WO2008087784A1

WO2008087784A1 - Stabilizing agent for chlorine-containing polymer, and chlorine-containing polymer composition

Info

Publication number: WO2008087784A1
Application number: PCT/JP2007/071858
Authority: WO
Inventors: Seiji Wakaki; Toshihiro Yamamoto; Hiroshi Enoki
Original assignee: Mizusawa Industrial Chemicals, Ltd.
Priority date: 2007-01-19
Filing date: 2007-11-05
Publication date: 2008-07-24

Abstract

Disclosed is a stabilizing agent for a chlorine-containing polymer, which comprises (A) an epoxy-containing acrylic resin having an epoxy equivalent of not smaller than 100 and less than 250 and (B) an aminocrotonic acid ester in an amount of 0.5 to 70 parts by weight based on 100 parts by weight of the epoxy-containing acrylic resin as the main components and further comprises (C) a polyhydric alcohol in an amount of 0.5 to 70 parts by weight or (D) hindered amine or phenylindole in an amount of 0.1 to 70 parts by weight, both based on 100 parts by weight of the epoxy-containing acrylic resin as an auxiliary component. The stabilizing agent contains no metal, and therefore has no adverse influence on the environment, has a high effect of preventing the initial coloring, has high heat resistance or sustained heat resistance, and can prevent the coloration of a vinyl chloride resin effectively when the vinyl chloride resin is maintained at a high temperature for a long term.

Description

Specification Stabilizer for chlorine-containing polymer and chlorine-containing polymer composition

"Technical field"

[0001]

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.

《Background technology》

[0002]

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]

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]

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]

In order to improve the above drawbacks, various organic stabilizers have been studied. For example, Patent Document 3 discloses amino alcohol, dihydropyridine, amino hydrochloride, 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]

Patent Document 1: Japanese Patent Laid-Open No. 5 7-2 3 6 4 7

Patent Document 2 _: JP-A-6 1-2-4 7 7 4 8

Patent Document 3: Japanese Patent Laid-Open No. 2 0 06-1 0 4 4 7 4

<< Disclosure of Invention >>

[0007]

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]

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]

As a result of various investigations on non-metallic stabilizers, the present inventors have found that epoxy group-containing acryl resin having a specific epoxy equivalent and an amino chlorophosphoric acid ester in a specific quantitative ratio. When combined with the main stabilizer component combined with a specific amount of at least one of polyhydric alcohol, hindered amine, and phenylindole as an auxiliary component and blended with a chlorine-containing polymer, heat resistance or It has been found that the heat-resistant durability is remarkably improved and the coloring tendency when kept at a high temperature for a long time is effectively suppressed, and the initial coloring property is further effectively suppressed, and the present invention has been completed. It was.

[0010]

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 mainly stable. In addition, as an auxiliary component, it contains (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 or phenylindole. A stabilizer for a chlorine-containing polymer is provided.

[0011]

According to the invention, the chlorine-containing polymer stabilizer is combined with the chlorine-containing polymer, and the chlorine-containing polymer stabilizer is an epoxy group-containing acryl in the stabilizer. There is provided a chlorine-containing polymer composition characterized in that 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.

[0012]

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 I ^ l, dipentaerythryl I ^ l or partial esters thereof, and a hydroxyl group-containing isocyanurate;

(3) Hinderdamine (D) is a tetramethylpiperidine-based hindered amine There is,

(4) The auxiliary component contains (C) a polyhydric alcohol and (D) a hindered amine and / or phenylindole,

(5) The phenylindole is 2_phenylindole,

Is preferred.

[0013]

The stabilizer for chlorine-containing polymer of the present invention contains (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 main stabilizer component, (C) polyhydric alcohol or (D) hindered amine or phenylindole is added as an auxiliary component, effectively suppressing the initial coloration of the chlorine-containing polymer. At the same time, it has excellent heat resistance and heat durability.

[0014]

As is 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, The degree of coloring in the held state 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 kept in a light-colored state close to white.

[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.

<< Best Mode for Carrying Out the Invention >>

[0016]

The stabilizer for chlorine-containing polymer of the present invention comprises (A) an epoxy group-containing acryl resin, (B) A main stabilizer component containing an aminocrotonic acid ester in a predetermined amount ratio, and further, (C) a polyhydric alcohol and / or (D) a hindered amine or phenylindole in a predetermined amount ratio as an auxiliary component. By blending, it is possible to improve the initial coloring prevention effect and heat resistance or heat resistance durability.

