WO2008075510A1 - Stabilizer for chlorinated polymer and chlorinated-polymer composition - Google Patents

Stabilizer for chlorinated polymer and chlorinated-polymer composition Download PDF

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Publication number
WO2008075510A1
WO2008075510A1 PCT/JP2007/071854 JP2007071854W WO2008075510A1 WO 2008075510 A1 WO2008075510 A1 WO 2008075510A1 JP 2007071854 W JP2007071854 W JP 2007071854W WO 2008075510 A1 WO2008075510 A1 WO 2008075510A1
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Prior art keywords
stabilizer
chlorine
containing polymer
component
group
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PCT/JP2007/071854
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French (fr)
Japanese (ja)
Inventor
Seiji Wakaki
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Mizusawa Industrial Chemicals, Ltd.
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Priority claimed from JP2007202029A external-priority patent/JP5294586B2/en
Application filed by Mizusawa Industrial Chemicals, Ltd. filed Critical Mizusawa Industrial Chemicals, Ltd.
Publication of WO2008075510A1 publication Critical patent/WO2008075510A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings

Definitions

  • the present invention relates to a stabilizer for a chlorine-containing polymer, and more specifically, a non-metallic stabilizer for a chlorine-containing polymer that does not contain a metal component, and the stabilizer is blended and thermally stabilized.
  • the present invention relates to a modified chlorine-containing polymer composition.
  • metal salts or metal oxides such as Pb, Cd, and Sn have been widely used as stabilizers for chlorine-containing polymers such as polyvinyl chloride, but from the viewpoint of adverse effects on the environment.
  • the use of these metal salts or metal oxides has been avoided, and instead of these, calcium and zinc-based stabilizers have been used.
  • environmental issues have become more important and the use of zinc tends to be restricted.
  • non-metallic stabilizers for chlorine-containing polymers are attracting attention, and typical examples of such non-metallic stabilizers include aminouracil and its derivatives such as amino crotonates.
  • System stabilizers are known (see Patent Documents 1 and 2).
  • the amino stabilizers as described above are unsatisfactory in heat resistance or heat durability even if they can effectively suppress initial coloration immediately after kneading and molding when blended with a chlorine-containing polymer. If held at a high temperature, the color changes immediately, and after a certain amount of time has passed, the color changes to black.
  • Patent Document 3 describes amino alcohol, dihydropyridine, aminocrotonate, aminouracil, and phenyl.
  • a chlorine-containing polymer composition in which at least two selected from the group consisting of indole and a perchlorate containing substantially no metal is blended has been proposed, and this chlorine-containing polymer composition includes It is described that the epoxy compound may be blended up to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.
  • Patent Document 1 Japanese Patent Publication No. BS 5 7-2 3 6 4 7
  • Patent Document 2 Japanese Patent Application Laid-Open No. Sho 6 1-2 4 7 7 8
  • a chlorine-containing polymer composition containing a non-metallic stabilizer that does not contain a metal component can improve the heat resistance or heat resistance to some extent, but the degree is still insufficient.
  • the coloring tendency when kept in a high temperature atmosphere is not effectively suppressed.
  • the chlorine-containing polymer composition of Patent Document 3 described above when it is held in a high-temperature atmosphere, it takes a considerable amount of time to change to black, but the degree of coloring is relatively high (short time) It becomes a state close to black), and further improvement is necessary.
  • 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 must be used such as perchlorate.
  • 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.
  • the present inventors have added a two-component combination of a specific epoxy group-containing acryl resin and an amino compound, or further added a specific auxiliary component. It is surprising that the combination of ternary components significantly improves heat resistance and heat durability and effectively suppresses the tendency to color when held at high temperature (185 ° C) for a long time. In addition, the inventors have found that the initial colorability can be further effectively suppressed, and have completed the present invention.
  • a stabilizer for a two-component chlorine-containing polymer is provided.
  • the total amount (B + C) of the amino stabilizer (B) and the auxiliary component (C) is in the range of 0.5 to 95 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin (A). And the weight ratio of the auxiliary component (C) to the amino stabilizer (B) [CZ
  • a stabilizer for a three-component chlorine-containing polymer characterized in that (B + C)] is blended so as to be 0.30 to 0.95.
  • the stabilizer for chlorine-containing polymer of the present invention is (1)
  • the epoxy equivalent of the epoxy group-containing acrylic resin is in the range of not less than 100, less than 25,
  • Aminouracil or its derivative (B) is represented by the following general formula (1):
  • R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, a phenyl group substituted with a halogen, and R 1 and R 2 are They may be the same as or different from each other,
  • auxiliary component (C) is 2-phenylindole
  • the two-component or three-component stabilizer for the chlorine-containing polymer is further blended with the chlorine-containing polymer, and the stabilizer for the chlorine-containing polymer is the stabilizer.
  • a chlorine-containing polymer composition characterized in that the epoxy group-containing acrylic resin (A) therein is blended in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer. Is done.
  • the stabilizer for a chlorine-containing polymer of the present invention can effectively suppress the initial coloring of the chlorine-containing polymer with a combination of only two components or three components, and at the same time has excellent heat resistance or heat durability, which will be described later.
  • the chlorine-containing polymer composition containing this stabilizer is held in a high temperature atmosphere, it takes a long time to discolor to black, and the state is maintained in a high temperature atmosphere.
  • the degree of coloring at is very small and can be maintained for a long time in an achromatic state.
  • the stabilizer of the present invention is a non-metallic stabilizer that does not contain lead, zinc, tin, or other metal components, and does not adversely affect the environment.
  • a compound that is difficult to handle and has a safety problem is not blended, and its production is very easy.
  • a two-component compound is extremely advantageous in terms of cost.
  • the stabilizer for a chlorine-containing polymer of the present invention contains only two components (A) an epoxy group-containing acryl resin and (B) an amino-based stabilizer component in a predetermined amount ratio. By using it, it is possible to remarkably improve the effect of preventing the initial coloring and the heat resistance or heat durability.
  • the epoxy group-containing acryl resin used in the present invention is the main component of this non-metallic stabilizer, and contributes particularly to improvement of heat resistance or heat durability.
  • an epoxy group-containing acrylic resin having a (meth) acrylic ester unit such as (meth) acrylic acid glycidyl is selectively used.
  • a bisphenol type epoxy resin when used, the time to reach blackening when kept in a high temperature atmosphere may be relatively long. The degree of coloring in a short time is increased, and sufficient heat resistance cannot be obtained.
  • an epoxy group-containing acrylic resin when used, not only the time to reach blackening is further extended, but also the degree of coloring in the middle is considerably suppressed, and extremely excellent heat durability is achieved. Obtainable.
  • Examples of the epoxy group-containing acrylic resin used in the present invention include polymers comprising at least one of glycidyl (meth) acrylate,) 8-methylglycidyl (meth) acrylate, and acylglycidyl (meth) acrylate, and the like.
  • a copolymer of a polymer and an alkyl (meth) acrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, etc. Can be mentioned.
  • the molecular weight (weight average) of these epoxy group-containing acryl resins is preferably from 1,000 to 100,000.
  • M-proof G-01100 (Nippon Yushi Co., Ltd .; epoxy equivalent 1700), Metaprene KP-6562 (Mitsubishi Rayon Co., Ltd .; epoxy equivalent 2 0 0), Blemmer CP-5 0
  • M-proof G-01100 (Nippon Yushi Co., Ltd .; epoxy equivalent 1700)
  • Metaprene KP-6562 (Mitsubishi Rayon Co., Ltd .; epoxy equivalent 2 0 0)
  • Blemmer CP-5 0 Commercially available products such as M (manufactured by NOF Corporation; epoxy equivalent 3 10) are preferably used.
  • the epoxy equivalent of such an epoxy group-containing acryl resin is preferably in the range of 100 to 500, particularly in the range of 100 to less than 25, and if the epoxy equivalent is out of the above range, the heat resistance is maintained. The performance is greatly reduced.
  • the amino stabilizer component used in the present invention is aminouracil or a derivative thereof, and this amino stabilizer component is known to have a function of preventing the initial coloration of the vinyl chloride polymer. Then, the combination with the epoxy group-containing acrylic resin (A) described above can not only effectively prevent the initial coloring, but also can significantly improve the heat resistance durability.
