JP3250905B2 - Vinyl chloride resin composition - 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 vinyl chloride resin composition which is stabilized by adding an epoxy-modified block copolymer having a specific structure. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and have characteristics such as excellent weatherability, moldability and gas barrier properties, and have been widely used as films, sheets and various molded products. However, when heat processing is performed, thermal decomposition mainly due to dehydrochlorination is apt to occur, which causes a decrease in mechanical properties of the processed product and deterioration of color tone, resulting in a significant disadvantage. In order to avoid such disadvantages, it is necessary to add one or several kinds of heat stabilizers to the vinyl chloride resin to suppress deterioration in the processing step.

Conventionally, various organic acid metal salts have been used for this purpose,
Organotin compounds and the like have been used. As a result, almost satisfactory results were obtained in terms of thermal stability.

[0004]

However, these metal salts, especially cadmium salts or lead salts, have serious toxicity problems in recent years, and their use has been limited.

[0005] For this purpose, it has been proposed to use various metal salts other than cadmium salts or lead salts in various combinations, for example, Ba / Zn type and Ca / Zn type. However, the performance of these combinations is not yet sufficient, and the use of various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, phenol compounds, and β-diketone compounds has been proposed. However, it has not been sufficient, and further improvement has been desired.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to improve the thermal stability, which is a disadvantage of vinyl chloride resins, and as a result, have found that an epoxy-modified block copolymer having a specific structure has been obtained. The inventors have found that the thermal stability can be remarkably improved by the addition, and have reached the present invention.

That is, the present invention relates to "(a) a polymer mainly comprising a vinyl aromatic compound and (A) a polymer mainly comprising a conjugated diene compound in the same molecule as a vinyl chloride resin (ii). A vinyl chloride resin composition comprising an epoxy-modified block copolymer obtained by epoxidizing a conjugated diene component of a block copolymer comprising a block (B) ".

The vinyl chloride resin as the component (a) used in the present invention may be a homopolymer of vinyl chloride, a copolymer of vinyl chloride with ethylene, propylene, vinyl acetate, or the like, or vinyl chloride and vinyl ethers, acrylic It includes a copolymer with an acid or an ester of methacrylic acid, acrylamide, acrylonitrile, a maleimide compound, or the like, and may be obtained by any production method such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. The degree of polymerization is not particularly limited, but those having a degree of polymerization of about 600 to 2500 are preferable. In applications where high heat resistance is desired, a chlorinated vinyl chloride resin obtained by post-chlorinating a vinyl chloride resin can be used.

Next, the epoxy-modified block copolymer (b) used in the present invention will be described.

The vinyl aromatic compound of the block polymer used for the component (b) constituting the present invention includes, for example, styrene, α-methylstyrene, vinyltoluene, p-
One of tertiary butylstyrene, divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene, etc.
The species or two or more species can be selected, and among them, styrene is preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, and 3-butyl-
One or more of 1,3-octadiene, phenyl-1,3-butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

The term "block copolymer" as used herein means a block copolymer consisting of a polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a conjugated diene compound. The copolymerization ratio between the group III compound and the conjugated diene compound is from 5/95 to 70/30, particularly preferably from 10/90 to 60/40.

The number average molecular weight of the block copolymer used in the present invention is 5,000 to 600,000, preferably 1
The molecular weight distribution [ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)] is 10 or less. The molecular structure of the block polymer may be linear, branched, radial, or any combination thereof. For example, ABA, BABA, (AB-) ₄ S
i, a vinyl aromatic compound-conjugated diene compound block polymer having a structure such as ABABA. Further, the unsaturated bond of the conjugated diene compound of the block polymer may be partially hydrogenated.

As a method for producing the block polymer used in the present invention, any production method having the above-mentioned structure can be adopted. For example, Japanese Patent Publication No. 40-2
According to the method described in Japanese Patent No. 3798, a vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst or the like.
Further, Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6
No. 636 or JP-A-59-133203, a partially hydrogenated block used in the present invention is subjected to hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. Polymers can be synthesized.

In the present invention, the epoxy-modified block copolymer used in the present invention is obtained by epoxidizing the above-mentioned block copolymer.

The epoxy-modified block copolymer of the present invention can be obtained by reacting the above-mentioned block copolymer with an epoxidizing agent such as a hydroperoxide or a peracid in an inert solvent.

The peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is available at low cost, and has high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

At the time of epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

In the case of hydroperoxides,
A mixture of tungstic acid and caustic soda with hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using an organic acid in combination with hydrogen peroxide or using molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide.