[0017]

(A) Epoxy group-containing acrylic resin

The epoxy group-containing acryl 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 or heat durability. Examples of epoxy group-containing resins include bisphenol I type A epoxy resins, phenol novolac type epoxy resins, cresol nopolac type epoxy resins, and epoxy group-containing styrene resins. As is apparent from the comparative examples described later, the heat resistance persistence decreases.

[0018]

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 demonstrated in other epoxy group-containing resins is not clearly clarified. Perhaps the epoxy group-containing acryl 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.

[0019]

In the present invention, the epoxy group-containing acrylic resin includes, for example, a polymer comprising at least one of glycidyl (meth) acrylate,) 3-methyldaricidyl (meth) acrylate, and acylglycylidyl (meth) acrylate, and these polymers and And copolymers with alkyl (meth) acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, acrylonitrile, methacrylonitrile, and the like. In general, the molecular weight (weight average) is preferably from 1,000 to 1,000,000. [0020]

In the present invention, it is also important that the epoxy equivalent of the epoxy group-containing acrylic resin is 100 or more and 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 variation is likely to occur. Because it becomes.

[0021]

Epoxy group-containing acryl resins having an epoxy equivalent as described above include, for example, Marproof G-0101 (manufactured by NOF Corporation; epoxy equivalent 170), Metaprene KP-6562 (manufactured by Mitsubishi Rayon Co., Ltd.): It is commercially available under the trade name such as epoxy equivalent 200).

[0022]

(B) Aminocrotonate

The aminocrotonic acid ester, which is another main component used in the present invention, is known to have a function of preventing the initial coloration of the vinyl chloride polymer. In the present invention, the above-mentioned epoxy group-containing acrylic resin and In combination, the initial coloring can be more effectively prevented.

[0023]

In the present invention, the above-mentioned aminocrotonic acid ester (S-aminocrotone) is 0.5 to 70 parts by weight, particularly 10 to 50 parts by weight, per 100 parts by weight of the above-mentioned epoxy group-containing acrylic resin (A). Used in quantity. If the amount is less than this range, the initial coloration prevention performance is lowered, and if 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 is accelerated.

[0024]

In addition, 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 from 1 to 6,

Specific examples thereof include stearyl alcohol) 8-aminocrotonate ester, 1,4-monobutanediol diaminocrotonate ester, thiojetanol diaminocrotonate ester, trimethylolpropane) S Examples include —aminocrotonate, pentaerythritol I ^ monotetra-aminocrotonate, dipentaerythritol I ^ lhexa) s-aminocrotonate, and the like. Of these, 1,4-monobutanediol di) 8-aminocrotonic acid ester is particularly preferred.

[0025]

The above aminocrotonate is effective as a stabilizer for vinyl chloride resin among various chlorine-containing polymers.

[0026]

Auxiliary ingredients>

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

[0027]

(C) Polyhydric alcohol

The polyhydric alcohol is a component for supplementarily improving heat resistance or heat durability, and is an amount of 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. That is, when the amount of the polyhydric alcohol used is outside the above range, the heat resistance or heat resistance persistence decreases, for example, the tendency of coloring when the polymer composition is held in a high temperature atmosphere increases, The time until it deteriorates becomes shorter.

[0028]

Examples of such polyhydric alcohols include ethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, teramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, and diglycerin. , Pentaerythritol, dipen Taerythritol I, Pentaerythri I Ruadipate, etc. And hydroxyl group-containing isocyanurate compounds. Examples of the hydroxyl group-containing isocyanurate compound include the following formula (2):

Where RR ² and R. Each is preferably a hydroxyalkyl group, and is preferably 卜 ris (hydroxyalkyl) isocyanurate, and suitable examples thereof are tris (hydroxyethyl) isocyanurate, 卜 ris (hydroxypropyl) Examples include isocyanurate, tris (hydroxybutyl) isocyanurate, tris (2,3-dihydroxypropyl) isocyanurate, tris (glycidyl) isocyanurate, and the like.

