JPS6049223B2 - thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent impact resistance and high-temperature molding processability, and more specifically, (a) a thermoplastic resin, (b) a conjugated diene and a carbonized vinyl aromatic resin. The present invention relates to a thermoplastic resin composition comprising a block copolymer comprising hydrogen, (c) at least one amine stabilizer selected from phenothiazine or a phenothiazine derivative, or a combination system of the stabilizer and a radical polymerization inhibitor.

Traditionally, thermoplastic resins such as styrene resins and olefin resins have been used as materials for food packaging containers, household goods, electrical parts, industrial parts, etc. because they can be easily molded by extrusion molding, injection molding, blow molding, vacuum molding, etc. It is used for a wide range of purposes.

However, depending on the application, these thermoplastic resins lack impact resistance, and may cause cracks or fractures during molding, or breakage due to impact such as dropping when using molded products. This is occurring. It is an effective method to improve the impact resistance of thermoplastic resins such as styrene resins and olefin resins by blending a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon. Already known.

For example, Japanese Patent Publication No. 44-7126, Japanese Patent Publication No. 47
Japanese Patent Publication No. 143618 and Japanese Patent Publication No. 52-2101 disclose a method of improving impact resistance by blending the above block copolymer with polystyrene or rubber-modified polystyrene. Similarly, Japanese Patent Publication No. 42-19935, Japanese Patent Publication No. 45-4624, Japanese Patent Publication No. 5067-1987, Japanese Patent Publication No. 1867-1977, Japanese Patent Publication No. 48-6285
Publication No. 1 contains polypropylene, polyethylene,
Attempts have been made to improve the properties of acrylic resins, vinyl chloride resins, and polyphenylene ether resins by blending them with the above block copolymers. However, recently, when manufacturing molded products from thermoplastic resin compositions containing block copolymers, impact resistance suddenly decreases when molded at relatively high temperatures for the purpose of improving productivity. Even if a block copolymer is blended into an engineering resin or the like that requires molding and molded, a sufficient improvement in impact resistance cannot be expected. In view of the current situation, the present inventors have made intensive studies on a method that enables high-temperature molding of a composition consisting of a thermoplastic resin and a block copolymer, and obtains a composition that has excellent impact resistance even after molding. , arrived at the present invention.

That is, the present invention provides at least one amine stabilizer selected from (a) a thermoplastic resin, (b) a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, and (C) a phenothiazine or a phenothiazine derivative. or a composition comprising the amine stabilizer and a radical polymerization inhibitor combination system, characterized in that component (c) is blended in an amount of 0.001 to 10 parts by weight per 100 parts by weight of component (b); The present invention relates to a plastic resin composition.

The present invention will be explained in detail below. The block copolymer composed of a conjugated diene and a vinyl aromatic trihydrocarbon used in the present invention has a vinyl aromatic hydrocarbon content of 5 to 95
% by weight, preferably 10-90% by weight, more preferably 15-85% by weight.

Such a block copolymer exhibits properties as a thermoplastic elastomer when the vinyl aromatic hydrocarbon content is 60% by weight or less, preferably 55% by weight or less; If it exceeds 65% by weight, preferably 65% by weight or more, it exhibits properties as a thermoplastic resin. Method for producing block copolymers used in the present invention 4
For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, and Japanese Patent Publication No. 49-36957.
Publication No. 48-2423, Special Publication No. 48-4
Examples include the method described in Publication No. 106 and the like.

All of these are methods of block copolymerizing a conjugated diene and a vinyl aromatic hydrocarbon using an anionic polymerization initiator such as an organolithium compound in a hydrocarbon solvent, and have the general formula (A-B)1A+. B-A), B-(A-B)n (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, and B is a polymer block mainly composed of conjugated diene.

