JP3336021B2 - Vinyl chloride resin composition containing diene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized vinyl chloride resin composition, and more particularly, to a stabilized vinyl chloride resin composition containing a diene polymer as an impact modifier. About.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive, and have characteristics such as excellent weather resistance and moldability. Polyvinyl chloride resin is frequently used in dashboards, armrests, headrests, ceilings, doors, glove box lids, rear basel, and the like. In particular, since a dashboard mounts various instruments, speakers, and various other components as necessary, the mounting portion and the entire panel are required to have a performance capable of withstanding the weight of these components. In addition, performance under temperature conditions from high temperature to minus low temperature that can endure climatic conditions in various parts of the world is required.

Further, when an automobile collides, a certain degree of impact resistance is required in consideration of the case where the driver and the passenger in the passenger seat hit their heads on the upper surface or the front surface of the panel. For this reason, acrylonitrile-styrene-butadiene copolymer (ABS), acrylonitrile-butadiene copolymer rubber (NBR), methyl methacrylate-butadiene-styrene terpolymer (MBS), and the like are usually compounded as impact resistance improvers. It is widely practiced to improve impact resistance.

However, although the impact resistance of vinyl chloride resins is improved by the addition of ABS, NBR, MBS, etc., the added diene polymers remain chemically active in the main chain. Since the bond remains, it is easily oxidized by oxygen in the air. This tendency is accelerated at higher temperatures. Further, it is easily affected by light, and not only quickly yellows due to the action of sunlight, but also causes crosslinking and decomposition, leading to a decrease in physical properties of the vinyl chloride resin.

To remedy these disadvantages, for example,
Polynuclear polyhydric phenol esters of alkyl mercaptopropionic acid and the like have been proposed (JP-A-1-284540).
Publication), but the physical properties after heat aging are still insufficient,
Improvement was strongly desired.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to improve these drawbacks, and as a result, have found that a specific inorganic compound, a specific phenolic antioxidant and a specific sulfuric antioxidant have been replaced with diene. The present inventors have found that the physical properties of a vinyl chloride resin after heat aging can be remarkably improved by using it in combination with a polymer.

That is, the present invention provides a vinyl chloride resin 1
5 to 150 parts by weight of a diene polymer obtained by polymerizing a monomer having a polymerizable unsaturated double bond containing (a) a conjugated diene compound as an essential component,
(B) 0.01 to 10 parts by weight of an inorganic compound selected from a hydrotalcite compound and a zeolite compound, (c)
The following pentaerythritol of 0.01 to 5 parts by weight of a phenolic antioxidant represented by the general formula (I) represented by the following chemical formula (I) and (d) alkylthiopropionic acid
To provide a stabilized diene-based polymer-containing vinyl chloride-based resin composition to which 0.01 to 5 parts by weight of an ester of diene is added.

[0008]

Embedded image

(R represents an alkyl group having 1 to 4 carbon atoms, n represents 1 to 4, and R ′ represents a residue of a monovalent to tetravalent alcohol.)

[0010] The (a) of the vinyl chloride resin composition of the present invention
Examples of the conjugated diene compound constituting the diene polymer as a component include butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, and 1,3.
-Pentadiene, 1,3-hexadiene, ethylidene norbornene, dicyclopentadiene and the like,
Particularly common ones include butadiene, isoprene and the like.

The above-mentioned component (a) may be obtained by polymerizing not only one kind of these conjugated diene compounds but also a monomer obtained by mixing two or more kinds of these conjugated diene compounds. It may be copolymerized with an ethylenically unsaturated monomer.

These ethylenically unsaturated monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene and divinylbenzene; methyl acrylate,
Ethyl acrylate, butyl acrylate, acrylic acid-2
Alkyl acrylates such as -ethylhexyl; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate; acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate and the like; May be a vinyl monomer having, for example, acrylic acid, methacrylic acid, itaconic acid,
Ethylenically unsaturated carboxylic acids such as fumaric acid; hydroxyalkyl acrylates such as -β-hydroxyethyl acrylate and hydroxypropyl acrylate; vinyl compounds having a glycidyl group such as glycidyl methacrylate and glycidyl acrylate; acrylamide; Compounds having an amide group such as methylol acrylamide may be mentioned.