[0029]

In the present invention, preferably used polyhydric alcohols are pentaerythritol, dipentaerythritol and partial esters thereof, and hydroxyl group-containing isocyanurate compounds, and these may be used alone or in combination of two or more. A hydroxyl group-containing isocyanurate compound is most preferably used.

[0030]

(D) hindered amine, phenylindole

In the present invention, instead of the polyhydric alcohol (C) or together with the polyhydric alcohol (C), a hindered amine or fluoricylindole is used as an auxiliary component in combination with the main stabilizer component. It can also be used as [0031]

This hindered amine, together with the above-mentioned aminocrotonic acid ester (B), can greatly improve the initial coloration tendency, but this significantly increases the effect of preventing the initial coloration, and when kept in a high-temperature atmosphere. Thus, the color tendency of the polymer composition can be effectively suppressed, the color of the polymer composition can be maintained in a nearly achromatic state, and the time until black can be extended.

[0032]

As such hindered amines, those known per se can be used, but particularly preferred is a tetramethylpiperidine-based hindered amine having a tetramethylpiperidine structure. Examples of tetramethylpiperidine-based hindered amines include the following.

1, 2, 2, 6, 6-pentamethyl mono 4-piberidyl stearate

2, 2, 6, 6— 亍卜 ramyl mono 4-piperidyl benzoate

N— (2, 2, 6, 6-tetramethyl-4-piperidyl) dodecyl succinic acid imide

1- [(3,5-Ditertiarybutyl-4-hydroxyphenyl) propionyloxetyl] 1,2,6,6-Tetramethyl-4-piperidylone (3,5-Ditertiary 4-hydroxyphenyl) Propionate

Bis (2, 2, 6, 6-Tetramethyl-4-piperidyl) Sebake Ichi Bis (1, 2, 2, 6, 6-Pentamethyl-4-piperidyl) Sebetsu Ichi 1-[2 [3 (3, 5-G t-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] —4 1 [3— (3, 5 _di-t 1 butyl, 4-hydroxyphenyl) propionyloxy] 1, 2, 2, 6, 6-tetramethylpi Peridine

Tetra (2, 2, 6, 6-tetramethyl-4-piperidyl) butane

Tetra (1, 2, 2, 6, 6-pentamethyl-1-4-piperidyl) butante 卜 Lacarpoxylate, bis (2.2,6.6-tetramethyl-1-piperidyl) 'Di (tridecyl) butane Tracarboxylate Bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) 'di (tridecyl) butane 亍 tracarboxylate

1, 1 '1 (1, 2-Etanjir) screw (3, 3, 5, 5-Tetramethyl rubiperradione)

Bis (2, 2, 6, 6- 亍 tramethyl-1-4-piberidinyl) Sebaketo Bis (N-methyl-1, 2, 2, 6, 6-tetramethyl-4-piperidinyl) Sebuke

Bis (1, 2, 2, 6, 6-pentamethyl-1-4-piperidyl) [[3,5 1-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalone

Condensation of 1, 2, 3, 4-butanecarboxylic acid with 2, 2, 6, 6-tetramethyl-4-piperidinol and tridecyl alcohol

Condensation product of 1, 2, 3, 4-butanecarbonic acid with 1, 2, 2, 6, 6-pentamethyl mono-4-piperidinol and rididyl alcohol

Tetrakis (2, 2. 6, 6-tetramethyl-1-piperidyl) 1, 2, 3, 4-butanetetracarboxylate

1, 2, 2, 6, 6-pentamethyl-4-piperidyltridecyl 1.

2, 3, 4-Butante la carpoxy

Poly [[{6— (1, 1, 3, 3, 3-tetramethylbutyl) monoamino} — 1.