The boundary between A block and B block does not necessarily need to be clearly distinguished. Further, n is an integer of 1 or more. ) or the general formula [(
B-A)n〒X1 [(A-B)n〒X1 [(B-AhB〒X (In the above formula, A and B are the same as above, and X is, for example, silicon tetrachloride, tin tetrachloride, etc.) It shows the residue of a coupling agent or the residue of an initiator such as a polyfunctional organolithium compound.

m and n are integers of 1 or more. ) is obtained as a radial block copolymer.

In the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons refers to a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing 5 weight percent or more of vinyl aromatic hydrocarbons, or a vinyl aromatic A polymer block mainly composed of a conjugated diene refers to a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing a conjugated diene in an amount exceeding 5% by weight, or a conjugated group hydrocarbon homopolymer block. Shows a diene homopolymer block. The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered. Examples of the vinyl aromatic hydrocarbons used in the method of the present invention include styrene, cm-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc. One of the most common is styrene.

These may be used not only alone, but also as a mixture of two or more. The conjugated diene used in the method of the present invention is a diolefin having a pair of conjugate double bonds, for example, 1,3
-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 1,3-hexadiene, etc., but particularly common ones are 1,3-butadiene,
Isoprene is mentioned.

These may be used not only alone, but also as a mixture of two or more. The molecular weight of the block copolymer used in the present invention is 50
00-10000001 preferably 10000-800
000, more preferably 30,000 to 500,000.

In addition, the Protsukuno copolymer can be treated with hydroxyl groups, thiol groups, nitrile groups, Modifications such as introduction of functional groups such as sulfonic acid groups and amino groups may also be performed. In the present invention, the vinyl aromatic hydrocarbon content of the block copolymer is 5 to 6% by weight (preferably 10% by weight).
~50% by weight), the block copolymer is blended in an amount of 1 to 10 parts, preferably 5 to 5 parts, per 100 parts by weight of the thermoplastic resin to improve impact resistance and tensile strength. preferred in order to obtain a composition with excellent properties.

If the amount of the block copolymer is less than the above range, the effect of improving impact resistance will not be sufficient, while if it exceeds the above range, mechanical strength such as tensile strength will tend to decrease. In addition, when the content of vinyl aromatic hydrocarbon in the block copolymer is more than 60% by weight and 95% by weight or less (preferably 65 to 85% by weight), the block copolymer and the thermoplastic resin are Blending at a weight ratio of 1/99 to 99/1, preferably 10/90 to 90/10,
Recommended for obtaining impact-resistant resin compositions with good surface gloss. The thermoplastic resins used in the present invention include polystyrene, impact-resistant rubber-modified stainless steel polymer, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene. - Polystyrene resins such as styrene copolymers, polyethylene, copolymers of ethylene containing 50% or more of ethylene and other monomers that can be copolymerized with it, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers Polyethylene resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene, polypropylene, and copolymers of propylene containing 50% or more of propylene and monomers copolymerizable with it, such as propylene-ethylene. Copolymers, polypropylene resins such as propylene-ethyl acrylate copolymers and chlorinated polypropylene, polybutene-1, polybutene-based resins that are copolymers of butene-1 and other monomers copolymerizable with it, polychlorinated Vinyl, polyvinylidene chloride, vinyl chloride and/or polyvinyl chloride resin which is a copolymer of vinyl chloride and/or vinylidene chloride containing 50% or more of vinylidene chloride and other monomers copolymerizable with it, acetic acid Polyvinyl acetate resin, which is a copolymer of vinyl acetate with a vinyl content of 50% or more and other copolymerizable monomers, and its hydrolyzate, acrylic acid and its esters and amides, methacrylic acid and its esters polyacrylate resins that are copolymers with other copolymerizable monomers containing 50% or more of these acrylic acid monomers, polymers of acrylonitrile and/or methacrylonitrile, and these acrylonitrile-based A nitrile resin that is a copolymer with a copolymerizable monomer containing 50% or more of the monomer, a linear polymer in which the constituent units of the polymer are bonded by repeated amide group bonds,
For example, ring-opened polymers of ε-aminocaprolatatum and ω-aminolaurolactam, condensation polymers of ε-aminoundecanoic acid, condensation polymers of hexamethylene diamine and dibasic acids such as adipic acid and sebacic acid, etc. polyamide resin,
Linear polymers in which the structural units of the polymer are bonded by repeating ester bonds, such as dibasic acids such as phthalic acid and isophthalic acid, or derivatives thereof, and ethylene glycol, propylene glycol, butylene glycol, etc. Polyester resins that are condensates with glycol components, polyphenylene ether resins, grafted polyphenylene ether resins obtained by graft polymerizing vinyl-substituted aromatic hydrocarbons to these resins, polyphenylene sulfide resins, polyoxy(O-methylene), trioxane and alkylene oxides. Polyacetal resins such as copolymers,
Linear polymers in which the constituent units of the polymer are bonded by repeating carbonate type bonds, for example, dihydroxy compounds such as 4,4''-dihydroxydiphenylalkane, 4,4''-dihydroxydiphenyl sulfide, and phosgene. or polycarbonate resins such as polymers obtained by transesterification of the dihydroxy compound and diphenyl carbonate, polysulfone resins such as polyether sulfone and polyallylsulfone, and diisocyanate components. Thermoplastic polyurethane resins obtained by polyaddition reaction with glycol components, polybutadiene resins such as trans polybutadiene and 1,2-polybutadiene, and polyarylate resins that are polycondensation polymers consisting of bisphenol A and phthalic acid components. , a fluororesin having a structure in which part or all of the hydrogen in a chain hydrocarbon polymer compound is replaced with fluorine, a polyoxybenzoyl resin, a polyimide resin, and the like.