Accordingly, as the diene polymer which is the component (a) of the vinyl chloride resin composition of the present invention, for example,
Styrene-butadiene copolymer, methyl methacrylate-
Butadiene copolymer, acrylonitrile-butadiene copolymer, vinylidene chloride-styrene-butadiene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene-ethylidene norbonene And copolymers.

The amount of these diene polymers is 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The hydrotalcite compound, which is the component (b) of the vinyl chloride resin composition of the present invention, contains a hydrous compound containing magnesium and aluminum represented by the following general formula (II). It is a double salt compound.

[0016]

Embedded image Mg _1-x Al _x (OH) ₂ A _{x / 2} · mH ₂ O (II) (where x is a real number in the range of 0 <x ≦ 0.5;
Represents CO ₃ or SO ₄ , and m represents a real number. )

The hydrotalcite compound may be a natural product or a synthetic product. Examples of the synthesis method include known methods described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129. Further, in the present invention, it is possible to use without being limited by its crystal structure, crystal particle diameter and the like.

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

Further, a hydrotalcite compound partially modified with another metal such as zinc can also be used.

The zeolite compound as the component (b) of the vinyl chloride resin composition of the present invention is an aluminosilicate having a unique three-dimensional zeolite crystal structure,
Typical examples thereof include A-type, X-type, Y-type and P-type zeolites, monodenite, analsite, sodalite group aluminosilicates, clinobutyrolite, erionite and chabazite, and the like. A metal-substituted type in which all or part of the Group Ia metal is ion-exchanged with a Group II or Group IV metal ion can be used. These zeolite compounds are hydrates having water of crystallization (so-called zeolite water). Alternatively, any of anhydrides from which water of crystallization has been removed may be used.

The amount of the hydrotalcite compound or zeolite compound to be added depends on the vinyl chloride resin 10
It is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 0 parts by weight.

In the general formula (I) representing the phenolic antioxidant which is the component (c) of the vinyl chloride resin composition of the present invention, the alkyl group having 1 to 4 carbon atoms represented by R is , Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and isobutyl. Examples of the mono- to tetra-valent alcohol giving the residue R ′ include methanol, ethanol, butanol, octanol, and 2-ethyl. Hexanol, isooctanol,
Monohydric alcohols such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-
Decanediol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiethylene glycol, 3,9-bis (2-hydroxy-1,1-
Dihydric alcohols such as dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and 2,2-bis [4- (hydroxyethoxy) phenyl] propane; glycerin, trimethylolethane, triglycol Trihydric alcohols such as methylolpropane and tris (2-hydroxyethyl) isocyanurate; pentaerythritol,
And tetrahydric alcohols such as diglycerin and ditrimethylolpropane.

These phenolic antioxidants are added in an amount of 0.01 to 100 parts by weight of the vinyl chloride resin.
To 5 parts by weight, preferably 0.05 to 3 parts by weight.

Furthermore, the in minutes (d) formation of the vinyl chloride resin composition of the present invention, for example, blanking Chiruchiopuro pin propionic acid, octylthiopropionic acid, lauryl-thio acid, alkylthio such as distearyl acid esters of Bae Ntaerisurito Le propionic acid.

The amount of the component (d) is 0.01 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin.
Preferably it is 0.05 to 3 parts by weight.

The vinyl chloride resin to be stabilized in the present invention includes vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene vinyl acetate copolymer, vinyl chloride-ethylene chloride. Copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylic acid Ester copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated Propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic Ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride copolymers such as vinyl chloride-maleimide copolymers, and the above resins and polyethylene, polypropylene, polybutene, poly- Α-olefin polymers such as 3-methylbutene or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer and their copolymers, polystyrene, acrylic resin, polyurethane, styrene and other monomers ( (E.g., maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-styrene-butadiene copolymer, acrylate-styrene-butadiene copolymer, and methacrylate-styrene-butadiene copolymer. Etc. Kill.