3, 5— 卜 riadine 1, 2, 4-diyl] [(2, 2, 6. 6-tetramethyl — 4-piperidyl) imino] hexamethylene [(2, 2, 6, 6— 亍 trametyl 4-pipe Lysyl) Imino]

Poly [(6-Morpholino S-Riazine 1,2,4-Diyl) [2, 2, 6, 6-Tetramethyl-1-4-Piperidyl] imino] —Hexamethylene [(2. 2, 6, 6— Tetramethyl-4-piperidyl] imino]

1, 2, 3, 4-Butantellacarboxylic acid and ί, 2, 2, 6, 6-Tetramethyl mono 4-piberidinol and 3, β, β ', β' — Tetramethyl _ 3, 9 one (2, 4, 8, 1 0— 亍 Troxaspiro [5, 5] undecane) Condensate with Diethanol N, N '—Bis (3-aminopropyl) ethylenediamine 2, 4-bis [N-butyl-1-N— (1, 2, 2, 6, 6-pentamethyl-1-4-piperidyl) amino] — 6-black mouth 1,3,5-triazine condensate

Dimethyl succinate 1- (2-hydroxyethyl) 1-hydroxy 1 2, 2, 6, 6-tetramethylpiperidine polycondensate

1, 2, 3, 4-butanetetracarboxylic acid and 1, 2, 2. 6, 6-pentamethyl mono-4-piberidinol and i8, β, β ', β' — 亍卜 ramethyl-3, 9-(2, 4, 8, 1 0—Tetraoxaspiro [5, 5] undecane) Condensate with Diethanol

Polymethylpropyl 3-oxyl [4 (2, 2, 6, 6-tetramethyl) piperidinyl] siloxane

[0033]

The phenylindole contributes to a significant improvement in heat resistance, and the use of phenylindole is not the same as the heat resistance. It also improves sex.

[0034]

Examples of the phenylindole include the following.

2- (4, 1 dodecyl 1 phenyl) 1 indole

2- (3'-Methoxy-1 4'-Hydroxyphenyl) One indole

2— (3, 1-methyl, 1-methyl 4-phenyl)

2—Henrilou 5—Methoxy Indole

2— (3, 1 dodecyl, 4, 1 methoxy, 1 phenyl)

2- (3 ', 4' one xyxy phenyl) one indole

2- (3, 1 methoxy 4 '1 propoxy 1 phenyl) 1 indole

2- (3, 1-methyl 1- 4 '1-ethoxyphenyl) 1-indole

2— (3, -Methyloxy 4'-Ethoxy monophenyl) One indole

2-(4'-Methylhof:!: Nil) One indole

2— (4'-methyl monophenyl) 1 5-methyl-indole

Of these, 2_phenylindole is particularly preferred. [0035]

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 use this, so that the improvement of initial coloration by hindered amine and the improvement of heat resistance by phenylindole are most effectively manifested.

[0036]

In the present invention, it is preferable to use hindered amine and phenylindole in combination as an auxiliary component (D), whereby both initial colorability and heat resistance durability can be remarkably increased.

[0037]

When hindered amine and phenylindole are used in combination, the total amount is within the above range, but the weight ratio of hindered amine and phenylindole (D ₂ ) (D When ZD ^ is in the range of 0.01 to 0.8, especially 0.05 to 0.5, the effect of improving the initial colorability of hindered amine and the effect of improving the heat durability of vinylindole are maximized. This is preferable.

[0038]

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).

[0039]

<Chlorine-containing polymer>

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, and chlorinated poly. Ethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene Copolymer, vinyl chloride monosalt vinylidene chloride copolymer, vinyl chloride-styrene monomaleic anhydride terpolymer, vinyl chloride-styrene-acrylodiaryl copolymer, vinyl chloride-butadiene copolymer, Chlorinated vinyl monopropylene chloride copolymer, vinyl chloride monovinylidene chloride —vinyl acetate terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride monomaleate ester copolymer, vinyl chloride monomethacrylic acid Ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plasticized polyvinyl chloride, etc. Rukoto can.

[0040]

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. Polymer: olefin-based copolymer such as ethylene monoacetate vinyl copolymer, ethylene monopropylene copolymer; polystyrene; acrylic resin; styrene and other monomers (eg maleic anhydride, butadiene, acrylonitrile, etc.) And acrylonitrile / butadiene / styrene copolymer; acrylate ester / butadiene / styrene copolymer; methacrylate ester / butadiene / styrene copolymer; and the like.