  • the amino stabilizer component is used in an amount of 0.5 to 50 parts by weight, particularly 10 to 30 parts by weight, per 100 parts by weight of the epoxy group-containing acryl resin. Is done. When the amount is less than this range, the initial coloration prevention performance deteriorates. When the amount is more 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 it deteriorates to black. The time to end up will be faster.
  • aminouracil or a derivative thereof has the general formula (1), that is,
  • R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, a phenyl group substituted with a halogen, and R 1 and R 2 are
  • the alkyl group may be the same or different, and the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, or an octyl group, and the aralkyl group may be a benzyl group, a phenethyl group, or a cumyl group.
  • Examples of the alkenyl group include a vinyl group and a allyl group
  • examples of the substituted or unsubstituted phenyl group include a phenyl group, a tolyl group, a xylyl group, and a chlorophenyl group.
  • aminouracil or derivatives thereof include 1,3-dimethyl-4-aminouracil, 1,3-jetyl-4-aminouracil, 1,3-diisopropyl-4-aminouracil, In addition, 1,3-dimethyl-4-thiouracil, 1,3-jetyl-4-thiouracil, 1,3-diisopropyl-4-thiouracil can be used. Preferably, 1,3-dimethyl-1,4-aminouracil is used.
  • the stabilizer for a chlorine-containing polymer of the present invention can remarkably improve heat resistance and heat durability by using the two components as described above.
  • an auxiliary component composed of (C) phenylindole heat resistance or heat resistance can be maintained. Property can be further improved.
  • the phenylindole used as an auxiliary component in the present invention contributes particularly to the improvement of heat durability, and the use of phenylindole can improve the initial colorability in addition to the heat resistance durability. it can.
  • phenylindole examples include the following.
  • 2-phenylindole is particularly preferred.
  • the auxiliary component (C) is an amino-based stabilizer (B).
  • the auxiliary component (C) in a total amount (B + C) in the range of 0.5 to 95 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin, and the auxiliary component (C) and It is blended in such a ratio that the weight ratio [CZ (B + C)] to the amino stabilizer (B) is 0.30 to 0.95.
  • auxiliary component (C) When the auxiliary component (C) is blended in a larger amount than this range, the initial coloration prevention performance decreases, and when used in a smaller amount than the above range, the heat resistance persistence decreases, for example, in a high temperature atmosphere.
  • the coloring tendency cannot be suppressed, and the time for deterioration to black becomes faster.
  • the chlorine-containing polymer composition of the present invention has various additives known per se, such as plasticizers, phenolic oxidations, and the like, as long as the excellent characteristics obtained by the non-metallic stabilizer component described above are not impaired.
  • additives such as inhibitors, lubricants, flame retardants, fillers, colorants, UV absorbers, antistatic agents, modifying resins or rubbers, impact strengthening agents, polyhydric alcohols, nitrogen-containing compounds, and other organic compounding agents
  • the resin compounding agent can be compounded according to a formulation known per se.
  • Examples of the chlorine-containing polymer in which each component of the above-mentioned nonmetallic stabilizer is blended include polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, and chlorinated rubber.
  • Vinyl chloride-vinyl acetate copolymer Vinyl chloride-ethylene copolymer, Vinyl chloride-propylene copolymer, Vinyl styrene copolymer, Vinyl chloride-isobutylene copolymer, Vinyl chloride monochloride vinylidene chloride copolymer Polymer, Vinyl chloride-styrene-maleic anhydride terpolymer, Vinyl chloride-styrene-acrylonitrile copolymer, Vinyl chloride-butadiene copolymer, Chlorinated vinyl-propylene chloride copolymer, Vinyl chloride-vinylidene chloride Monoacetic acid Vinyl terpolymer, vinyl chloride monoacrylate copolymer, vinyl chloride Rumaleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, and internally plasticized polyvinyl chloride.
  • the chlorine-containing polymer as described above may be a blend of various resins.
  • resins include monoolefins such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene.
  • monoolefins such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene.
  • Polymers; olefin copolymers such as ethylene monoacetate vinyl copo
  • the chlorine-containing polymer composition of the present invention is obtained by blending the above-mentioned non-metallic stabilizer with the chlorine-containing polymer as described above.
  • an epoxy group-containing acryl resin ( A) is added to the chlorine-containing polymer such that the amount of A) is from 1.0 to 30 parts by weight, particularly from 1.0 to 10 parts by weight, per 100 parts by weight of the chlorine-containing polymer.
  • various characteristics of each component are exerted in a well-balanced manner and are synergistically enhanced, and excellent initial coloration prevention properties, heat resistance and heat resistance durability are imparted to the chlorine-containing polymer.
  • 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 conservation.
  • the chlorine-containing polymer composition of the present invention is produced by melt-kneading the various compounding agents such as the above-mentioned non-metallic stabilizer components, and is formed into a film or sheet or other shape by means known per se. Molded and used for various purposes.
  • the invention is illustrated by the following examples and comparative examples.
  • evaluation method of the composition prepared by the Example and the comparative example is as follows.
  • the stabilizer of the formulation shown in each example or comparative example was mixed with vinyl chloride resin and polyethylene wax at a temperature of 160 ° C. for 5 minutes.
  • a uniform vinyl chloride gel with a thickness of 1 mm was made by kneading with a roll mill.
  • Vinyl chloride resin (polymerization degree 1050); 100 parts by weight
  • test piece was put into a gear oven set at 1 85 ° C. and taken out every predetermined time, and the colored state was visually observed from the initial stage until blackening was judged.
  • the color of the sea bream was evaluated in the following seven stages.
  • Resin 1 Malproof G—01 1 00 (Nippon Yushi Co., Ltd .: Epoxy equivalent 1 70)
  • Resin 2 Metaprene KP-6562 (Mitsubishi Rayon Co., Ltd .; epoxy equivalent 200)
  • Resin 3 Blemma I CP-5 OM (Nippon Yushi Co., Ltd .:
  • Resin 4 Epomic R— 1 40 (Mitsui Chemicals, Inc .:
  • Epoxidized soybean oil W-100EL (Dainippon Ink Chemical Co., Ltd.)
  • Resin 1 Maple-F G-01100 (Eho. Xi equivalent 170)
  • Aminouracil 1,3-cy'methyl-4-amino-uracil (manufactured by Tateyama Kasei Co., Ltd.) [0043]
  • Resin 1 M-proof G-01100 (Ejo. Pheasant equivalent 1 TO)
  • Resin 2 Metaphlene KP-6562 (Ejo's xy equivalent 200)
  • Resin 3 Prelemma-GP-50M (Ejo's pheasant equivalent 310)
  • Resin 4 I'Mick R-140 has xy equivalent 190)
  • Ejo'-oxygenated soybean oil W-100EL (manufactured by Dainippon Ink and Chemicals) 2-Fluindle (Wako Pure Chemical Industries, Ltd.)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A stabilizer for chlorinated polymers which is characterized by comprising two ingredients, i.e., (A) 100 parts by weight of an epoxidized acrylic resin having an epoxy equivalent of 100-500 and (B) 0.5-50 parts by weight of an amino compound stabilizer ingredient selected among aminouracil and derivatives thereof. This stabilizer is free from metal and exerts no adverse influence on the environment. Furthermore, it is highly effective in preventing initial discoloration and is high in heat resistance or heat resistance retentivity. This stabilizer can effectively diminish the tendency of vinyl chloride resins and the like to discolor when held at a high temperature for long.

Description

明細書 塩素含有重合体用安定剤及び塩素含有重合体組成物  Specification Stabilizer for chlorine-containing polymer and chlorine-containing polymer composition
《技術分野》 "Technical field"
[0001]  [0001]
本発明は、 塩素含有重合体用安定剤に関するものであり、 より詳細には、 金属 成分を含有していない非金属系の塩素含有重合体用安定剤及び該安定剤が配合さ れて熱安定化された塩素含有重合体組成物に関するものである。  The present invention relates to a stabilizer for a chlorine-containing polymer, and more specifically, a non-metallic stabilizer for a chlorine-containing polymer that does not contain a metal component, and the stabilizer is blended and thermally stabilized. The present invention relates to a modified chlorine-containing polymer composition.
