabilizer is blended and heat-stabilized. Relates to a prepared chlorine-containing polymer composition.

  Conventionally, metal salts or metal oxides such as Pb, Cd, Sn, etc. have been widely used as stabilizers for chlorine-containing polymers such as polyvinyl chloride. Through the use of metal oxides, calcium or zinc stabilizers have been used instead. However, in recent years, environmental issues have become more important and the use of zinc tends to be limited.

  Therefore, at present, non-metallic stabilizers for chlorine-containing polymers are attracting attention, and typical examples of such non-metallic stabilizers include aminouracil and its derivatives, aminocrotonates, and other amino acids. System stabilizers are known (see Patent Documents 1 and 2).

  However, in the amino stabilizer as described above, when blended with a chlorine-containing polymer, even if the initial coloration immediately after kneading and molding can be effectively suppressed, the heat resistance or heat resistance persistence is unsatisfactory, If kept at a high temperature, the color is immediately changed, and after a certain period of time, there is a disadvantage that the color is finally changed to black.

In order to improve the above drawbacks, various organic stabilizers have been studied. For example, Patent Document 3 includes amino alcohol, dihydropyridine, aminocrotonate, aminouracil, and phenylindole. A chlorine-containing polymer composition is proposed in which at least two selected from the group and a perchlorate substantially free of metal are blended, and the chlorine-containing polymer composition includes an epoxy compound. It is described that up to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer may be blended.
Japanese Patent Laid-Open No. 57-23647 JP 61-247748 A JP 2006-104474 A

  However, the chlorine-containing polymer composition containing a non-metallic stabilizer that does not contain a metal component can improve the heat resistance or heat durability to some extent, but the degree is still insufficient. The coloring tendency when kept in a high temperature atmosphere is not effectively suppressed. For example, in the chlorine-containing polymer composition of Patent Document 3 described above, when it is held in a high-temperature atmosphere, it takes a long time to change to black, but the degree of coloring is relatively high in a short time (in a short time). Further improvement is necessary. In addition, the chlorine-containing polymer composition of Patent Document 3 has a drawback that a compound that is difficult to handle and has a safety problem such as perchlorate must be used.

  Accordingly, an object of the present invention is to provide a non-metallic chlorine-containing polymer that has a high effect of preventing initial coloring, has high heat resistance or high heat durability, and can effectively suppress coloring tendency when held at a high temperature for a long time. And a chlorine-containing polymer composition containing the stabilizer.

  As a result of various studies on nonmetallic stabilizers, the present inventors have combined an epoxy group-containing acrylic resin having a specific epoxy equivalent and an aminocrotonic acid ester in a specific quantitative ratio. When the stabilizer component is further used in combination with a specific amount of at least one of polyhydric alcohol, hindered amine and phenylindole as an auxiliary component, and these are blended with the chlorine-containing polymer, the heat resistance or the heat resistance durability is remarkable. As a result, the present inventors have found that not only the coloring tendency when effectively held at a high temperature for a long time but also the initial coloring property is further effectively suppressed, and completed the present invention.

  According to the present invention, (A) 100 parts by weight of an epoxy group-containing acrylic resin having an epoxy equivalent of 100 to less than 250, and (B) 0.5 to 70 parts by weight of an aminocrotonic acid ester are used as main stabilizer components. And (C) 0.5 to 70 parts by weight of a polyhydric alcohol and / or (D) 0.1 to 70 parts by weight of a hindered amine or phenylindole. A stabilizer for chlorine-containing polymers is provided.

  According to the present invention, the chlorine-containing polymer is blended with the chlorine-containing polymer stabilizer, and the chlorine-containing polymer stabilizer is an epoxy group-containing acrylic resin (A in the stabilizer). Is provided in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.