There is no strict regulation on the amount of epoxidizing agent, and the optimum amount in each case will vary depending on the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, etc. Depends on factors.

As the inert solvent, it can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and in the case of peracetic acid, aromatic compounds, ethers, esters and the like are used. Can be used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride and chloroform. There is no strict regulation on the epoxidation reaction conditions. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, the temperature of peracetic acid is preferably from 0 to 70 ° C., the reaction is slow at 0 ° C. or lower, and the decomposition of peracetic acid occurs at over 70 ° C. Also, tert-butyl hydroperoxide which is an example of hydroperoxide
For molybdenum dioxide diacetylacetonate system, 20 ° C to 150 ° C is preferable for the same reason. No special operation of the reaction mixture is required, for example, the mixture may be stirred for 2 to 10 hours. Isolation of the resulting epoxy-modified copolymer is a suitable method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water under stirring and distilling off the solvent,
It can be performed by a direct desolvation method or the like.

The vinyl chloride resin composition of the present invention comprises:
It is prepared by blending the above-mentioned epoxy-modified block copolymer as the component (b) with the vinyl chloride resin as the component (a) and uniformly melting and mixing these components.

Here, the mixing ratio of each component is such that the component (b) is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the component (a). If the component (b) is less than 1 part by weight, the stability will not be improved, and if the component (b) exceeds 50 parts by weight, the processability will deteriorate.

(A) and (B) The method of uniformly mixing the components is not particularly limited, and the components are well mixed in advance with a Henschel mixer, a ribbon blender or the like, and the resulting mixture is used as a Banbury mixer, extruder, roll, or the like. , Or may be melt-mixed while quantitatively supplying each component to a continuous kneader.

Further, by adding a metal salt of a carboxylic acid, an organic phosphoric acid or a phenol or an organic tin-based stabilizer to the vinyl chloride resin composition of the present invention, the effect of heat stability is further enhanced. These carboxylic acids,
Metals of organic phosphoric acids or phenols (Li, Na,
K, Ca, Ba, Mg, Sr, Zn, Sn) As the carboxylic acid constituting the salt, for example, caproic acid, pelargonic acid, 2-ethylhexyl 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, oleic acid, arachiic acid, behenic acid, erucic acid, brassic acid Mixtures of the above naturally occurring acids, such as and similar acids and tallow fatty acid coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids,
Benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid,
Monovalent carboxylic acids such as isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Divalent carboxylic acids such as 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 and aconitic acid And the like.

Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di (nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate, and the like. can give.

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

As the organic tin-based stabilizer, for example,
Mono- or dialkyltin compounds such as mono- or dimethyltin-, mono- or dibutyltin- or mono- or dioctyltin compounds, more specifically mono- or dialkyltin sulfides, oxides or sulfide-oxides; Carboxylates such as octoate, laurate, malate-laurate, stearate, isostearate, crotonate, oleate, basic laurate; cyclic malate or malate polymers of dialkyltin; butylmalate, octylmalate, malate-octylma of dialkyltin Ester malates such as acrylate, stearyl malate, oleyl malate, basic butyl malate; mono- or dialkyltin octyl mercaptide, lauryl mercaptide, stearyl Alkyl mercaptan Tide such Rukaputaido; mono- or isooctyl thioglycolate dialkyl tin 2-ethylhexyl thioglycolate,
Thioglycolic acid ester salts such as tetradecylthioglycolate and isooctylthioglycolate-sulfide; thioglycolates such as isooctylthiopropionate, 2-ethylhexylthiopropionate and tetradecylthiopropionate of mono- or dialkyltin; Propionate; mercaptoethanol ester such as 2-mercaptoethyl oleate of mono- or dialkyltin; and among these organic tin-based stabilizers, malate-based, ester-malate-based and thiocarboxylate-based salts are particularly preferred. Are preferred.

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

In addition, the composition of the present invention includes inorganic metal salts such as hydrotalcite; higher fatty acids such as stearic acid; higher alcohols such as stearyl alcohol; waxes such as montan wax, paraffin wax and polyethylene wax; Lubricants such as amides such as acid amide, methylene bisstearic acid amide and ethylene bisstearic acid amide can also be added.If necessary, pigments, dyes, fillers, antistatic agents, flame retardants, etc. It can also be added.

[Examples] Next, the present invention will be described specifically with reference examples, examples and comparative examples. In the following, parts and% mean parts by weight and% by weight, respectively.