In the present invention, the thermoplastic resin is a high-density polyethylene resin,
Crystalline polypropylene resin, thermoplastic polyester resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyamide resin, polyarylate resin, polysulfone resin, polyoxybenzoyl resin, polyacetal resin, nitrile It can be effectively used in applications where the molding temperature is generally high, such as polyimide-based resins, polyimide-based resins, fluororesins, etc., and where conventional compositions cannot sufficiently improve their properties by blending block copolymers.

In the present invention, at least one amine stabilizer selected from phenothiazine or phenothiazine derivatives, or the amine stabilizer and a radical polymerization inhibitor are added in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the block copolymer. , preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

If the amount of the amine stabilizer or the amine stabilizer and radical polymerization inhibitor used is less than the above range, a composition with excellent impact resistance and high temperature moldability cannot be obtained; If this is the case, the thermoplastic resin composition will be colored, resulting in deterioration of its appearance characteristics, which is undesirable. Four specific examples of the phenothiazine derivatives used in the present invention include alkyl groups having 1 to 30 carbon atoms, alkenyl groups, aryl groups, alkylaryl groups, arylalkyl groups, cycloalkyl groups, hydroxyalkyl groups, cyano groups, and amides. Examples include phenothiazine derivatives containing a substituent selected from the group consisting of acyl group, acyl group, alkoxy group, heterocyclic sulfur-containing group, and halogen.

Furthermore, the radical polymerization inhibitor used in the present invention is generally used as a radical polymerization inhibitor for monomers, and is a reagent that quickly reacts with radicals to convert them into stable radicals or neutral substances. .

Specifically, diphenylpicrylhydrazyl, Tory P
-nitrophenylmethyl, benzoquinone, p-Ter
Examples include t-butylcatechol, hydroquinone, hydroquinone monoalkyl ether, nitrobenzene, and dialkyldithiocarbamic acid metal salts. Particularly preferred radical polymerization inhibitors are hydroquinone, hydroquinone monoalkyl taether, p-tert-butylcatechol, and dialkyldithiocarbamate metal salts. In the present invention, it is preferable to use an amine stabilizer and a radical polymerization inhibitor in combination because impact resistance and high temperature moldability are synergistically improved.