[0041]

<Chlorine-containing polymer composition>

The chlorine-containing polymer composition of the present invention is a mixture of the above-described chlorine-containing polymer with a nonmetallic stabilizer containing each of the components (A) to (D) described above. Among the above components, the amount of the epoxy group-containing acrylic resin (A) 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. Thus, it is blended in the chlorine-containing polymer. As a result, various characteristics of each component are exhibited in a balanced manner and are synergistically enhanced, and excellent initial coloration preventing property, heat resistance and heat resistance durability are imparted to the chlorine-containing polymer. And the important thing is this Such excellent properties are imparted without the addition of a metal stabilizer containing a metal salt or the like that adversely affects the environment. Therefore, the chlorine-containing polymer composition of the present invention is suitable for environmental conservation and the like. It is also useful from a viewpoint.

[0042]

In addition, the chlorine-containing polymer composition of the present invention has various known additives such as plasticizers and phenolic antioxidants as long as they do not hinder the excellent characteristics obtained by the above-described nonmetallic stabilizer component. Well-known resin compounding agents such as additives, lubricants, flame retardants, fillers, colorants, UV absorbers, antistatic agents, modifying resins or rubbers, impact strengthening agents, and other organic compounding agents are known per se. According to the prescription of

[0043]

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

[0044]

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

[0045]

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.

"Example"

[0046]

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.

[0047]

(1) Gear oven heat resistance test (G.O)

The stabilizer of each example or comparative example was kneaded with a vinyl chloride resin in a roll mill at a temperature of 1600C for 5 minutes according to the following formulation 1 or 2, and a uniform vinyl chloride resin having a thickness of 0.7 mm Created a sheet.

Formulation 1:

Vinyl chloride resin (degree of polymerization 1 050); 1 00 parts by weight

Polyethylene wax (lubricant); 0.8 parts by weight

Stabilizer of each example or comparative example: described in each table

Formulation 2:

Vinyl chloride resin (degree of polymerization 1 050): 100 parts by weight

DOP (plasticizer) 50 parts by weight

Polyethylene wax (lubricant): 0.8 part by weight

Stabilizer of each example or comparative example; described in each table

The vinyl chloride resin sheet prepared above was placed in a gear oven set at 1 85 ° C., taken out every predetermined time, and its color state was visually observed until it turned black and judged.

[0048]

The color of the sea bream was evaluated in the following seven stages.

1: White

2: Light yellow

3: Yellow

4: Light brown

5: Brown

6: Dark brown

7: Blackening

[0049]

(2) Thermal stability test (H. T) In accordance with JIS-K-6723, the salt ^; vinyl resin sheet (soft vinyl chloride sheet) prepared with the above formula 2 was cut into 1. Ommx i. The tube was filled with 2 g of sample tip, heated to 1800C, and the hydrogen chloride desorption time due to the thermal decomposition of vinyl chloride was measured.

[0050]

The components shown below were used as stabilizers in the blending amounts shown in Table 1, vinyl chloride resin sheets were produced according to the blending formulation 1, and a gear oven heat 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.

[0051]

(1) Epoxy group-containing resin (A):

Resin 1: Marproof G—01 1 00 (Nippon Yushi Co., Ltd. epoxy group-containing acrylic resin)

Epoxy equivalent 1 70

Resin 2: Blemmer CP-5 OM (Epoxy group-containing acryl resin manufactured by NOF Corporation)

Epoxy equivalent 31 0

Resin 3: Epomic R—140 (Bisphenol type epoxy resin manufactured by Mitsui Chemicals, Inc.)

Epoxy equivalent 1 90

Resin 4: Epomic R—304 P (Bisphenol type epoxy resin manufactured by Mitsui Chemicals, Inc.)

Epoxy equivalent 875-1, 000

Resin 5: Marproof G-0250S (epoxy modified by NOF Corporation)

Styrene resin)

Epoxy equivalent 31 0

Resin 6: Marproof G—01 3 OS (epoxy modified by NOF Corporation)

Styrene resin) Epoxy equivalent 530

[0052]

(2) Aminocrotonate (B):

1,4-Butanediol bis (j8-aminocrotone)

[Noise riser 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]

[0053]

(3) Polyhydric alcohol (C):

卜 Risichi (2-Hydroxyl) Isocyanurate

[TH E I C-PW (manufactured by Shikoku Chemicals Co., Ltd.)]