《背景技術》 《Background technology》
[0002]  [0002]
従来、 ポリ塩化ビニル等の塩素含有重合体の安定剤としては、 P b , C d， S n等の金属塩乃至金属酸化物などが広く使用されていたが、 環境に対する悪影 響の点から、 これらの金属塩乃至金属酸化物の使用が避けられるようになり、 こ れらの代わりに、 カルシウムや亜鉛系の安定剤が使用されるようになってきた。 しかしながら、 近年では環境問題の重要性が一層高まり、 亜鉛の使用が制限され る傾向にある。  Conventionally, metal salts or metal oxides such as Pb, Cd, and Sn have been widely used as stabilizers for chlorine-containing polymers such as polyvinyl chloride, but from the viewpoint of adverse effects on the environment. The use of these metal salts or metal oxides has been avoided, and instead of these, calcium and zinc-based stabilizers have been used. However, in recent years, environmental issues have become more important and the use of zinc tends to be restricted.
[0003]  [0003]
従って、 現在では、 非金属系の塩素含有重合体用安定剤が注目されており、 こ のような非金属系安定剤の代表的なものとして、 アミノウラシル乃至その誘導体 ゃァミノクロトン酸エステルなどのアミノ系安定剤が知られている（特許文献 1、 2参照） 。  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 such as amino crotonates. System stabilizers are known (see Patent Documents 1 and 2).
[0004]  [0004]
しかしながら、 上記のようなアミノ系安定剤では、 塩素含有重合体に配合した とき、混練'成形直後における初期着色を有効に抑制することができるとしても、 耐熱性或いは耐熱持続性が不満足であり、 高温に保持されると、 直ちに変色を生 じてしまい、 ある程度の時間が経過すると、 最終的には黒色にまで変色してしま うという欠点がある。 [0005] However, the amino stabilizers as described above are unsatisfactory in heat resistance or heat durability even if they can effectively suppress initial coloration immediately after kneading and molding when blended with a chlorine-containing polymer. If held at a high temperature, the color changes immediately, and after a certain amount of time has passed, the color changes to black. [0005]
上記のような欠点を改善するために、 種々の有機系安定剤についての検討がな されており、 例えば、 特許文献 3には、 ァミノアルコール、 ジヒドロピリジン、 アミノクロトネート、 アミノウラシル、 及びフエニルインドールからなる群より 選択された少なくとも 2種と、 実質的に金属を含まない過塩素酸塩とが配合され た塩素含有重合体組成物が提案されており、 この塩素含有重合体組成物には、 ェ ポキシ化合物を、 塩素含有重合体 1 0 0重量部当り 3 0重量部まで配合してよい ことが記載されている。  In order to improve the above drawbacks, various organic stabilizers have been studied. For example, Patent Document 3 describes amino alcohol, dihydropyridine, aminocrotonate, aminouracil, and phenyl. A chlorine-containing polymer composition in which at least two selected from the group consisting of indole and a perchlorate containing substantially no metal is blended has been proposed, and this chlorine-containing polymer composition includes It is described that the epoxy compound may be blended up to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.
[0006]  [0006]
特許文献 1 ： 特開 BS 5 7— 2 3 6 4 7号公報  Patent Document 1: Japanese Patent Publication No. BS 5 7-2 3 6 4 7
特許文献 2 ： 特開昭 6 1 - 2 4 7 7 8号公報  Patent Document 2: Japanese Patent Application Laid-Open No. Sho 6 1-2 4 7 7 8
¼許文献 3 ： 特開 2 0 0 6— 1 0 4 4 7 4号公報  ¼ Permitted Document 3: Japanese Patent Laid-Open No. 2 0 06-1 0 4 4 7 4
《発明の開示》 << Disclosure of Invention >>
[0007]  [0007]
しかしながら、 金属成分を含有していない非金属系の安定剤を配合した塩素含 有重合体組成物では、 ある程度、 耐熱性乃至耐熱持続性を向上させ得るものの、 その程度は未だ不十分であり、 特に、 高温雰囲気に保持したときの着色傾向が有 効に抑制されていない。 例えば、 上記特許文献 3の塩素含有重合体組成物では、 高温雰囲気に保持したとき、 黒色に変色するまでにはかなりの長時間要するもの の、 比較的短時間で着色の程度が高く （短時間で黒色に近い状態となる） 、 さら なる改善が必要である。 また、 特許文献 3の塩素含有重合体組成物では、 過塩素 酸塩の如き、 取り扱いが困難であり且つ安全性に難点のある化合物を使用しなけ ればならないという欠点もある。  However, a chlorine-containing polymer composition containing a non-metallic stabilizer that does not contain a metal component can improve the heat resistance or heat resistance to some extent, but the degree is still insufficient. In particular, 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 considerable amount of time to change to black, but the degree of coloring is relatively high (short time) It becomes a state close to black), and 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 must be used such as perchlorate.
[0008]  [0008]
従って、 本発明の目的は、 初期着色の防止効果が高く、 しかも耐熱性乃至耐熱 持続性が高く、 高温に長時間保持したときの着色傾向を有効に抑制し得る非金属 系の塩素含有重合体用安定剤及び該安定剤が配合された塩素含有重合体組成物を 提供することにある。 [0009] 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. [0009]
本発明者等は、 非金属系の安定剤について様々な検討を行った結果、 特定のェ ポキシ基含有ァクリル樹脂とアミノ系化合物との二成分系の組み合わせ、 或いは さらに特定の助剤成分を加えた三成分系の組み合わせによリ、 極めて意外なこと に、 耐熱性乃至耐熱持続性が顕著に向上し、 高温 （1 85°C) に長時間保持した ときの着色傾向が有効に抑制されるばかりか、 初期着色性も一層効果的に抑制さ れることを見出し、 本発明を完成させるに至った。  As a result of various studies on non-metallic stabilizers, the present inventors have added a two-component combination of a specific epoxy group-containing acryl resin and an amino compound, or further added a specific auxiliary component. It is surprising that the combination of ternary components significantly improves heat resistance and heat durability and effectively suppresses the tendency to color when held at high temperature (185 ° C) for a long time. In addition, the inventors have found that the initial colorability can be further effectively suppressed, and have completed the present invention.
[0010]  [0010]
本発明によれば、  According to the present invention,
(A) 1 00乃至 500のエポキシ当量を有しているエポキシ基含有ァクリル 樹脂 1 00重量部；及び  (A) 100 parts by weight of an epoxy group-containing acryl resin having an epoxy equivalent of 100 to 500; and
(B) ァミノゥラシル乃至その誘導体から選択されたァミノ系安定剤成分 0. 5乃至 50重量部；  (B) 0.5 to 50 parts by weight of an amino stabilizer component selected from amaminouracil or a derivative thereof;
からなることを特徴とする二成分系塩素含有重合体用安定剤が提供される。 A stabilizer for a two-component chlorine-containing polymer is provided.
[0011]  [0011]
本発明によれば、 また、  According to the invention,
(A) 1 00乃至 500のエポキシ当量を有しているエポキシ基含有アクリル 樹脂；  (A) an epoxy group-containing acrylic resin having an epoxy equivalent of 100 to 500;
(B) アミノウラシル乃至その誘導体から選択されたァミノ系安定剤成分：及 び  (B) an amino stabilizer component selected from aminouracil or a derivative thereof: and
(C) フ Iニルインドールからなる助剤成分；  (C) Auxiliary component consisting of Hu Nilindole;
からなリ、 Karanari,
前記アミノ系安定剤 （B) 及び助剤成分 （C) は、 その合計量 （B + C) が、 前記エポキシ基含有アクリル樹脂 （A) 1 00重量部当り 0. 5乃至 95重量部 の範囲にあり、 且つ該助剤成分 （C) とァミノ系安定剤 （B) との重量比 [CZ The total amount (B + C) of the amino stabilizer (B) and the auxiliary component (C) is in the range of 0.5 to 95 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin (A). And the weight ratio of the auxiliary component (C) to the amino stabilizer (B) [CZ
(B + C) ] が 0. 30乃至 0. 95となるように配合されていることを特徴と する三成分系塩素含有重合体用安定剤が提供される。 There is provided a stabilizer for a three-component chlorine-containing polymer, characterized in that (B + C)] is blended so as to be 0.30 to 0.95.