When used in combination, the composition ratio of these is 99/1 to 10/9.
0 (weight ratio), preferably 90/5 to 30/70, more preferably 90/10 to 50/50. In the present invention, a phenol stabilizer, a phosphorus stabilizer, a sulfur stabilizer, and an amine stabilizer other than those specified in the present invention may be used in combination, if necessary.

The thermoplastic resin composition of the present invention may contain any additives, if necessary.

The type of additive is not particularly limited as long as it is commonly used in the formulation of thermoplastic resins, but examples include calcium carbonate, zinc oxide, titanium oxide, clay, talc, inorganic fillers such as glass beads, carbon black, etc. organic reinforcing agents, inorganic fibers such as glass fibers, organic fibers such as carbon fibers and synthetic fibers, adhesives such as coumaron indene resin and terpene resin, paraffinic, naphthenic and aromatic oils, various pigments and dyes. , flame retardant, antistatic agent,
Lubricants, plasticizers, softeners, other fillers, etc. (For details, see 1. Practical Handbook of Additives for Plastics and Rubber J (published by Kagaku Kogyo Co., Ltd.) and 0. Rubber and Plastic Compounding Chemicals (published by Rubber Digest Co., Ltd.) additives) can be used. In the present invention, it is not preferable to use maleic anhydride or other maleic heptacid compounds as additives because the final composition will undergo severe discoloration.

Therefore, it is recommended in the present invention to avoid the use of maleic acid compounds. The thermoplastic resin composition of the present invention includes:
It can be produced by any conventionally known compounding method.

For example, melt-kneading methods using general kneading machines such as open rolls, intensive mixers, internal mixers, co-kneaders, continuous kneaders with twin-screw rotors, extruders, etc., each component is dissolved or dispersed in a solvent, and then mixed with a solvent. A method of removing the particles by heating is used. The thermoplastic resin composition of the present invention thus obtained can be processed by any conventionally known molding method.
For example, extrusion molding, injection molding, blow molding, etc. produce a wide variety of practically useful products such as sheets, foams, films, injection molded products of various shapes, blow molded products, pressure molded products, vacuum molded products, etc. It can be easily molded.

The temperature at which the thermoplastic resin composition of the present invention is molded can be arbitrarily selected depending on the type of thermoplastic resin used, but the composition of the present invention may suffer from a decrease in impact resistance or a decrease in impact resistance compared to known compositions. It is also possible to easily perform molding at high temperatures, where the appearance characteristics are extremely deteriorated due to the formation of gel-like substances.

Examples of the present invention are shown below to explain the present invention in more detail, but it goes without saying that the content of the present invention is not limited to these Examples.

The block copolymers used in the examples of the present invention were produced in the following manner.

[Bujitsuku copolymer prisoner]

In a nitrogen gas atmosphere, n-hexane solution containing 15 parts by weight of 1,3-butadiene and 2 parts by weight of styrene was added with n-
Add 0.09 parts by weight of butyllithium and heat at 70°C for 2 hours.
After polymerization for an hour, an n-hexane solution containing 45 parts by weight of 1,3-butadiene and 2 parts by weight of styrene was added for 70 hours.
Polymerization was carried out at ℃ for 2 hours.

The obtained polymer was B-A-B with a styrene content of 4%.
It was a block copolymer with -A structure. [Block copolymer (B)] In a nitrogen gas atmosphere, 0.15 parts by weight of n-butyllithium was added to a cyclohexane solution containing 4 parts of styrene, and after polymerization at 70°C for 1 hour, 1,3 - Add a cyclohexane solution containing 6 parts of butadiene to 70°C.
Polymerization was carried out for 2 hours.

Thereafter, tetrachlorosilane was added in an amount of 114 equivalents of the n-butyllithium used to obtain a block copolymer of (A-B+-4Si structure) with a styrene content of 40% by weight.
Block copolymer (C)] The amount of styrene added was 3 parts by weight, the amount of butadiene added was 7 parts by weight, and the same as block copolymer (B) except that diprombutane was used as a coupling agent. By the same method, styrene content 3
A block copolymer having an ABA structure with a weight of % was obtained.