These vinyl chloride resins may be those obtained by any of conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

The diene polymer-containing vinyl chloride resin composition of the present invention may contain a halogen oxyacid, an organic carboxylic acid,
By adding a metal salt such as an organic phosphoric acid or a phenol or an organic tin-based stabilizer, the heat stabilizing effect can be further increased.

These halogen oxyacids, organic carboxylic acids, organic phosphoric acids or phenolic metals (Li, Na,
(K, Ca, Ba, Mg, Sr, Zn, Sn) Salts include, for example, halogen oxyacids such as perchloric acid, periodic acid, chloric acid, bromic acid, iodic acid, chlorous acid, and hypochloroic acid. And bromic acid.

Examples of the organic carboxylic acids include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid,
Chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachiic acid, behenic acid, erucic acid, brassic acid and similar acids, as well as tallow, coconut, and tung oil A mixture of the above naturally occurring acids such as soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-tert-octylsalicylic acid , Naphthenic acid, monocarboxylic acids such as cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, Oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid Fumaric acid, citraconic acid, metaconic acid, itaconic acid, monoesters of divalent carboxylic acids such as aconitic acid.

The organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid,
Mono or dioctadecyl phosphoric acid, mono or di (nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate and the like can be mentioned.

Further, examples of the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

Examples of the organotin-based stabilizer include, for example, mono- or dimethyltin-, mono- or dibutyltin-
Or mono- or dialkyltin compounds such as mono- or dioctyltin compounds, more specifically, mono- or dialkyltin sulfides, oxides or sulfide-oxides; dialkyltin octoates,
Carboxylate such as laurate, malate-laurate, stearate, isostearate, crotonate, oleate, basic laurate; cyclic malate or malate polymer of dialkyltin; butylmalate of dialkyltin, octylmalate, malate-octylmalate, Ester malates such as stearyl malate, oleyl malate, basic butyl malate; alkyl mercaptides such as mono- or dialkyltin octyl mercaptide, lauryl mercaptide, stearyl mercaptide; isooctylthio mono- or dialkyltin Thioglycolic acid ester salts such as glycolate, 2-ethylhexylthioglycolate, tetradecylthioglycolate, isooctylthioglycolate-sulfide; mono- or dialkyl Thiopropionate salts such as isooctylthiopropionate, 2-ethylhexylthiopropionate and tetradecylthiopropionate; and mercaptoethanol ester salts such as mono- or dialkyltin 2-mercaptoethyl oleate. Among these organotin-based stabilizers, particularly preferred are malate-based, ester malate-based and thiocarboxylic acid ester-based stabilizers.

The amount of the metal salt of a halogen oxyacid, an organic carboxylic acid, an organic phosphoric acid or a phenol or an organic tin-based stabilizer is preferably 0.01 to 10 parts by weight based on 100 parts by weight of a vinyl chloride-based resin. Parts by weight, more preferably 0.1 to 5 parts by weight.

In addition, the composition of the present invention includes higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, waxes such as montan wax, paraffin wax and polyethylene wax, stearic acid amide, methylene bisstearic acid amide, Lubricants such as amides such as ethylenebisstearic acid amide; polyhydric alcohols such as pentaerythritol, dipentaerythritol, dipentaerythritol adipate, mannitol, sorbitol and ester compounds or partial ester compounds thereof, dehydroacetic acid, dibenzoylmethane ,
Pure β-diketone compounds such as benzoylacetone and stearoylbenzoylmethane, and organic nitrogen-containing compounds such as 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid dodecyl ester, 2-phenylindole and melamine. An organic stabilizing aid may be added.

If necessary, for example, a cross-linking agent, a pigment, a filler, a foaming agent, an antistatic agent, an anti-mist agent, a plasticizer, a plate-out inhibitor, a surface treating agent, a flame retardant, a fluorescent agent, and a fungicide , Bactericides, other antioxidants, ultraviolet absorbers, light stabilizers, light degrading agents, metal deactivators, processing aids, release agents, reinforcing agents, and the like.

[0037]

Next, the stabilizing effect of the vinyl chloride resin composition of the present invention will be specifically shown by way of examples. However, the present invention is not limited by the following examples.

Example 1 [combination] parts by weight PVC (degree of polymerization 1300) 100 ABS resin 45 NBR 15 tri (C7-9 alkyl) trimellitate 30 barium stearate 2 barium perchlorate 0.3 zinc laurate 0.5 DHT-4A * 0.3 Tetra (C12-15 alkyl) bisphenol A diphosphite 1.0 β- (3,5-Ditert-butyl-4-hydroxyphenyl) propionic acid tridecyl ester 0.1 Sulfur antioxidant (Table 1) 0.15 2-hydroxy-4-octoxybenzophenone 0.2 *: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry

The above composition was kneaded with a roll at 180 ° C. to produce a sheet. The sheet was subjected to a heat aging test for 400 hours in a gear oven at 120 ° C., and the degree of coloring before and after the heat aging was measured using a digital color meter TC-360DP manufactured by Tokyo Denshoku Co., Ltd. The color difference was determined.

The tensile strength before and after the heat aging was measured, and the residual elongation was determined. The results are shown in Table 1 below.

[0041]

[Table 1]

Example 2 [Compound] Parts by weight PVC (degree of polymerization: 1000) 100 ABS resin 30 NBR 25 Trioctyl trimellitate 30 Barium stearate 1.5 Basic zinc octylate 1.0 Inorganic compound (Table 2) 1 0.0 tetrakis (3,5-di-tert-butyl-4-phenylpropionic acid) pentaerythritol tetraester 0.1 pentaerthritol tetra (laurylthio pyropionate) 0.2 trisnonylphenyl phosphite 1.0 2-hydroxy -4-octoxybenzophenone 0.2 bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate 0.15

After the above composition was roll-kneaded, it was subjected to press working to prepare a sheet having a thickness of 1 mm. The sheet was set in a mold, and the polyol for urethane foam and the isocyanate were quickly poured into the mold while stirring, and the urethane foam was cured to form a urethane backing sheet (urethane layer 10 mm). The urethane sheet was placed in an oven at 120 ° C. and subjected to a heat aging test for 400 hours and 600 hours. The degree of coloration and tensile strength were measured, and the color difference and residual elongation before and after heat aging were determined. Was.

The results are shown in Table 2 below.

[0045]

From the results of the above Examples, it is clear that the diene polymer-containing vinyl chloride resin composition of the present invention contains a hydrotalcite compound or a zeolite compound, a specific phenolic antioxidant and a sulfuric antioxidant in combination. By doing so, it is evident that it has characteristics that do not reduce physical properties such as colorability and tensile strength after heat aging.

On the other hand, phenolic antioxidants and / or
Alternatively, when no sulfur-based antioxidant is added, the physical properties after heat aging are remarkably reduced, resulting in lack of practicality as a diene polymer-containing vinyl chloride resin.

[0048]

Industrial Applicability The vinyl chloride resin composition containing a diene polymer of the present invention has sufficient impact resistance, not only excellent coloring properties after heat aging, but also excellent physical properties such as tensile strength. It is a thing.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 55/02 C08L 55/02 (56) References JP-A-61-34042 (JP, A) JP-A-53-73241 (JP) JP-A-58-122951 (JP, A) JP-A-61-31466 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06 C08L 55/02

Claims (1)

(57) [Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 5-150 parts by weight of a diene polymer obtained by polymerizing a monomer having a polymerizable unsaturated double bond containing a conjugated diene compound as an essential component, and (b) a hydrotalcite compound and a zeolite compound. 0.01 to 10 parts by weight of a selected inorganic compound, (c) a phenolic antioxidant represented by the following general formula (I):
01 to 5 parts by weight and (d) alkylthiopropionic acid
A stabilized diene polymer-containing vinyl chloride resin composition comprising 0.01 to 5 parts by weight of pentaerythritol ester . Embedded image (R represents an alkyl group having 1 to 4 carbon atoms, and n represents 1 to
And R ′ represents a monovalent to tetravalent alcohol residue. )