In the stabilizer for chlorine-containing polymer of the present invention,
(1) The epoxy group-containing acrylic resin (A) has an epoxy equivalent of 100 to 200,
(2) The polyhydric alcohol (C) is at least one selected from the group consisting of pentaerythritol, dipentaerythritol or a partial ester thereof, and a hydroxyl group-containing isocyanurate,
(3) The hindered amine (D) is a tetramethylpiperidine-based hindered amine,
(4) As the auxiliary component, (C) containing a polyhydric alcohol and (D) a hindered amine and / or phenylindole,
(5) The phenylindole is 2-phenylindole,
Is preferred.

  The stabilizer for a chlorine-containing polymer of the present invention comprises (A) an epoxy group-containing acrylic resin having a predetermined epoxy equivalent and (B) an aminocrotonic acid ester as main stabilizer components. In addition to the components, (C) polyhydric alcohol or (D) hindered amine or phenylindole is blended as an auxiliary component, so that the initial coloring of the chlorine-containing polymer can be effectively suppressed and at the same time excellent heat resistance Thorough heat resistance. As will be apparent from the examples described later, when the chlorine-containing polymer composition containing this stabilizer is held in a high-temperature atmosphere, it takes a long time to change to black, and the state is maintained in a high-temperature atmosphere. The degree of coloring is extremely small, and a state close to an achromatic color can be maintained for a long time. For example, when the above auxiliary component is not blended, the color changes from yellow to light brown in a relatively short time (about 10 to 20 minutes). It is held in a light color state close to.

  Further, the stabilizer of the present invention is a non-metallic stabilizer that does not contain a metal component such as lead, zinc, tin, etc., and does not adversely affect the environment. Such a compound which is difficult to handle and has a safety problem is not blended, and its production is very easy.

  The stabilizer for a chlorine-containing polymer of the present invention includes (A) an epoxy group-containing acrylic resin and (B) an aminocrotonic acid ester in a predetermined amount ratio, and further, as an auxiliary component. By blending (C) polyhydric alcohol and / or (D) hindered amine or phenylindole in a predetermined amount ratio, the effect of preventing initial coloring and heat resistance or heat durability can be improved.

<Main stabilizer component>
(A) Epoxy group-containing acrylic resin The epoxy group-containing acrylic resin used in the present invention is one of the main components of this non-metallic stabilizer, and contributes particularly to improvement of heat resistance and heat durability. As epoxy group-containing resins, bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, epoxy group-containing styrene resins, and the like are also known. As is clear from the comparative example, the heat resistance persistence decreases.

  In the present invention, the epoxy group-containing acrylic resin has a remarkable improvement in heat resistance or heat durability, and the reason why such an improvement in properties is not clearly understood in other epoxy group-containing resins is not clearly elucidated. Probably, the epoxy group-containing acrylic resin is most compatible with chlorine-containing resins such as vinyl chloride resin, and as a result, it is uniformly dispersed in the chlorine-containing polymer in the form of incorporating other stabilizer components. It seems to be for this.

  In the present invention, as the epoxy group-containing acrylic resin, for example, a polymer comprising at least one of glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and acylglycidyl (meth) acrylate, these polymers, and methyl Examples thereof include copolymers with alkyl (meth) acrylates such as acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, acrylonitrile and methacrylonitrile. This molecular weight (weight average) is generally preferably from 1,000 to 100,000.

  In the present invention, it is also important that the epoxy equivalent of the epoxy group-containing acrylic resin is in the range of 100 to less than 250, particularly 100 to 200. That is, when the epoxy equivalent is larger than the above range, the heat resistance or the heat resistance persistence is lowered, and when the epoxy equivalent is smaller than the above range, the dispersibility with respect to the chlorine-containing polymer is lowered, and characteristic variations are likely to occur. Because.

  Epoxy group-containing acrylic resins having an epoxy equivalent as described above are, for example, Marproof G-01100 (manufactured by NOF Corporation; epoxy equivalent 170), METABRENE KP-6562 (manufactured by Mitsubishi Rayon Co., Ltd .; epoxy equivalent 200) ) And the like.