[0012]  [0012]
本発明の塩素含有重合体用安定剤は、 ( 1 ) 前記エポキシ基含有アクリル樹脂のエポキシ当量が 1 0 0以上、 2 5 0未 満の範囲にあること、 The stabilizer for chlorine-containing polymer of the present invention is (1) The epoxy equivalent of the epoxy group-containing acrylic resin is in the range of not less than 100, less than 25,
( 2 ) アミノウラシル乃至その誘導体 （B) が、 下記一般式 （1 ) ：  (2) Aminouracil or its derivative (B) is represented by the following general formula (1):
Figure imgf000005_0001
式中、 R 1及び R 2は、炭素数 1乃至 8のアルキル基、 ァラルキル基、 アル ケニル基及び非置換或いはアルキル基、 ハロゲンで置換されたフエニル 基を示し、 R 1と R 2とは、 互いに同一でも異なっていてもよい、 で表される化合物であること、
Figure imgf000005_0001
In the formula, R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, a phenyl group substituted with a halogen, and R 1 and R 2 are They may be the same as or different from each other,
( 3 ) 助剤成分 （C ) が 2—フエニルインドールであること、  (3) The auxiliary component (C) is 2-phenylindole,
が好適である。 Is preferred.
[0013]  [0013]
本発明によれば、 さらに、 塩素含有重合体に、 前記二成分系或いは三成分系の 塩素含有重合体用安定剤が配合されており、 該塩素含有重合体用安定剤は、 該安 定剤中のエポキシ基含有アクリル樹脂 （A) が塩素含有重合体 1 0 0重量部当り 1 . 0乃至 3 0重量部となる量で配合されていることを特徴とする塩素含有重合 体組成物が提供される。  According to the present invention, the two-component or three-component stabilizer for the chlorine-containing polymer is further blended with the chlorine-containing polymer, and the stabilizer for the chlorine-containing polymer is the stabilizer. Provided is a chlorine-containing polymer composition characterized in that the epoxy group-containing acrylic resin (A) therein is blended in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer. Is done.
[0014]  [0014]
本発明の塩素含有重合体用安定剤は、 僅か二成分或いは三成分の組み合わせで 塩素含有重合体の初期着色を有効に抑制し得ると同時に、 優れた耐熱性乃至耐熱 持続性を有し、 後述する実施例からも明らかな通り、 この安定剤が配合された塩 素含有重合体組成物を高温雰囲気に保持した場合において、 黒色に変色するまで に長時間要するばかりか、 高温雰囲気に保持した状態での着色の程度も極めて小 さく、 無彩色に近い状態に長時間維持することができる。  The stabilizer for a chlorine-containing polymer of the present invention can effectively suppress the initial coloring of the chlorine-containing polymer with a combination of only two components or three components, and at the same time has excellent heat resistance or heat durability, which will be described later. As is clear from the examples, in the case where the chlorine-containing polymer composition containing this stabilizer is held in a high temperature atmosphere, it takes a long time to discolor to black, and the state is maintained in a high temperature atmosphere. The degree of coloring at is very small and can be maintained for a long time in an achromatic state.
[0015] また、 本発明の安定剤は、 鉛、 亜鉛、 錫等の金属成分を含有していない非金属 系の安定剤であり、 環境に対して悪影響を及ぼさないばかりか、 さらには過塩素 酸塩のような取り扱い困難で且つ安全性に問題のある化合物も配合されておらず、 その製造も至って容易であり、 特に二成分系のものは、 コスト的にも極めて有利 である。 [0015] In addition, the stabilizer of the present invention is a non-metallic stabilizer that does not contain lead, zinc, tin, or other metal components, and does not adversely affect the environment. Such a compound that is difficult to handle and has a safety problem is not blended, and its production is very easy. In particular, a two-component compound is extremely advantageous in terms of cost.
《発明が実施しょうとする最良の形態》 << Best Mode for Invention to Implement >>
[0016]  [0016]
<二成分系安定剤 > <Two-component stabilizer>
本発明の塩素含有重合体用安定剤は、（A )エポキシ基含有ァクリル樹脂と（B ) アミノ系安定剤成分との二成分のみを所定量比で含有するものであり、 僅か二成 分の使用で、 初期着色防止効果や耐熱性乃至耐熱持続性を著しく向上させること ができる。  The stabilizer for a chlorine-containing polymer of the present invention contains only two components (A) an epoxy group-containing acryl resin and (B) an amino-based stabilizer component in a predetermined amount ratio. By using it, it is possible to remarkably improve the effect of preventing the initial coloring and the heat resistance or heat durability.
[0017]  [0017]
( A ) エポキシ基含有アクリル樹脂：  (A) Epoxy group-containing acrylic resin:
本発明において用いるエポキシ基含有ァクリル樹脂は、 この非金属系安定剤の 主成分であり、 特に耐熱性乃至耐熱持続性の向上に寄与する。  The epoxy group-containing acryl resin used in the present invention is the main component of this non-metallic stabilizer, and contributes particularly to improvement of heat resistance or heat durability.
[0018]  [0018]
かかるエポキシ基含有ァクリル樹脂としては、 （メタ） ァクリル酸グリシジル などの （メタ） アクリル酸エステル単位を有しているエポキシ基含有アクリル樹 脂が選択的に使用され、 このようなエポキシ基含有アクリル樹脂は、 例えば特開 昭 6 3— 1 0 6 4 8号公報などに開示されている。 即ち、 後述する実施例及び比 較例から明らかなように、 ビスフエノール型エポキシ樹脂を使用した場合には、 高温雰囲気に保持したときの黒色化に達するまでの時間は比較的長くなるにして も、 短時間での着色の程度が高くなつてしまい、 充分な耐熱持続性を得ることが できない。 これに対して、 エポキシ基含有アクリル樹脂を使用した場合には、 黒 色化に達するまでの時間が更に延長するばかりか、 中間での着色の程度もかなり 抑制され、 著しく優れた耐熱持続性を得ることができる。  As such an epoxy group-containing acryl resin, an epoxy group-containing acrylic resin having a (meth) acrylic ester unit such as (meth) acrylic acid glycidyl is selectively used. Is disclosed in, for example, Japanese Patent Application Laid-Open No. 63-161084. That is, as will be apparent from the examples and comparative examples described later, when a bisphenol type epoxy resin is used, the time to reach blackening when kept in a high temperature atmosphere may be relatively long. The degree of coloring in a short time is increased, and sufficient heat resistance cannot be obtained. On the other hand, when an epoxy group-containing acrylic resin is used, not only the time to reach blackening is further extended, but also the degree of coloring in the middle is considerably suppressed, and extremely excellent heat durability is achieved. Obtainable.
[0019] 本発明で用いられるエポキシ基含有アクリル樹脂としては、 例えば、 グリシジ ル （メタ） ァクリレート、 ）8 -メチルグリシジル （メタ） ァクリレ一卜、 ァシルグ リシジル （メタ） ァクリレートの少なくともいずれかからなる重合体、 これら重 合体と、 メチルァクリレート、 メチルメタァクリレート、 ェチルァクリレート、 ェチルメタァクリレート等のアルキル（メタ）ァクリレート、ァクリルニトリル、 メタァクリロ二トリル等との共重合体等が挙げられる。 これらのエポキシ基含有 ァクリル樹脂の分子量（重量平均）は、 1 , 0 0 0〜 1 0 0 , 0 0 0が好ましい。 具体的には、マ一プルーフ G- 01100 (日本油脂（株）製；エポキシ当量 1 7 0 )、 メタプレン KP-6562 (三菱レイヨン （株） 製；エポキシ当量 2 0 0 ) 、 ブレンマー C P - 5 0 M (日本油脂 （株） 製；エポキシ当量 3 1 0 ) 等の商品名で市販され ているものが好適に使用される。 [0019] Examples of the epoxy group-containing acrylic resin used in the present invention include polymers comprising at least one of glycidyl (meth) acrylate,) 8-methylglycidyl (meth) acrylate, and acylglycidyl (meth) acrylate, and the like. A copolymer of a polymer and an alkyl (meth) acrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, etc. Can be mentioned. The molecular weight (weight average) of these epoxy group-containing acryl resins is preferably from 1,000 to 100,000. Specifically, M-proof G-01100 (Nippon Yushi Co., Ltd .; epoxy equivalent 1700), Metaprene KP-6562 (Mitsubishi Rayon Co., Ltd .; epoxy equivalent 2 0 0), Blemmer CP-5 0 Commercially available products such as M (manufactured by NOF Corporation; epoxy equivalent 3 10) are preferably used.
[0020]  [0020]
また、かかるエポキシ基含有ァクリル樹脂のエポキシ当量は 1 0 0乃至 5 0 0、 特に 1 0 0以上、 2 5 0未満の範囲にあることが好ましく、 エポキシ当量が上記 範囲外であると、 耐熱持続性が大きく低下してしまう。  In addition, the epoxy equivalent of such an epoxy group-containing acryl resin is preferably in the range of 100 to 500, particularly in the range of 100 to less than 25, and if the epoxy equivalent is out of the above range, the heat resistance is maintained. The performance is greatly reduced.
[0021]  [0021]
( B ) アミノ系安定剤成分：  (B) Amino stabilizer component:
本発明において用いるアミノ系安定剤成分は、 ァミノゥラシル乃至その誘導体 であり、 このアミノ系安定剤成分は、 塩化ビニル系重合体の初期着色を防止する 機能を有するものとして知られているが、 本発明では、 前述したエポキシ基含有 アクリル樹脂 （A ) との組み合わせにより、 初期着色を効果的に防止することが できるばかりか、 耐熱持続性を一層顕著に向上させることができる。  The amino stabilizer component used in the present invention is aminouracil or a derivative thereof, and this amino stabilizer component is known to have a function of preventing the initial coloration of the vinyl chloride polymer. Then, the combination with the epoxy group-containing acrylic resin (A) described above can not only effectively prevent the initial coloring, but also can significantly improve the heat resistance durability.
[0022]  [0022]
本発明において、 上記のアミノ系安定剤成分は、 前述したエポキシ基含有ァク リル樹脂 1 0 0重量部当り、 0 . 5乃至 5 0重量部、 特に 1 0乃至 3 0重量部の 量で使用される。 この範囲よりも少量の場合には、 初期着色防止性能が低下し、 また上記範囲よりも多量に使用すると、 初期着色を効果的に防止することはでき ても、 耐熱持続性が低下してしまい、 例えば、 高温雰囲気に塩素含有重合体組成 物を保持したときの着色傾向を抑制することができず、 また黒色にまで劣化して しまう時間が速くなつてしまう。 In the present invention, the amino stabilizer component is used in an amount of 0.5 to 50 parts by weight, particularly 10 to 30 parts by weight, per 100 parts by weight of the epoxy group-containing acryl resin. Is done. When the amount is less than this range, the initial coloration prevention performance deteriorates. When the amount is more 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 it deteriorates to black. The time to end up will be faster.
[0023]  [0023]
かかるァミノ系安定剤の内、アミノウラシル乃至その誘導体は、前記一般式（ 1 )、 即ち、  Among such amino stabilizers, aminouracil or a derivative thereof has the general formula (1), that is,
Figure imgf000008_0001
Figure imgf000008_0001
式中、 R 1及び R 2は、炭素数 1乃至 8のアルキル基、 ァラルキル基、 アル ケニル基及び非置換或いはアルキル基、 ハロゲンで置換されたフエニル 基を示し、 R 1と R 2とは、 互いに同一でも異なっていてもよい、 で表される化合物であり、 アルキル基としては、 メチル基、 ェチル基、 プロピル 基、ブチル基、ォクチル基が、ァラルキル基としてはべンジル基、フエネチル基、 クミル基が、 アルケニル基としては、 ビニル基、 ァリル基が、 置換または未置換 のフエニル基としては、 フエニル基、 トリル基、 キシリル基、 クロ口フエニル基 が挙げられる。 In the formula, R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, a phenyl group substituted with a halogen, and R 1 and R 2 are The alkyl group may be the same or different, and the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, or an octyl group, and the aralkyl group may be a benzyl group, a phenethyl group, or a cumyl group. Examples of the alkenyl group include a vinyl group and a allyl group, and examples of the substituted or unsubstituted phenyl group include a phenyl group, a tolyl group, a xylyl group, and a chlorophenyl group.
[0024]  [0024]
このようなアミノウラシル乃至その誘導体の具体例としては、 1 , 3—ジメチ ル一4—アミノ一ゥラシル、 1 , 3—ジェチル一 4—アミノーゥラシル、 1 , 3 —ジイソプロ ルー 4一アミノーゥラシルが挙げられ、 更に 1 , 3—ジメチルー 4一チォゥラシル、 1 , 3—ジェチル一 4—チォゥラシル、 1 , 3—ジイソプロ ピル一 4—チォ一ゥラシルも使用できる。 好ましくは 1 , 3—ジメチル一4—ァ ミノーゥラシルが使用される。  Specific examples of such aminouracil or derivatives thereof include 1,3-dimethyl-4-aminouracil, 1,3-jetyl-4-aminouracil, 1,3-diisopropyl-4-aminouracil, In addition, 1,3-dimethyl-4-thiouracil, 1,3-jetyl-4-thiouracil, 1,3-diisopropyl-4-thiouracil can be used. Preferably, 1,3-dimethyl-1,4-aminouracil is used.
[0025]  [0025]
<三成分系安定剤 > <Three-component stabilizer>
本発明の塩素含有重合体用安定剤は、 前記の二成分の使用で、 初期着色防止効 果ゃ耐熱性乃至耐熱持続性を著しく向上させることができる。し力、し、更に、 ( C ) フエニルインドールからなる助剤成分を配合させることで、 耐熱性乃至耐熱持続 性を一層向上させることができる。 The stabilizer for a chlorine-containing polymer of the present invention can remarkably improve heat resistance and heat durability by using the two components as described above. By adding an auxiliary component composed of (C) phenylindole, heat resistance or heat resistance can be maintained. Property can be further improved.
[0026]  [0026]
(C) フヱ二ルインドール  (C) Fuji Ruin Doll
本発明において助剤成分として用いられる、 フエニルインドールは、 特に耐熱 持続性の向上に寄与するものであり、 フヱニルインドールの使用は、 耐熱持続性 のほかに初期着色性も向上させることができる。  The phenylindole used as an auxiliary component in the present invention contributes particularly to the improvement of heat durability, and the use of phenylindole can improve the initial colorability in addition to the heat resistance durability. it can.
[0027]  [0027]
フエニルインドールとしては、 以下のものを例示することができる。  Examples of the phenylindole include the following.
2— ( 4'—ドデシルーフエニル） 一インドール  2— (4'—dodecyl roofenyl) one indole
2 - (3，一メ トキシ一 4，一ヒドロキシ一フエニル） 一インドール  2-(3, 1 methoxy, 1, 1 hydroxy, 1 phenyl) 1 indole
2— (3'—メチル一4，一メ 卜キシ一フエニル） 一インドール  2— (3′—Methyl-1,4, 1-phenyl) 1-indole
2—フエニル一 5—メ トキシ一インドール  2-Phenyl-1-Methoxyindole
2- (3，一ドデシルー 4，一メ 卜キシ一フエニル） 一インドール  2- (3, 1 dodecyl-4, 1 methoxy 1 phenyl) 1 indole
2— (3', 4，一ジエトキシ一フエニル） 一インド一ル  2— (3 ', 4, 1 diethoxy 1 phenyl) 1 India 1
2— (3'—メ トキシ一 4，一プロポキシ一フエニル） 一^ Γンドール  2— (3'—Methoxy-1,4, propoxy, phenyl)
2— (3，一メチル一4，一エトキシ一フエニル） 一インド一ル  2— (3, 1-methyl, 4-, 1-ethoxy, 1-phenyl)
2 - (3，一メ トキシ一 4，一エトキシ一フエニル） 一インドール  2-(3, 1 methoxy, 1, 1 ethoxy, 1 phenyl) 1 indole
2 - (4'—メチル一フエニル） 一インド一ル  2-(4'-methyl monophenyl)
2- (4'—メチル一フエニル） 一5—メチル一インドール  2- (4'-Methyl 1-phenyl) 1-Methyl 1-indole
これらの中では、 特に 2—フエ二ルインドールが好適である。  Of these, 2-phenylindole is particularly preferred.
[0028]  [0028]
前述した （A) 及び （B) 成分に加えて、 このような助剤成分 （C) が配合さ れる三成分系安定剤においては、 助剤成分 （C) は、 アミノ系安定剤 （B) と助 剤成分 （C) との合計量 （B + C) が、 前記エポキシ基含有アクリル樹脂 1 00 重量部当り 0. 5乃至 95重量部の範囲にあり、 且つ該助剤成分 （C) とァミノ 系安定剤 （B) との重量比 [CZ (B + C) ] が 0. 30乃至 0. 95となる割 合で配合される。 この範囲よりも多量に助剤成分 （C) が配合された場合には、 初期着色防止性能が低下し、 また上記範囲より少量で使用すると、 耐熱持続性が 低下してしまい、 例えば、 高温雰囲気に塩素含有重合体組成物を保持したときの 着色傾向を抑制することができず、 また黒色にまで劣化してしまう時間が速くな つてしまう。 In addition to the components (A) and (B) described above, in the three-component stabilizer in which such an auxiliary component (C) is blended, the auxiliary component (C) is an amino-based stabilizer (B). And the auxiliary component (C) in a total amount (B + C) in the range of 0.5 to 95 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin, and the auxiliary component (C) and It is blended in such a ratio that the weight ratio [CZ (B + C)] to the amino stabilizer (B) is 0.30 to 0.95. When the auxiliary component (C) is blended in a larger amount than this range, the initial coloration prevention performance decreases, and when used in a smaller amount than the above range, the heat resistance persistence decreases, for example, in a high temperature atmosphere. When holding a chlorine-containing polymer composition The coloring tendency cannot be suppressed, and the time for deterioration to black becomes faster.
[0029]  [0029]
くその他の成分 > Other ingredients>
本発明の塩素含有重合体組成物は、 上述した非金属系安定剤成分によリ得られ る優れた特性を阻害しない範囲で、それ自体公知の各種添加剤、例えば、可塑剤、 フエノール系酸化防止剤、 滑剤、 難燃剤、 充填剤、 着色剤、 紫外線吸収剤、 帯電 防止剤、 改質用樹脂乃至ゴム、 耐衝撃強化剤、 多価アルコール、 含窒素化合物、 その他有機配合剤等の公知の樹脂配合剤を、 それ自体公知の処方に従って配合で きる。  The chlorine-containing polymer composition of the present invention has various additives known per se, such as plasticizers, phenolic oxidations, and the like, as long as the excellent characteristics obtained by the non-metallic stabilizer component described above are not impaired. Known additives such as inhibitors, lubricants, flame retardants, fillers, colorants, UV absorbers, antistatic agents, modifying resins or rubbers, impact strengthening agents, polyhydric alcohols, nitrogen-containing compounds, and other organic compounding agents The resin compounding agent can be compounded according to a formulation known per se.
[0030]  [0030]
<塩素含有重合体 > <Chlorine-containing polymer>
上述した非金属系安定剤の各成分が配合される塩素含有重合体としては、 例え ば、 ポリ塩化ビニル、 ポリ塩化ビニリデン、 塩素化ポリ塩化ビニル、 塩素化ポリ エチレン、 塩素化ポリプロピレン、 塩素化ゴム、 塩化ビニル一酢酸ビニル共重合 体、 塩化ビニルーエチレン共重合体、 塩化ビニル一プロピレン共重合体、 塩化ビ 二ルースチレン共重合体、 塩化ビニルーイソブチレン共重合体、 塩化ビニル一塩 化ビニリデン共重合体、 塩化ビニル一スチレン一無水マレイン酸三元共重合体、 塩化ビニル一スチレン一ァクリロニトリル共重合体、 塩化ビニルーブタジエン共 重合体、 塩素化ビニルー塩化プロピレン共重合体、 塩化ビニルー塩化ビニリデン 一酢酸ビニル三元共重合体、 塩化ビニル一アクリル酸エステル共重合体、 塩化ビ 二ルーマレイン酸エステル共重合体、 塩化ビニル一メタクリル酸エステル共重合 体、 塩化ビニルーアクリロニトリル共重合体、 内部可塑化ポリ塩化ビニルなど挙 げることができる。  Examples of the chlorine-containing polymer in which each component of the above-mentioned nonmetallic stabilizer is blended include polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, and chlorinated rubber. , Vinyl chloride-vinyl acetate copolymer, Vinyl chloride-ethylene copolymer, Vinyl chloride-propylene copolymer, Vinyl styrene copolymer, Vinyl chloride-isobutylene copolymer, Vinyl chloride monochloride vinylidene chloride copolymer Polymer, Vinyl chloride-styrene-maleic anhydride terpolymer, Vinyl chloride-styrene-acrylonitrile copolymer, Vinyl chloride-butadiene copolymer, Chlorinated vinyl-propylene chloride copolymer, Vinyl chloride-vinylidene chloride Monoacetic acid Vinyl terpolymer, vinyl chloride monoacrylate copolymer, vinyl chloride Rumaleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, and internally plasticized polyvinyl chloride.
また、 上記のような塩素含有重合体は、 各種の樹脂がブレンドされたものであ つてもよく、 このような樹脂としては、 ポリエチレン、 ポリプロピレン、 ポリブ テン、 ポリ一 3—メチルブテンなどのひ一ォレフィン重合体；エチレン一酢酸ビ ニル共重合体、 エチレン一プロピレン共重合体などのォレフィン系共重合体； ポ リスチレン；アクリル樹脂；スチレンと他の単量体 （例えば無水マレイン酸、 ブ タジェン、 アクリロニトリルなど） との共重合体；アクリロニトリルーブタジェ ン一スチレン共重合体；ァクリル酸エステル一ブタジエン一スチレン共重合体； メタクリル酸エステル一ブタジエン一スチレン共重合体；などを挙げることがで きる。 In addition, the chlorine-containing polymer as described above may be a blend of various resins. Examples of such resins include monoolefins such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene. Polymers; olefin copolymers such as ethylene monoacetate vinyl copolymer and ethylene monopropylene copolymer; polystyrene; acrylic resin; styrene and other monomers (eg maleic anhydride, Tagene, acrylonitrile, etc.); acrylonitrile-butadiene-styrene copolymer; acrylate ester-butadiene-styrene copolymer; methacrylate ester-butadiene-styrene copolymer; wear.
[0031]  [0031]
<塩素含有重合体組成物 >  <Chlorine-containing polymer composition>
本発明の塩素含有重合体組成物は、 上記のような塩素含有重合体に、 前述した 非金属系安定剤を配合したものであるが、 該安定剤成分の内、 エポキシ基含有ァ クリル樹脂 （A ) の配合量が、 塩素含有重合体 1 0 0重量部当り、 1 · 0乃至 3 0重量部、 特に 1 . 0乃至 1 0重量部となるように塩素含有重合体に配合され る。 これにより、 各成分の諸特性がバランスよく発揮され、 且つ相乗的に高めら れ、 塩素含有重合体に優れた初期着色防止性、 耐熱性乃至耐熱持続性が付与され ることとなる。 しかも、 重要なことは、 このような優れた特性は、 環境に悪影響 を与える金属塩などを含有する金属系安定剤を配合することなく付与されるので あり、 このため、 本発明の塩素含有重合体組成物は、 環境保全などの観点からも 有用である。  The chlorine-containing polymer composition of the present invention is obtained by blending the above-mentioned non-metallic stabilizer with the chlorine-containing polymer as described above. Among the stabilizer components, an epoxy group-containing acryl resin ( A) is added to the chlorine-containing polymer such that the amount of A) is from 1.0 to 30 parts by weight, particularly from 1.0 to 10 parts by weight, per 100 parts by weight of the chlorine-containing polymer. As a result, various characteristics of each component are exerted in a well-balanced manner and are synergistically enhanced, and excellent initial coloration prevention properties, 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 conservation.
[0032]  [0032]
本発明の塩素含有重合体組成物は、 上述した非金属系安定剤成分等の各種配合 剤を、 溶融混練することにより製造され、 それ自体公知の手段によって、 フィル ム乃至シート、 その他の形状に成形され、 種々の用途に供される。  The chlorine-containing polymer composition of the present invention is produced by melt-kneading the various compounding agents such as the above-mentioned non-metallic stabilizer components, and is formed into a film or sheet or other shape by means known per se. Molded and used for various purposes.
《実施例》 "Example"
[0033]  [0033]
本発明を、 以下の実施例及び比較例により説明する。  The invention is illustrated by the following examples and comparative examples.
尚、 実施例及び比較例で調製された組成物の評価方法は、 以下の通りである。  In addition, the evaluation method of the composition prepared by the Example and the comparative example is as follows.
[0034]  [0034]
( 1 ) ギヤオーブン耐熱試験 （G . O )  (1) Gear oven heat resistance test (G.O)
各実施例或いは比較例で示された配合組成の安定剤を、 下記に示す配合処方に したがって塩化ビニル樹脂及びポリエチレンワックスと、温度 1 6 0 °Cで 5分間、 ロールミルで混練し、 厚さ 1 mmの均一な塩化ビニルジー卜を作成した。 In accordance with the formulation shown below, the stabilizer of the formulation shown in each example or comparative example was mixed with vinyl chloride resin and polyethylene wax at a temperature of 160 ° C. for 5 minutes. A uniform vinyl chloride gel with a thickness of 1 mm was made by kneading with a roll mill.
配合処方：  Formulation:
塩化ビニル樹脂 (重合度 1050) ； 1 00重量部  Vinyl chloride resin (polymerization degree 1050); 100 parts by weight
ポリエチレンワックス （滑剤） ； 0. 8重量部  Polyethylene wax (lubricant); 0.8 parts by weight
各実施例或いは比較例の安定剤；表 1または表 2に記載  Stabilizer of each Example or Comparative Example; listed in Table 1 or Table 2
次に、 1 85°Cに設定したギヤオーブンに試験片を入れ所定時間毎に取り出し、 その着色状態を初期から黒化するまで目視観察し判定した。  Next, the test piece was put into a gear oven set at 1 85 ° C. and taken out every predetermined time, and the colored state was visually observed from the initial stage until blackening was judged.
[0035]  [0035]
シー卜の着色度は下記の 7段階に分けて評価した。  The color of the sea bream was evaluated in the following seven stages.
1 ：白色  1: White
2 ：淡黄色  2: Light yellow
3 ：黄色  3: Yellow
4 ：淡褐色  4: Light brown
5 ：褐色  5: Brown
6 ：濃褐色  6: Dark brown
7 ：黒化  7: Blackening
[0036]  [0036]
<実施例 "！〜 1 3、 比較例 1〜 5 >  <Examples !! to 1 3 and Comparative Examples 1 to 5>
安定剤として下記に示すエポキシ基含有アクリル樹脂 （A) 、 エポキシ樹脂、 エポキシ化合物、 アミノ系安定剤 （B) 或いはフエニルインドール （C) を、 表 1または表 2に記載の配合量で塩化ビニル樹脂に添加し、 ギヤオーブン耐熱試験 を行った。 結果を表 1または 2にそれぞれ示す。 なお、 配合量は塩化ビニル樹脂 1 00重量部当りの量で表している。  Use the following epoxy group-containing acrylic resin (A), epoxy resin, epoxy compound, amino stabilizer (B) or phenylindole (C) as stabilizers in the amounts shown in Table 1 or Table 2. It was added to the resin and a gear oven heat test was conducted. The results are shown in Table 1 or 2, respectively. The compounding amount is expressed as an amount per 100 parts by weight of the vinyl chloride resin.
[0037]  [0037]
(1 ) エポキシ基含有アクリル樹脂 （A)  (1) Epoxy group-containing acrylic resin (A)
樹脂 1 ：マ一プルーフ G— 01 1 00 (日本油脂 （株） 製：エポキシ 当量 1 70)  Resin 1 ： Malproof G—01 1 00 (Nippon Yushi Co., Ltd .: Epoxy equivalent 1 70)
樹脂 2 ： メタプレン KP— 6562 (三菱レイヨン （株） 製； エポキシ当量 200) 樹脂 3 ： ブレンマ一 CP— 5 OM (日本油脂 （株） 製： Resin 2: Metaprene KP-6562 (Mitsubishi Rayon Co., Ltd .; epoxy equivalent 200) Resin 3: Blemma I CP-5 OM (Nippon Yushi Co., Ltd .:
エポキシ当量 31 0)  Epoxy equivalent 31 0)
[0038]  [0038]
(2) エポキシ樹脂  (2) Epoxy resin
樹脂 4 ：ェポミック R— 1 40 (三井化学 （株） 製：  Resin 4: Epomic R— 1 40 (Mitsui Chemicals, Inc .:
エポキシ当量 1 90、 ビスフエノール型、 液状タイプ)  (Epoxy equivalent 1 90, bisphenol type, liquid type)
[0039]  [0039]
(3) エポキシ化合物  (3) Epoxy compounds
エポキシ化大豆油： W- 100EL (大日本インキ化学工業 （株） 製）  Epoxidized soybean oil: W-100EL (Dainippon Ink Chemical Co., Ltd.)
[0040]  [0040]
(4) アミノ系安定剤 （B)  (4) Amino stabilizer (B)
アミノウラシル： 1,3 -ジメチル- 4-アミノ-ゥラシル  Aminouracil: 1,3-dimethyl-4-amino-uracil
(立山化成 （株） 製）  (Manufactured by Tateyama Kasei Co., Ltd.)
[0041]  [0041]
(5) フエ二ルインドール （C)  (5) Huenil Indore (C)
2—フ Iニルインドール （和光純薬工業 （株） 製）  2-Fu Nilindole (Wako Pure Chemical Industries, Ltd.)
[0042]  [0042]
— ，一  —, One
Figure imgf000013_0001
Figure imgf000013_0001
樹脂 1：マ-プル-フ G- 01100(エホ。キシ当量 170)  Resin 1: Maple-F G-01100 (Eho. Xi equivalent 170)
アミノウラシル： 1 ,3-シ'メチル -4-ァミノ-ゥラシル (立山化成 (株)製) [0043] Aminouracil: 1,3-cy'methyl-4-amino-uracil (manufactured by Tateyama Kasei Co., Ltd.) [0043]
一表 2—Table 2—
Figure imgf000014_0001
Figure imgf000014_0001
樹脂 1：マ—プルーフ G - 01100 (エホ。キジ当量 1 TO) 樹脂 2：メタフ'レン KP - 6562 (エホ'キシ当量 200) 樹脂 3：プレンマ- GP-50M (エホ 'キジ当量 310) 樹脂 4： Iホ'ミック R-140はホ 'キシ当量 190)  Resin 1: M-proof G-01100 (Ejo. Pheasant equivalent 1 TO) Resin 2: Metaphlene KP-6562 (Ejo's xy equivalent 200) Resin 3: Prelemma-GP-50M (Ejo's pheasant equivalent 310) Resin 4 : I'Mick R-140 has xy equivalent 190)
エホ'キシ化大豆油: W-100EL (大日本インキ化学工業 (株)製) アミノウラシル： 1 ,3 -シ'メチル -4-アミ ウラシル (立山化成 (株)製） フ 1 インド-ル： 2-フ ルインド-ル (和光純薬工業 (株)製）  Ejo'-oxygenated soybean oil: W-100EL (manufactured by Dainippon Ink and Chemicals) 2-Fluindle (Wako Pure Chemical Industries, Ltd.)

Claims

請求の範囲 The scope of the claims
1. (A) 1 00乃至 500のエポキシ当量を有しているエポキシ基含有 アクリル樹脂 1 00重量部；及び 1. (A) 100 parts by weight of an epoxy group-containing acrylic resin having an epoxy equivalent of 100 to 500; and
(B) アミノウラシル乃至その誘導体から選択されたァミノ系安定剤 成分 0. 5乃至 50重量部；  (B) an amino stabilizer selected from aminouracil or a derivative thereof, component 0.5 to 50 parts by weight;
からなることを特徴とする二成分系塩素含有重合体用安定剤。 A stabilizer for a two-component chlorine-containing polymer comprising:
2. 前記エポキシ基含有アクリル樹脂（A)のエポキシ当量が 1 00以上、 250未満の範囲にある請求項 1に記載の二成分系塩素含有重合体用安定剤。  2. The stabilizer for a two-component chlorine-containing polymer according to claim 1, wherein the epoxy equivalent of the epoxy group-containing acrylic resin (A) is in the range of 100 or more and less than 250.
3. アミノウラシル乃至その誘導体 （B) が、 下記一般式 （1 ) ：  3. Aminouracil or its derivative (B) is represented by the following general formula (1):
Figure imgf000015_0001
Figure imgf000015_0001
式中、 R1及び R2は、炭素数 1乃至 8のアルキル基、 ァラルキル基、 アル ケニル基及び非置換或いはアルキル基、 ハロゲンで置換されたフ: cニル 基を示し、 R1と R2とは、 互いに同一でも異なっていてもよい、 で表される化合物である請求項 1に記載の二成分系塩素含有重合体用安定剤。 In the formula, R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, a halogen substituted phenyl group, and R 1 and R 2 2. The stabilizer for a two-component chlorine-containing polymer according to claim 1, which is a compound represented by the following formula, which may be the same as or different from each other.