[Block copolymer (D)] 3 parts of styrene and 0.0 parts of tetrahydrofuran were mixed in a nitrogen gas atmosphere. Add 0.0 of n-butyllithium to the cyclohexane solution containing the slag.
After adding a heel portion and polymerizing at 70°C for 1 hour, 1,3
- A cyclohexane solution containing 2 parts by volume of butadiene and 5 parts by volume of styrene was added and polymerized at 70°C for 2 hours. The obtained polymer was a block copolymer having an A-B-A structure with a styrene content of 8% by weight. [Examples 1 to 9 and Comparative Examples 1 to 8] According to the compounding method shown in Table 1, the thermoplastic resin, block copolymer, and stabilizers were mixed using a Henschel mixer, and then extruded at 40 WLφ. It was pelletized by a machine.

The obtained pellets were injection molded using a 5-ounce injection molding machine, and the Izod impact strength of the molded product was examined. 5. As a result, the thermoplastic resin composition of the present invention had better Izot impact strength than the comparative example.

[Examples 10 to 16] After mixing the thermoplastic resin, block copolymer, and stabilizers in a Henschel mixer according to the compounding method shown in Table 2, 407,017! It was pelletized using a Yu-yu extruder.

The obtained pellets were molded into a film of about 50p using a 40m extruder. Next, for comparison, instead of the stabilizers listed in Table 2, TNP. The total amount of DLTP was 0.1 parts by weight per 10 parts of the block copolymer.
A film containing the weight part was molded in the same manner as above, but there were many gel-like substances and hard eyes, and not only the appearance properties but also the mechanical strength (tear strength, puncture strength) were lower than that of the composition of the present invention. It was inferior. [Examples 17 and 18] Consisting of 100 parts by weight of nylon 66, 2 parts by weight of block copolymer (4), 0.1 parts by weight of phenothiazine, and 50 parts by weight of glass fiber (short fiber with a diameter of 9p) The molded article was injection molded.

The obtained injection molded piece had an Izot impact strength of 20.5k.
It was 9.Cm/d (with notch). Further, 10 parts by weight of polyethylene terephthalate, 1 part by weight of block copolymer (4), 0.05 parts by weight of phenothiazine, and 4 parts by weight of glass fiber were injection molded in the same manner as above.

The obtained injection molded piece had an Izot impact strength of 19.3k9.
．． cm/d (with notch). Next, for comparison, injection molded products were made using DLTP instead of phenothiazine, but the Izod impact strength of each product was 20 to 30% lower than that obtained by the method of the present invention.

Claims (1)

[Claims] 1. At least one amine type selected from (a) a thermoplastic resin, (b) a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, and (c) a phenothiazine or a phenothiazine derivative. In a composition composed of a stabilizer or a combination system of the amine stabilizer and a radical polymerization inhibitor, component (c) is added at 0.0 parts by weight per 100 parts by weight of component (b).
A thermoplastic resin composition characterized in that it is blended in an amount of 01 to 10 parts by weight. 2. The composition according to claim 1, wherein the composition ratio of the amine stabilizer and the radical polymerization inhibitor is 99/1 to 10/90 (weight ratio). 3. The composition according to claim 1, wherein the radical polymerization inhibitor is hydroquinone, hydroquinone monoalkyl ether, P-tert-butylcatechol, or dialkyldithiocarbamate metal salt. 4 The thermoplastic resin is high-density polyethylene resin, crystalline polypropylene resin, thermoplastic polyester resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyamide resin, polyarylate resin, polysulfone resin The composition according to claim 1, which is a thermoplastic resin containing at least one selected from polyoxybenzoyl resin, polyacetal resin, nitrile resin, and polyimide resin.