(B) Aminocrotonic acid ester Aminocrotonic acid ester, which is another main component used in the present invention, is known to have a function of preventing initial coloration of the vinyl chloride polymer. By using together with the epoxy group-containing acrylic resin, the initial coloring can be more effectively prevented.

  In the present invention, the aminocrotonic acid ester (β-aminocrotonate) is 0.5 to 70 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of the epoxy group-containing acrylic resin (A). Used in. When the amount is less than this range, the initial coloring prevention performance is lowered, and when it is used in a larger amount than the above range, the initial coloration can be effectively prevented, but the heat resistance durability is lowered. For example, the coloring tendency when the chlorine-containing polymer composition is held in a high-temperature atmosphere cannot be suppressed, and the time for deterioration to black becomes faster.

The aminocrotonic acid ester has the following general formula (1):
_{[CH 3 -C (NH 2)} = CH-COO] n -R ... (1)
In the formula, R is a residue of a monovalent to hexavalent alcohol,
n is an integer of 1 to 6,
Specific examples thereof include stearyl alcohol β-aminocrotonate, 1,4-butanediol diβ-aminocrotonate, thiodiethanol diβ-aminocrotonate, trimethylolpropane. Examples thereof include tri-β-aminocrotonate, pentaerythritol tetra-β-aminocrotonate, dipentaerythritol hexa-β-aminocrotonate, and the like. Among these, 1,4-butanediol di β-aminocrotonic acid ester is particularly preferable.

  The aminocrotonic acid ester is effective as a stabilizer for vinyl chloride resin among various chlorine-containing polymers.

<Auxiliary component>
In the present invention, (C) polyhydric alcohol and / or (D) hindered amine or phenylindole is used as an auxiliary component together with the main stabilizer component.

(C) Polyhydric alcohol Polyhydric alcohol is a component that supplementarily improves heat resistance or heat durability, and is 5 to 70 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of the epoxy group-containing acrylic resin. Used in quantity. That is, if the amount of the polyhydric alcohol used is outside the above range, the heat resistance or the heat resistance persistence is lowered, for example, the color tendency when the polymer composition is held in a high temperature atmosphere is increased, and the black color is changed to black. Time until it deteriorates is shortened.

式中、Ｒ^１、Ｒ^２及びＲ^３の各々は、ヒドロキシアルキル基である、
で表されるトリス（ヒドロキシアルキル）イソシアヌレートであることが好ましく、その適当な例としては、トリス（ヒドロキシエチル）イソシアヌレート、トリス（ヒドロキシプロピル）イソシアヌレート、トリス（ヒドロキシブチル）イソシアヌレート、トリス（２，３−ジヒドロキシプロピル）イソシアヌレート、トリス（グリシジル）イソシアヌレート等が挙げられる。 Examples of such polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, diglycerin, pentaerythritol, dipentaerythritol. Examples thereof include partial esters of pentaerythritol such as pentaerythritol adipate, partial esters of dipentaerythritol such as dipentaerythritol adipate, mannitol, sorbitol, trimethylolpropane, ditrimethylolpropane, and hydroxyl group-containing isocyanurate compounds. Examples of the hydroxyl group-containing isocyanurate compound include the following formula (2):

Wherein each of R ¹ , R ² and R ³ is a hydroxyalkyl group,
The tris (hydroxyalkyl) isocyanurate represented by the formula is preferable, and suitable examples thereof include tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, tris (hydroxybutyl) isocyanurate, tris ( 2,3-dihydroxypropyl) isocyanurate, tris (glycidyl) isocyanurate and the like.

  In the present invention, pentaerythritol, dipentaerythritol and partial esters thereof, and hydroxyl group-containing isocyanurate compounds are preferred as the polyhydric alcohol preferably used. These may be used alone or in combination of two or more. Most preferably, a hydroxyl group-containing isocyanurate compound is used.

(D) Hindered amine, phenylindole In the present invention, in place of the polyhydric alcohol (C) or together with the polyhydric alcohol (C), the hindered amine or phenylindole is combined with the main stabilizer component as an auxiliary agent. It can also be used as an ingredient.

  Although this hindered amine can greatly improve the initial coloring tendency together with the aminocrotonic acid ester (B) described above, the effect of preventing the initial coloring is remarkably increased, and coloring when kept in a high-temperature atmosphere is achieved. The tendency can be effectively suppressed, the color of the polymer composition can be maintained in a state close to an achromatic color, and the time until the color can be black can be extended.

  As such a hindered amine, those known per se can be used, and particularly preferred is a tetramethylpiperidine-based hindered amine having a tetramethylpiperidine structure. Examples of tetramethylpiperidine-based hindered amines include 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2 , 6,6-tetramethyl-4-piperidyl) dodecyl succinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl -4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6 , 6-pentamethyl-4-piperidyl) sebacate, 1- [2 [3 (3,3-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, tetra (2,2,6,6-tetramethyl- 4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl). Di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperradione), bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (N-methyl- , 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] butyl malonate, a condensate of 1,2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2, Condensation product of 3,4-butanecarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1 , 2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate, poly [[{ -(1,1,3,3-tetramethylbutyl) -amino} -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino ] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [(6-morpholino-S-triazine-2,4-diyl) [2,2,6,6- Tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl] imino], 1,2,3,4-butanetetracarboxylic acid and 1,2,2 , 6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol and N, N′-bis (3-aminopropyl) Ethylenediamine 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, dimethyl succinate -1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 A condensate of 6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol; Examples thereof include polymethylpropyl 3-oxy- [4 (2,2,6,6-tetramethyl) piperidinyl] siloxane.

Phenylindole contributes to the significant improvement in heat resistance, and the use of phenylindole is not as good as heat resistance, but also improves the initial colorability. Bring.
Examples of phenylindole include 2- (4′-dodecyl-phenyl) -indole, 2- (3′-methoxy-4′-hydroxy-phenyl) -indole, and 2- (3′-methyl-4′-methoxy). -Phenyl) -indole, 2-phenyl-5-methoxy-indole, 2- (3'-dodecyl-4'-methoxy-phenyl) -indole, 2- (3 ', 4'-diethoxy-phenyl) -indole, 2- (3′-methoxy-4′-propoxy-phenyl) -indole, 2- (3′-methyl-4′-ethoxy-phenyl) -indole, 2- (3′-methoxy-4′-ethoxy-phenyl) ) -Indole, 2- (4′-methyl-phenyl) -indole, 2- (4′-methyl-phenyl) -5-methyl-indole and the like.
Of these, 2-phenylindole is particularly preferable.

  In the present invention, such an auxiliary component (D) is used in an amount of 0.1 to 70 parts by weight, particularly 1.0 to 60 parts by weight, per 100 parts by weight of the epoxy group-containing acrylic resin (A). It is important to improve the initial colorability by hindered amine and the improvement of heat durability by phenylindole.

Further, in the present invention, it is preferable to use hindered amine and phenylindole as the auxiliary component (D), whereby both the initial coloring property and the heat resistance durability can be remarkably increased. When hindered amine and phenylindole are used in combination, the total amount is within the above range, but the weight ratio (D ₁ / D ₂ ) of hindered amine (D ₁ ) and phenylindole (D ₂ ). ) Is preferably in the range of 0.01 to 0.8, particularly 0.05 to 0.5 in order to maximize the effect of improving the initial colorability of hindered amine and the effect of improving the heat durability of phenylindole.