[0054]

(4) Hinder Domin (H A LS) (D T):

Poly [[{6— (1,1,3,3-Teramethylbutyl) monoamino} —1,3,5— 卜 riadine 2.4-zyl] [(2,2,6,6-te 卜Rametyl _4-piperidyl) imino] hexamethylene [(2, 2, 6. 6-tetramethyl-1-piperidyl) imino]]

[Chi ma s so r b 944 L D (C i b a. S. C)

[0055]

(5) Epoxy compounds:

Epoxidized soybean oil

[W-1 00 EL (Dainippon Ink Chemical Co., Ltd.)]

Resin 1: Marproof G—01 100 (Efoxy equivalent 1 70)

Resin 2: Flemma CP-50M (Eho's xy equivalent 310)

Resin 3: I'Mick R-140 (Ejo's xy equivalent 1 90)

Resin 4: Jeho Mick R-304P (Jeho xy equivalent: 875 to 1,000)

Resin 5: Marble-Fur 0-02505 (Eho xy equivalent 310)

Resin 6: Muff 'Roof G-01 30S (Eho' xy equivalent 530)

Eho'xoxylated soybean oil: W-100EL (Dainippon Ink Chemical Co., Ltd.)

Ami-based stabilizer: Baraisa'-4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

Multivalent alcohol: THEIC-PW (manufactured by Shikoku Chemicals Co., Ltd.)

Hinta '-To'amin: Chimassorb944LD (Ciba.S.C)

ll [0057]

Examples 3-5, Comparative Examples 9-14>

The components shown below were used as stabilizers in the blending amounts shown in Table 2, vinyl chloride resin sheets were prepared according to the blending formulation 1, and a gear oven heat 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.

[0058]

(1) Epoxy group-containing resin (A):

Resin 1: Marproof G— 0 1 1 00 (Nippon Yushi Co., Ltd. epoxy group-containing acrylic resin)

Epoxy equivalent 1 70

Resin 2: Metaprene KP— 6562 (Mitsubishi Rayon Co., Ltd. epoxy group-containing acrylic resin)

Epoxy equivalent 200

Resin 3: BLEMMER CP—5 OM (Nippon Yushi Co., Ltd. epoxy group-containing acryl resin)

Epoxy equivalent 3 1 0

Resin 4: Epomic R—140 (Bisphenol type epoxy resin manufactured by Mitsui Chemicals, Inc.)

Epoxy equivalent 1 90

Resin 5: j E R-1 001 (Japan epoxy resin Co., Ltd.

Nord type epoxy resin)

Epoxy equivalent 469

Resin 6: Marproof G— 0 1 3 O S (Epoxy modified by NOF Corporation)

Styrene resin)

Epoxy equivalent 530

Resin 7: Marproof G-0250 S (epoxy modified by NOF Corporation)

Styrene resin)

Epoxy equivalent 3 1 0 [0059]

(2) Aminocrotonate (B):

1. 4-Butanediolbis (jS-Aminocrotone)

[Noise riser 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]

[0060]

(3) Polyhydric alcohol (C):

卜 Risichi (2-hydroxylethyl) isocyanurate

[TH E I C-PW (manufactured by Shikoku Chemicals Co., Ltd.)]

[0061]

(4) Hinder Domin (HA LS) (D,):

Poly [[{6— (1. 1. 3, 3-tetramethylbutyl) monoamino) 1 1,3,5-triazine 1 2.4-diyl] [(2, 2. 6, 6-tetramethyl 4-piperidyl) imino] hexamethylene [(2, 2, 6, 6-tetramethyl-1-piperidyl) imino]]

[Chi ma s so r b 944 L D (C i b a. S. C)

[0062]

(5) Phenylindole (D ₂ )

2-F: r Nylindole (Wako Pure Chemical Industries, Ltd.)

[0063]

(6) Epoxy compounds:

Epoxidized soybean oil

[W-1 00 EL (Dainippon Ink Chemical Co., Ltd.)]

Resin 1: Muff 'Roof G-01 100 is' Hydroxy equivalent 1 70)

Resin 2: Methbrene KP-6562 (Efoxy equivalent 200)

Resin 3: Flemma-CP-50M (Ejo xoxy equivalent 310)

Resin 4: Jeho Mick R-140 (Jeho pheasant equivalent 190)

Resin 5: JER-1001 (Efoxy equivalent 469)

Resin 6: M-proof G-0130S (Ehoxy equivalent 530)

Resin 7: Malproof 0-02505 (Eho's xy equivalent 310)

Eho'xoxylated soybean oil: W-100EL (Dainippon Ink Chemical Co., Ltd.)