4. 塩素含有重合体に、 請求項 1の二成分系塩素含有重合体用安定剤が配 合されており、 該塩素含有重合体用安定剤は、 該安定剤中のエポキシ基含有ァク リル樹脂 （A) が塩素含有重合体 1 00重量部当り 1. 0乃至 30重量部となる 量で配合されていることを特徴とする塩素含有重合体組成物。  4. A stabilizer for a two-component chlorine-containing polymer according to claim 1 is combined with the chlorine-containing polymer, and the stabilizer for the chlorine-containing polymer is an epoxy group-containing acryl in the stabilizer. A chlorine-containing polymer composition, wherein the resin (A) is blended in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.
5. (A) 1 00乃至 500のエポキシ当量を有しているエポキシ基含有 ァクリル樹脂；  5. (A) Epoxy group-containing acryl resin having an epoxy equivalent of 100 to 500;
( B) アミノウラシル乃至その誘導体から選択されたァミノ系安定剤 成分；及び  (B) an amino stabilizer selected from aminouracil or a derivative thereof; and
(C) フエニルインドールからなる助剤成分；  (C) an auxiliary component comprising phenylindole;
からなリ、 前記アミノ系安定剤 （B) 及び助剤成分 （C) は、 その合計量 （B + C) が、 前記エポキシ基含有アクリル樹脂 （A) 1 00重量部当り 0. 5乃至 95重量部 の範囲にあり、 且つ該助剤成分 （C) とァミノ系安定剤 （B) との重量比 [CZ (B + C) ] が 0. 30乃至 0. 95となるように配合されていることを特徴と する三成分系塩素含有重合体用安定剤。 Karana, The total amount (B + C) of the amino stabilizer (B) and the auxiliary component (C) is in the range of 0.5 to 95 parts by weight per 100 parts by weight of the epoxy group-containing acrylic resin (A). And the weight ratio [CZ (B + C)] of the auxiliary component (C) and the amino stabilizer (B) is from 0.30 to 0.95. A stabilizer for a three-component chlorine-containing polymer.
6. 前記エポキシ基含有アクリル樹脂（A)のエポキシ当量が 1 00以上、 250未満の範囲にある請求項 5に記載の三成分系塩素含有重合体用安定剤。  6. The stabilizer for a three-component chlorine-containing polymer according to claim 5, wherein the epoxy equivalent of the epoxy group-containing acrylic resin (A) is in the range of 100 or more and less than 250.
7. アミノウラシル乃至その誘導体 （B) が、 下記一般式 （1 ) ：  7. Aminouracil or its derivative (B) is represented by the following general formula (1):
Figure imgf000016_0001
Figure imgf000016_0001
式中、 1及び 2は、 炭素数 1乃至 8のアルキル基、 ァラルキル基、 アル ケニル基及び非置換或いはアルキル基、 ハロゲンで置換されたフエニル 基を示し、 R1と R2とは、 互いに同一でも異なっていてもよい、 で表される化合物である請求項 5に記載の三成分系塩素含有重合体用安定剤。 In the formula, 1 and 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, and a phenyl group substituted with a halogen, and R 1 and R 2 are the same as each other 6. The stabilizer for a three-component chlorine-containing polymer according to claim 5, wherein the stabilizer is a compound represented by:
7. 前記助剤成分 （C) が、 2—フエニルインドールである請求項 5に記 載の三成分系塩素含有重合体用安定剤。  7. The ternary chlorine-containing polymer stabilizer according to claim 5, wherein the auxiliary component (C) is 2-phenylindole.
8. 塩素含有重合体に、 請求項 5に記載の三成分系塩素含有重合体用安定 剤が配合されており、 該塩素含有重合体用安定剤は、 該安定剤中のエポキシ基含 有アクリル樹脂 （A) が塩素含有重合体 1 00重量部当り 1. 0乃至 30重量部 となる量で配合されていることを特徴とする塩素含有重合体組成物。  8. The three-component chlorine-containing polymer stabilizer according to claim 5 is blended with the chlorine-containing polymer, and the chlorine-containing polymer stabilizer comprises an epoxy group-containing acrylic in the stabilizer. A chlorine-containing polymer composition, wherein the resin (A) is blended in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011099000A (en) * 2009-11-04 2011-05-19 Mizusawa Ind Chem Ltd Chlorinated vinyl chloride resin composition
CN102898741A (en) * 2012-10-08 2013-01-30 太原市塑料研究所 Polyvinyl chloride heat stabilizer and preparation method thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57200436A (en) * 1981-05-26 1982-12-08 Ciba Geigy Ag Composition for thermoplastic formation
JPS6310648A (en) * 1986-06-30 1988-01-18 Adeka Argus Chem Co Ltd Polyvinyl chloride resin composition
JPH0328250A (en) * 1989-06-26 1991-02-06 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH0726094A (en) * 1993-07-15 1995-01-27 Nippon Oil & Fats Co Ltd Chlorine-containing resin composition
JPH09125058A (en) * 1995-10-13 1997-05-13 Ciba Geigy Ag Stabilizer combination for chlorinated polymer
JP2000026681A (en) * 1998-06-26 2000-01-25 Witco Vinyl Additives Gmbh Composition containing chlorine-containing polymer and at least one 1,3-disubstituted 6-aminouracil, stabilization method for chlorine-containing polymer and use of 6- aminouracil compound
JP2000336076A (en) * 1999-04-06 2000-12-05 Witco Vinyl Additives Gmbh 4-aminopyrimidinone and oxazolidino-4aminoryrimidinone, method for producing these compounds, combination for stabilization, method for stabilizing chlorine-containing polymer and composition containing these compounds
JP2001106990A (en) * 1999-10-01 2001-04-17 Bando Chem Ind Ltd Substrate film for adhesive sheet and its production
JP2006508220A (en) * 2002-12-02 2006-03-09 クロンプトン ヴィニール アディティヴェス ゲーエムベーハー Monosubstituted 6-aminouracil for stabilizing halogenated polymers
JP2006513298A (en) * 2003-01-17 2006-04-20 クロンプトン ヴィニール アディティヴェス ゲーエムベーハー Stabilizer system for stabilizing PVC
JP2006104474A (en) * 2004-10-07 2006-04-20 Rohm & Haas Co Thermal stabilizer composition for halogen-containing vinyl polymer

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57200436A (en) * 1981-05-26 1982-12-08 Ciba Geigy Ag Composition for thermoplastic formation
JPS6310648A (en) * 1986-06-30 1988-01-18 Adeka Argus Chem Co Ltd Polyvinyl chloride resin composition
JPH0328250A (en) * 1989-06-26 1991-02-06 Sekisui Chem Co Ltd Vinyl chloride resin composition
JPH0726094A (en) * 1993-07-15 1995-01-27 Nippon Oil & Fats Co Ltd Chlorine-containing resin composition
JPH09125058A (en) * 1995-10-13 1997-05-13 Ciba Geigy Ag Stabilizer combination for chlorinated polymer
JP2000026681A (en) * 1998-06-26 2000-01-25 Witco Vinyl Additives Gmbh Composition containing chlorine-containing polymer and at least one 1,3-disubstituted 6-aminouracil, stabilization method for chlorine-containing polymer and use of 6- aminouracil compound
JP2000336076A (en) * 1999-04-06 2000-12-05 Witco Vinyl Additives Gmbh 4-aminopyrimidinone and oxazolidino-4aminoryrimidinone, method for producing these compounds, combination for stabilization, method for stabilizing chlorine-containing polymer and composition containing these compounds
JP2001106990A (en) * 1999-10-01 2001-04-17 Bando Chem Ind Ltd Substrate film for adhesive sheet and its production
JP2006508220A (en) * 2002-12-02 2006-03-09 クロンプトン ヴィニール アディティヴェス ゲーエムベーハー Monosubstituted 6-aminouracil for stabilizing halogenated polymers
JP2006513298A (en) * 2003-01-17 2006-04-20 クロンプトン ヴィニール アディティヴェス ゲーエムベーハー Stabilizer system for stabilizing PVC
JP2006104474A (en) * 2004-10-07 2006-04-20 Rohm & Haas Co Thermal stabilizer composition for halogen-containing vinyl polymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011099000A (en) * 2009-11-04 2011-05-19 Mizusawa Ind Chem Ltd Chlorinated vinyl chloride resin composition
CN102898741A (en) * 2012-10-08 2013-01-30 太原市塑料研究所 Polyvinyl chloride heat stabilizer and preparation method thereof
CN102898741B (en) * 2012-10-08 2015-03-25 太原市塑料研究所 Polyvinyl chloride heat stabilizer and preparation method thereof

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