<Other auxiliary ingredients>
In the present invention, a sulfur-containing compound such as N, N′-diphenylthiourea can be used as an auxiliary component, if necessary, in addition to the components (C) and (D). Such an auxiliary sulfur-containing compound contributes to the improvement of the initial colorability, and the initial colorability can be further improved by the combined use with the hindered amine described above. Such a sulfur-containing compound can be used, for example, in an amount of 5 to 50 parts by weight, particularly 10 to 20 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin (A).

[Chlorine-containing polymer]
Examples of the chlorine-containing polymer in which each component of the above-mentioned nonmetallic stabilizer is blended include, for example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, chlorinated Vinyl-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Vinyl-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate Original copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester Copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, polymers such as internally plasticized polyvinyl chloride, and these chlorine-containing polymers and polyethylene, polypropylene, polybutene, poly- Α-olefin polymers such as 3-methylbutene or polyolefins such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and copolymers thereof, polystyrene, acrylic resin, styrene and other monomers (for example, Copolymers with maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylate-butadiene-styrene copolymers, blends with methacrylate-butadiene-styrene copolymers, etc. Can be mentioned.

[Chlorine-containing polymer composition]
The chlorine-containing polymer composition of the present invention is obtained by blending the above-described chlorine-containing polymer with a nonmetallic stabilizer containing each of the components (A) to (D) described above. Among the above-mentioned components, the chlorine-containing acrylic resin (A) is contained in such a way that the blending amount is 1.0 to 30 parts by weight, particularly 1.0 to 10 parts by weight per 100 parts by weight of the chlorine-containing polymer. Blended into the polymer. Thereby, various characteristics of each component are exhibited in a well-balanced manner and are synergistically improved, and excellent initial coloration preventing property, heat resistance and heat resistance durability are imparted to the chlorine-containing polymer. Moreover, importantly, such excellent characteristics are imparted without blending a metal-based stabilizer containing a metal salt or the like that adversely affects the environment. The combined composition is also useful from the viewpoint of environmental protection.

  In addition, the chlorine-containing polymer composition of the present invention is a per se known additive such as a plasticizer or a phenolic antioxidant within a range that does not impair the excellent characteristics obtained by the nonmetallic stabilizer component described above. Known resin compounding agents such as additives, lubricants, flame retardants, fillers, colorants, ultraviolet absorbers, antistatic agents, modifying resins or rubbers, impact resistance enhancers, and other organic compounding agents are known per se. Can be blended according to prescription.

  In particular, in the present invention, the chlorine-containing polymer composition is described above for both a hard vinyl chloride resin composition containing no plasticizer and a soft vinyl chloride resin composition containing a large amount of plasticizer. An excellent effect can be exhibited.

  The above plasticizers include phthalate ester plasticizers, adipate ester plasticizers, polyester plasticizers, phosphate ester plasticizers, chlorine plasticizers, tetrahydrophthalic acid plasticizers, azelaic acid plasticizers. Typical examples include plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid, trimellitic acid plasticizers, and pyromellitic acid plasticizers. These plasticizers are blended in an amount of 30 to 70 parts by weight per 100 parts by weight of the vinyl resin.

  The chlorine-containing polymer composition of the present invention is produced by melt-kneading various compounding agents such as the above-mentioned non-metallic stabilizer components, and is formed into a film, sheet or other shape by means known per se. And used for various purposes.

The invention is illustrated by the following examples and comparative examples.
In addition, the evaluation method of the composition prepared by the Example and the comparative example is as follows.

(1) Gear oven heat resistance test (GO)
The composition having the composition shown below was kneaded with a roll mill at a temperature of 160 ° C. for 5 minutes to prepare a uniform vinyl chloride sheet having a thickness of 0.7 mm.
<Formulation 1>
Vinyl chloride resin (degree of polymerization 1050) 100 parts by weight Polyethylene wax (lubricant) 0.8 parts by weight Stabilizers listed in each table Next, put a test piece into a gear oven set at 185 ° C. and take it out every predetermined time, and color it The state was visually observed and judged from the initial stage until it turned black.
<Formulation 2>
Vinyl chloride resin (degree of polymerization 1050) 100 parts by weight DOP (plasticizer) 50 parts by weight Polyethylene wax (lubricant) 0.8 parts by weight Stabilizer Listed in each table Next, put a test piece in a gear oven set at 185 ° C The sample was taken out every predetermined time, and the coloration state was visually observed and judged from the initial stage until it turned black.
The degree of coloration of the sheet was evaluated in the following seven stages.
1: White 2: Pale yellow 3: Yellow 4: Pale brown 5: Brown 6: Dark brown 7: Blackening

(2) Thermal stability test (HT)
In accordance with JIS-K-6723, a soft vinyl chloride sheet is cut into 1.0 mm × 1.0 mm, a test tube equipped with Congo red paper is filled with 2 g of sample chips, heated to 180 ° C., and the heat of vinyl chloride The hydrogen chloride desorption time due to decomposition was measured.

(Examples 1-2, Comparative Examples 1-8)
Stabilizers shown below were added in the above formulation 1 in the amounts shown in Table 1, and a gear oven heat resistance test was performed. The results are shown in Table 1. The blending amount is expressed as an amount per 100 parts by weight of the vinyl chloride resin.
(1) Epoxy group-containing resin (A):
Resin 1: Marproof G-01100 (manufactured by NOF Corporation, epoxy
Equivalent 170, acrylic)
Resin 2: Blemmer CP-50M (Nippon Yushi Co., Ltd., epoxy equivalent)
310, acrylic)
Resin 3: Epomic R-140 (Mitsui Chemicals, epoxy equivalent)
190, bisphenol type)
Resin 4: Epomic R-304P (Mitsui Chemicals, epoxy equivalent)
875-1,000, bisphenol type)
Resin 5: Marproof G-0250S (manufactured by NOF Corporation, epoxy resin
310, styrene)
Resin 6: Marproof G-0130S (manufactured by NOF Corporation, epoxy resin
Amount 530, styrene)
(2) Aminocrotonic acid ester (B):
1,4-butanediol bis- (β-aminocrotonate)
[Neulizer 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]
(3) Polyhydric alcohol (C):
Tris- (2-hydroxylethyl) isocyanurate
[THEIC-PW (manufactured by Shikoku Chemicals Co., Ltd.)]
(4) Hindered amine (HALS) (D ₁ ):
Poly [[{6- (1,1,3,3-tetramethylbutyl) -amino} -1,
3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]]
[Chimassorb944LD (Ciba.SC Co., Ltd.)]
(5) Epoxy compound:
Epoxidized soybean oil
[W-100EL (Dainippon Ink Chemical Co., Ltd.)]

(Examples 3-5, Comparative Examples 9-14)
Stabilizers shown below were added in the above formulation 1 in the amounts shown in Table 2, and a gear oven heat resistance test was performed. The results are shown in Table 2. The blending amount is expressed as an amount per 100 parts by weight of the vinyl chloride resin.
(1) Epoxy group-containing resin (A):
Resin 1: Marproof G-01100 (manufactured by NOF Corporation, epoxy resin
Amount 170, acrylic)
Resin 2: Metabrene KP-6562 (Mitsubishi Rayon Co., Ltd., epoxy)
Equivalent 200, acrylic)
Resin 3: Blemmer CP-50M (Nippon Yushi Co., Ltd., epoxy equivalent)
310, acrylic)
Resin 4: Epomic R-140 (Mitsui Chemicals, epoxy equivalent)
190, bisphenol type)
Resin 5: jER-1001 (Japan Epoxy Resin Co., Ltd., Epoxy
Si equivalent 469, bisphenol type)
Resin 6: Marproof G-0130S (manufactured by NOF Corporation, epoxy resin
Amount 530, styrene)
Resin 7: Marproof G-0250S (manufactured by NOF Corporation, epoxy resin
310, styrene)
(2) Aminocrotonic acid ester (B):
1,4-butanediol bis- (β-aminocrotonate)
[Neulizer 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]
(3) Polyhydric alcohol (C):
Tris- (2-hydroxylethyl) isocyanurate
[THEIC-PW (manufactured by Shikoku Chemicals Co., Ltd.)]
(4) Hindered amine (HALS) (D ₁ ):
Poly [[{6- (1,1,3,3-tetramethylbutyl) -amino} -1,
3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino]]
[Chimassorb944LD (Ciba.SC Co., Ltd.)]
(5) Phenylindole (D ₂ )
2-Phenylindole (Wako Pure Chemical Industries, Ltd.)
(6) Epoxy compound:
Epoxidized soybean oil
[W-100EL (Dainippon Ink Chemical Co., Ltd.)]

(Examples 6-8, Comparative Examples 15-18)
Stabilizers shown below were added in the amounts shown in Table 3 in the above Formulation 2, and a gear oven heat test was performed. The results are shown in Table 3. The blending amount is expressed as an amount per 100 parts by weight of the vinyl chloride resin.
(1) Epoxy group-containing resin (A):
Resin 1: Marproof G-01100 (manufactured by NOF Corporation, epoxy resin
Amount 170, acrylic)
Resin 2: Metabrene KP-6562 (Mitsubishi Rayon Co., Ltd., epoxy)
Equivalent 200, acrylic)
Resin 3: Blemmer CP-50M (Nippon Yushi Co., Ltd., epoxy equivalent)
310, acrylic)
Resin 4: Epomic R-140 (Mitsui Chemicals, epoxy equivalent)
190, bisphenol type)
Resin 5: jER-1001 (Japan Epoxy Resin Co., Ltd., Epoxy
Si equivalent 469, bisphenol type)
(2) Aminocrotonic acid ester (B):
1,4-butanediol bis- (β-aminocrotonate)
[Neulizer 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]
(3) Polyhydric alcohol (C):
Tris- (2-hydroxylethyl) isocyanurate
[THEIC-PW (manufactured by Shikoku Chemicals Co., Ltd.)]
(4) Phenylindole (D ₂ )
2-Phenylindole (Wako Pure Chemical Industries, Ltd.)
(5) Epoxy compound:
Epoxidized soybean oil
[W-100EL (Dainippon Ink Chemical Co., Ltd.)]

Claims (7)

  (A) 100 parts by weight of an epoxy group-containing acrylic resin having an epoxy equivalent of 100 to less than 250, and (B) 0.5 to 70 parts by weight of an aminocrotonic acid ester as main stabilizer components, For a chlorine-containing polymer comprising (C) 0.5 to 70 parts by weight of a polyhydric alcohol and / or (D) 0.1 to 70 parts by weight of a hindered amine or phenylindole as an auxiliary component Stabilizer.   The stabilizer for chlorine-containing polymers according to claim 1, wherein the epoxy group-containing acrylic resin (A) has an epoxy equivalent of 100 to 200.   3. The chlorine-containing polymer according to claim 1, wherein the polyhydric alcohol (C) is at least one selected from the group consisting of pentaerythritol, dipentaerythritol or a partial ester thereof, and a hydroxyl group-containing isocyanurate. Stabilizer.   The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 3, wherein the hindered amine (D) is a tetramethylpiperidine-based hindered amine.   The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 4, comprising (C) a polyhydric alcohol and (D) a hindered amine and / or phenylindole as the auxiliary component.   The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 5, wherein the phenylindole is 2-phenylindole.   The chlorine-containing polymer stabilizer according to any one of claims 1 to 6 is blended with the chlorine-containing polymer, and the chlorine-containing polymer stabilizer is an epoxy group-containing acrylic resin in the stabilizer. A chlorine-containing polymer composition, wherein (A) is blended in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.