Amino stabilizer: Lysa'-4 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

Multivalent alcohol: THEIC-PW (manufactured by Shikoku Chemicals Co., Ltd.)

Hinta '-Doamine: Chimassorb944LD (Ciba.S.C)

Phenylinyl: 2-Finylin'-le (manufactured by Wako Pure Chemical Industries, Ltd.)

0604 [0065]

The ingredients shown below were used as stabilizers in the amounts shown in Table 3, vinyl chloride resin sheets (soft vinyl chloride sheets) were prepared according to the above formulation 2 and gear oven heat test and thermal stability test were conducted. . The results are shown in Table 3. The compounding amount is expressed as an amount per 100 parts by weight of the vinyl chloride resin.

[0066]

(1) Epoxy group-containing resin (A):

Resin 1: M-proof G—01 1 00 (Nippon Yushi Co., Ltd. epoxy group-containing acryl resin)

Epoxy equivalent 1 70

Epoxy equivalent 200

Resin 3: Blemmer CP-50M (Nippon Yushi Co., Ltd. epoxy group-containing acryl resin)

Epoxy equivalent 3 1 0

Epoxy equivalent 1 90

Resin 5: j ER-1 001 (Japan epoxy resin Co., Ltd.

Nord type epoxy resin)

Epoxy equivalent 469, bisphenol type)

[0067]

(2) Aminocrotonate (B):

1,4-Butanediolbis () 8-aminophosphate)

[Noise riser 4B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)]

[0068]

(3) Polyhydric alcohol (C): 卜 Risichi (2-hydroxylethyl) isocyanurate [THE I C-PW (manufactured by Shikoku Chemicals Co., Ltd.)]

[0069]

(4) Phenylindole (D ₂ )

2-phenylindole (Wako Pure Chemical Industries, Ltd.)

[0070]

(5) Epoxy compounds:

Epoxidized soybean oil

[W-1 00 EL (Dainippon Ink Chemical Co., Ltd.)]

[0071]

—Table 3—

Resin 1: Muff 'Roof G-01 100 (Ejo' xy equivalent 1 70)

Resin 2: Metallene KP-6562 (Ejo xy equivalent 200)

Resin 3: Flemma CP-50M (I xy equivalent 310)

Resin 4: Jeho Mick R-140 (Jeho xy equivalent 190)

Resin 5: jER-100K Ejo 'xy equivalent 469)

Ejoxoxylated soybean oil: W-10OEL (Dainippon Ink Chemical Co., Ltd.) Amino stabilizer: Neurysa'-4B (Nippon Gosei Chemical Co., Ltd.) (Shikoku Kasei Kogyo Co., Ltd.) F Nil India: 2-F I Nil India (Wako Pure Chemical Industries, Ltd.)

Claims

The scope of the claims

1. (A) 100 parts by weight of an epoxy group-containing acrylic resin having an epoxy equivalent of 100 or more and less than 250, and 0.5 to 70 parts by weight of an aminocrotonic acid ester as main stabilizer components, A chlorine component characterized by containing (C) 0.5 to 70 parts by weight of polyhydric alcohol and Z or (D) 0.1 to 70 parts by weight of hindered or phenylindole as auxiliary components Stabilizer for polymers.

2. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the epoxy-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 I ^ l, dipentaerythritol or a partial ester thereof, and a hydroxyl group-containing isocyanurate. Stabilizer for coalescence.

4. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the hindered amine (D) is a tetramethylpiperidine-based hindered amine.

5. The chlorine-containing polymer stabilizer according to claim 1, wherein the auxiliary component contains (C) a polyhydric alcohol and (D) a hindered amine and Z or phenylindole.

6. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the phenylindole is 2-F: L-nylindole.

7. A chlorine-containing polymer stabilizer according to claim 1 is blended with the chlorine-containing polymer, and the chlorine-containing polymer stabilizer comprises an epoxy group-containing acrylic resin (A ) Is contained in an amount of 1.0 to 30 parts by weight per 100 parts by weight of the chlorine-containing polymer.

twenty five

Corrected spear (Rule 91)