Reference Example 1 A jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer was charged with 300 g of a block copolymer of polystyrene-polybutadiene-polystyrene (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.), and acetic acid. 1500 g of ethyl was charged and dissolved.

Subsequently, 169 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer A (epoxy equivalent of the polymer is 470).

Reference Example 2 In a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer, 300 g of a block copolymer of polystyrene-polybutadiene-polystyrene [trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.], acetic acid 1500 g of ethyl was charged and dissolved.

Then, 43 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water and dried to obtain an epoxy-modified polymer (epoxy equivalent of polymer: 1820).

Reference Example 3 300 g of a block copolymer of polystyrene-polybutadiene-polystyrene [trade name: TR2400, manufactured by Nippon Synthetic Rubber Co., Ltd.] was placed in a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer, and acetic acid. 1500 g of ethyl was charged and dissolved.

Then, 113 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer B (epoxy equivalent of polymer: 695).

Reference Example 4 A block copolymer of polystyrene-polybutadiene-polystyrene [trade name: Shell Chemical Co., Ltd.] was placed in a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer.
300 g of CARIFLEX D1122] and 1500 g of cyclohexane were charged and dissolved. Then, 177 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously added dropwise, and the solution was stirred for 40 minutes.
The epoxidation reaction was performed at 3 ° C. for 3 hours.

The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer C (epoxy equivalent of polymer: 448).

REFERENCE EXAMPLE 5 A polystyrene-polyisoprene-polystyrene block copolymer [trade name: Shell Chemical Co., Ltd.] was placed in a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer.
300 g of CARIFLEX TR1111] and 1500 g of cyclohexane were charged and dissolved.

Subsequently, 222 g of a 30% by weight solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer D (epoxy equivalent of polymer: 362). Example 1 and Comparative Example 1 (Blending) PVC (Geon 103 EP) 100 parts by weight Epoxy-modified block copolymer (Table 1) 5 parts by weight Stearyl alcohol 0.5 parts by weight Polyethylene wax 0.3 parts by weight Perchlorine Barium acid 0.1 part by weight The above composition was kneaded with a roll at 190 ° C to prepare a sheet. This sheet was placed in a gear oven at 190 ° C., and the thermal stability (time until significant discoloration) was measured.

Further, the sheet was pressed at 190 ° C. for 4 minutes to prepare a test piece, and the Vicat softening point of the test piece was measured in accordance with JIS K-6740. The results are shown in Table 1 below.

Example 2 and Comparative Example 2 (Blending) PVC (Geon 103 EP) 100 parts by weight Epoxy-modified block copolymer (Table 2) 10 parts by weight Oxidized polyethylene wax 0.5 parts by weight Montanic acid wax 0.3 parts by weight perchloric acid Barium 0.1 part by weight The above composition was kneaded with a roll at 190 ° C to prepare a sheet. This sheet was subjected to the same test as in Example 1. The obtained sheet was heated at 190 ° C and 100 kg using a flat plate press.
A test piece was prepared by press working under the condition of / cm ² for 10 minutes, and the Izod impact strength (JIS K7110, with notch) was measured. The results are shown in Table 2 below.

Table 1 Thermal stability Softening point (min) (° C) Comparative Example 1-1 No additives 15 70 1-2 Epoxidized soybean oil added 45 65 Epoxy-modified block copolymer Kind Example 1 -1 A 65 70 1-2 B 60 72 1-3 C 60 70 1-4 D 60 69 Table 2 Thermal stability Softening point Izod (min) (° C) Impact strength comparison example 2-1 MBS resin 15 71 3.0 epoxy Modified block copolymer type Example 2-1 A 65 69 4.5 2-2 B 60 71 4.2 2-3 C 60 69 4.0 2-4 D 65 68 4.3 The unit of Izod impact strength is Kg · cm / cm Table 1 and From the results shown in Table 2, it can be seen that the vinyl chloride resin composition of the present invention has excellent thermal stability and improved impact resistance.

[0046]

As described above, the vinyl chloride resin composition of the present invention is excellent in both properties of heat resistance and workability, and also has good impact resistance. It can be widely used in various fields such as products and building materials.

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Claims (1)

(57) [Claims] (A) a vinyl chloride resin; and (B) a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound in the same molecule. A vinyl chloride resin composition comprising an epoxy-modified block copolymer obtained by epoxidizing a conjugated diene component of a block copolymer comprising: