JPS6072953A - Block copolymer composition - Google Patents

Abstract

PURPOSE:A conjugated diene-vinyl aromatic hydrocarbon block copolymer composition, having excellent weatherability and color, made by incorporating a higher fatty acid in combination with a hindered amine compound therein. CONSTITUTION:0.05-5pts.wt. higher fatty acid (e.g. capric, stearic, or tallow fatty acid) and 0.005-3pts.wt. hindered amine compound (e.g. 4-acetoxy-2,2,6-tetramethylpiperidine) are incorporated into 100pts.wt. conjugated diene-vinyl aromatic hydrocarbon block copolymer (e.g. a block copolymer with a molecular weight of about 5,000-1,000,000 consisting of about 5-95wt% butadiene and about 95-5wt% styrene). In addition, a benzophenone compound or a benozotriazole compound may also be incorporated together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a block copolymer composition with excellent weather resistance and color tone.

A block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon can exhibit elasticity similar to that of vulcanized natural rubber or synthetic rubber without vulcanization when the vinyl aromatic hydrocarbon content is relatively low. It is widely used in the fields of footwear, plastic modification, asphalt, adhesives, etc. because it has the same processability as thermoplastic resins at room temperature and at high temperatures. If the content of vinyl aromatic hydrocarbons is relatively high, a thermoplastic resin that is transparent and has excellent impact resistance can be obtained, so its use has increased in recent years, mainly in the food packaging container field, and at the same time its applications have also increased. It is becoming more diverse.

However, such block copolymers have a problem that they have poor weather resistance and cannot be used for long-term outdoor use. As a method for improving weather resistance, a method of adding a benzophenone compound or a benzotriazole compound is generally known, but the improvement effect of such compounds is not sufficient, and improvement thereof is desired.

In view of the current situation, the present inventors have conducted intensive studies on methods for improving the weather resistance of block copolymers, and have found that a composition with excellent weather resistance and color tone can be created by combining a hindered amine compound and a higher fatty acid. The present inventors have discovered that the present invention can be obtained, and have completed the present invention.

That is, in the present invention, for the block copolymer/θO weight part consisting of a conjugated diene and a vinyl aromatic hydrocarbon, + higher fatty acids θ, θ~! Part by weight (b) A block copolymer composition containing ~3 parts by weight of a hindered amine compound θ, OOS.

The composition of the present invention has almost no severe yellowing that occurs when only a block copolymer and a hindered amine compound are combined, and has excellent weather resistance, so it is suitable for various applications such as long-term outdoor use. It can be suitably used as a material in the field.

The present invention will be explained in detail below.

The block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon used in the present invention has a vinyl aromatic hydrocarbon content of j to 9 t% by weight, preferably /θ to dθ, More preferably, it is /j~♂o heavy IL round.

Such a block copolymer exhibits properties as a thermoplastic elastomer when the content of vinyl aromatic hydrocarbons is less than tosltes, preferably less than jj weight factor, and when the content of vinyl aromatic hydrocarbons is less than 60 weight factor. If it exceeds, it indicates favorable properties.

Methods for producing the block copolymer used in the present invention include, for example, Japanese Patent Publication No. 36-19216, Japanese Patent Publication No. 4T
3-/4t ri No. 2 Publication, Special Publication Showa Geta-3 to 9ri No. 2 Publication, Special Publication Sho 4t Za-2g No. 23, Special Publication Sho 4t/-4
Examples include the method described in Publication No. 1106 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, with the general formula %
(Formula %) (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated diene. The boundary between A block and B block is not always clear. n is an integer of 7 or more, generally an integer of /-, 1), or a linear block copolymer represented by the general formula %) (the above formula , A and B are the same as above, and X is, for example, a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, or epoxidized soybean oil, or a residue of an initiator such as a polyfunctional organic lithium compound. Indicates the group.

m and n are integers of 7 or more, and are generally integers of / to j. ) It is obtained as a radial block copolymer represented by: In the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons refers to a copolymer block of vinyl aromatic hydrocarbons and conjugated diene containing 10 weight percent or more of vinyl aromatic hydrocarbons, or vinyl aromatic hydrocarbons. It refers to a polymer block consisting of a hydrocarbon homopolymer block or a combination thereof, and a polymer block mainly consisting of a conjugated diene refers to a conjugated diene containing a conjugated diene in an amount exceeding 10 wt s, a vinyl aromatic hydrocarbon, and a polymer block mainly composed of a conjugated diene. A copolymer block, a conjugated diene homopolymer block, or a polymer block consisting of &+IIA combination thereof. The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed (bidistributed) or tapered.

The vinyl aromatic hydrocarbons used in the method of the present invention include styrene, O-methylstyrene, p-methylstyrene, p-methylstyrene,
Examples include -tcrt-butylstyrene, /, 3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, and styrene is particularly common.

These may be used not only in seven types but also in a mixture of λ or more types.

The conjugated diene used in the present invention is a diolefin having /pair of conjugated double bonds, such as /, 3-phtadiene, comethyl-/, 3-butadiene (isoprene).
, co, 3-dimethyl-8, 3-butadiene, 7,3-pentadiene, /, 3-hexadiene, and particularly common ones include he-3-butadiene and isoprene. 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
θ~/, 0θθ, θθθ, preferably 10,00θ~♂
θθ, ooθ, more preferably 3θ, θ0θ~SOθ
, θOO. In addition, block copolymers can be added with hydroxyl groups, thiol groups, nitrile groups, sulfonic acid groups, amino groups, etc. by hydrogenation, halogenation, hydrohalogenation, or chemical reactions within a range that does not impair their basic properties. Modification such as introduction of a functional group may also be performed.

The higher fatty acid as component (a) used in the present invention generally has 7θ to 26 carbon atoms, preferably 72 to λ. Higher fatty acids are usually obtained from animal or vegetable oils and fats, but in the present invention, other fatty acids such as dicarboxylic acids and tricarboxylic acids may also be used. Specific examples of such higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Examples include linoleic acid, phosphoric acid, ricinoleic acid, behenic acid, tallow fatty acid, castor hydrogenated fatty acid, or mixtures thereof. Higher fatty acids are block copolymer 700
o, or-, parts by weight relative to parts by weight, the amount of acid blended is 0
．． 0! If the amount is less than 5 parts by weight, yellowing due to the use of the hindered amine compound cannot be prevented, and if it exceeds 5 parts by weight, the higher fatty acids will lead to the surface of the molded product and deteriorate the appearance characteristics, which is not preferable.

The hindered amine compound of component (b) used in the present invention has at least seven groups represented by the following formula (1) in the molecule (wherein R1s R2, R3 and R4 are the same or different,
represents a straight-chain or branched alkyl group having y to 2 carbon atoms, or R1 and R2 together, together with the carbon atom to which they are attached, represents a cycloalkyl group having y to 2 carbon atoms; groups or the same or different, having 7 or more carbon atoms
) represents a straight-chain or branched-chain alkyl group]. X and X' represent hydrogen or oxygen atoms, or linear or branched alkyl groups having 7 to 7 carbon atoms, alkenyl groups or alkynyl groups having 3 to 2 carbon atoms, or /3 represents an alkyl group, a nitroso group, or a hydroxyalkyl group, an alkoxyalkyl group, or an acyloxyalkyl group, which may or may not be substituted with an aryl group. ). The group represented by (1) above (wherein R, is / when m is /: an acyl group derived from aliphatic, aromatic or heterocyclic monocarboxylic acid, N-substituted lupamic acid or N- Substituted carbamoyl groups or N-substituted thiocarbamoyl groups composed of substituted thiocarbamic acids, obtained by removing one hydroxyl group from an oxyacid such as sulfinic acid, sulfonic acid, phosphoric acid, phosphorous acid or boric acid A heptavalent group, an alkyl group such as methyl or stearyl, a cycloalkyl group such as cyclohexyl, an aralkyl group such as benzyl, ant 1 such as phenyl, chlorphenyl, tolyl or naphthyl has the same meaning as above. ).

-, '1:' When m is 2: diacyl group derived from aliphatic, aromatic or heterocyclic dicarboxylic acid, dicarpamoyl group derived from dicarboxylic acid or bisthiocarbamic acid, or derived from pistiocarbamic acid dicarpamoyl or bisthiocarbamoyl groups, carbonyl groups, disulfonic acid, covalent groups obtained by removing hydroxyl groups from oxyacids such as phosphoric acid, phosphorous acid or boric acid, methylene, ethylene or hexamethylene It represents an alkylene group such as, an arylene group such as p-phenylene, or an arylene group such as α·αl p-xylylene.

When m is 3: a triazyl group derived from an aliphatic, aromatic or heterocyclic tricarboxylic acid, a tricarbamoyl group or a tristhiocarbamoyl group derived from tricarbamic acid or hysterocarbamic acid,
trivalent groups obtained by removing three hydroxyl groups from oxyacids such as trisulfonic acid, phosphoric acid, phosphorous acid or boric acid, alkantriyl groups such as propane-/·co-3-yl, arenes; Indicates a triyl group or an arenetriyltrialkylene group. ), (wherein R6 is an alkyl group such as methyl, ethyl, propyl, cycloalkyl group such as cyclopentyl, cyclohexyl, or phenyl, tolyl, nitrophenyl, chlorphenyl, naphthyl when n is 7); An aryl group such as tokyphenylene, chlorphenylene, where n is
It represents an arylene group such as nitrophenylene and methylphenylene, or an alkylene group such as methylene, ethylene, and hexamethylene. ) piperidine-spiro-hydantoin derivatives represented by these, piperidine-spiro-imidazolidine derivatives represented by these, iminopiperidine derivatives represented by (wherein R7 represents an aryl group or a heterocyclic residue); Methylpiperidone derivative, (in the formula, R8 and R9 represent an alkoxy group, an acyloxy group, an aralalkoxy group, an alkylthio group, or an allylthio group) (in the formula, RIG and R11 are the same or different, and a cyano group,
It represents an aryl group such as phenyl, chlorphenyl, tolylmodyl or hanaphthyl, an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl or stearyloxycarbonyl, an acyl group or carbamoyl group such as acetyl or benzoyl. ) Examples include piperidine derivatives represented by

Specific hindered amine compounds include: ■ Guacetoxyco-co-Otsu-Otsu-tetramethylpiperidine ■ Coustearoyloxyco-2-Otsu-Otsu-tetramethylpiperidine ■ Guacryloyloxy-λ pieces Otsu-Go- Tetramethylbiperidine ■ Goupenzoyloxyco-6,6-tetramethylpiperidine (5) g -(p-chlorobenzoyloxy)-1,2
・Otsu・Otsu-Tetramethylpiperidine ω) Goomethoxy-2・Co・6・Otsu-Tetramethylpiperidine■Cucyclohequinyloxyco・λ・Go−ni−Tetramethylpiperidine＜+3)＜t-Benzyloxy−・λ・Otsu・Otsu-Tetramethylpiperidine■q-Phenoxyco・Co・Otsu・6-Tetramethylpiperidine+1(1-(phenylcarbamoyloxy)-2・λ
Otsu・6-titrametherbiperidine■Bis(2-,2-1,-i<-tetramethylda-piperidyl)oxalate@bis(,2・2-tetramethyl-gupiperidine)malonate■bis(,2・Co・Z bow-tetramethyl-Co, piperidyl) adipate ■Bis(2・λ・6,6-tetramethylda-piperidyl) sebacate [phase] Bis(2・co・6,6-tetramethylda-piperidyl) terephthalate [phase ]/・Corpis (2・Co・Otsu・ni-tetramethyl-
CupiperidylokiV)-ethane0α・α′-bis(2・-2-4-g-tetramethyl-
Goopiperidylokiv)-p-xylene■Bis(Ko・2bow・6-titramethel-goubiperidyl)hexamethylene−/・Otsu-dicarbamate 0tris(2・λ・Otsuyuki-tetramethyl-goo piperidyl) benzene-/・3・autricarboxylate [phase] tetra(2・2-60-tetramethyl-coupiperidyl)butane−/・”・3・gutetracarboxylate@11-(ethylcarbamoyloxy)- Ko・λ・go・
6-tetramethylpiperidine■Chu(cyclohexylcarbamoyloxy)-2・Co・6・Go-tetramethylbiperidine@&-(ethylthiocarbamoyloxy)-2・λ・6・O-tetramethylpiperidine Cu(phenylthiocarbamoyloxyv)-1.
λ・6・Otsu-Tetramethylpiperidine@Cubenzenesulfonyloxy-2-2-6-g-Tetramethylpiperidine [Co.] λ・No.6・ni-Tetramethylda gauge methoxypiperidine@Co・Co・6・6 -tetramethylda-gagenpropioxypiperidinelico-2-dimethylliggu-dimethoxy-ot-spiro-(/-cyclohexane)piperidine goo-butyliminoco-go-6-tetramethylpiperidine)gubenzylimino-λ β・6・6-Tetramethylpiperidine lig-(p-tolylimino)-2・λ・, <-g-tetramethylpiperidine-tetramethylpiperidine y-(α-cyano-α-ethoxycarbonylmethylene)-2・λ・z-6-tetramethylpiperidine■Chu(α・α-dimethoxycarbonylmethylene)-2
・2,6-6-Tetramethylpiperidine [Co., Ltd.] Ha3-f
-) Rear-no-oxo-3-phenyruderimino-2,7,2,9-tetramethyl-spiro[g.j]decane ■l.3.l-triazor-gudioxo-3-cyclohexyl-guimino-7・7U9・tertetramethyl-spiro [g! ] Decane The above-mentioned hindered amine compound is 0.0% per 700 parts by weight of the block copolymer.
005 to 3 parts by weight, preferably θ, θ/~- parts by weight. The amount of hindered amine compound is θ, θθ
If the amount is less than 3 parts by weight, the effect of improving weather resistance will not be sufficient, while if the amount exceeds 3 parts by weight, no significant improvement effect will be observed. Furthermore, hindered amine compound LS-ta4
t4t (Sankyo Co., Ltd., Tepa Geigi Co., Ltd.), mark LA-
s7 (Adeka Argus), etc., and these can be used as the component (b) of the present invention.

In the present invention, in addition to the hindered amine compound of component (bl), a benzophenone compound and/or a benzotriazole compound may be used in combination.When such compounds are used in combination, the effect of improving weather resistance is mutual. Even if the amount of the hindered amine compound is reduced, a product with good weather resistance can be obtained.When these compounds are used together, the amount of block copolymer/θ
The hindered amine compound of component (b) is o, o o s~/part by weight, preferably O3θ~ with respect to the θ weight part.
Suitable examples include O0♂ parts by weight, θ, Or-, 2 parts by weight, preferably 0.1 to 1.0 parts by weight of benzophenone compounds and/or benzotriazole compounds.

Seven examples of benzophenone compounds and/or benzotriazole compounds that can be used in the present invention include the following.

0-2. <1-dihydroxypentuphenone 02-hydroxy-goumethoxybenzophenone@cohydroxy-q-rooctoxybenzophenone@o2-hydroxy-II -n-dodecyloxybenzophenone (4,1) 2-hydroxy-goubenzyloxybenzophenone (422- C-2'-hydroxydermethylphenyl)-benzotriazole λ-(2'-hydroxy-3-j'-di-t-butylphenyl)-j-chloro-penztriazole 0,:2-<co'- Hydroxy-31-1-butyl-!
-methylphenyl)-! -Chlorobenzotriazole ■2- (2'-Hydroxy-3', O'-di[-amylphenyl)-penztriazole 2-(!-hydroxy-3-!-di[-butylphenyl)-benzotriazole■ 2-(2'-Hydroxy-de-t-butylphenyl)benzotriazole 2-(2'-hydroxy-guoctylphenyl)-
Benzotriazole Furthermore, the block copolymer composition of the present invention includes a P-phenylenediamine compound, a quinoline compound, a dithiocarbamate compound, /, 3-bis(dimethylaminopropyl)-2-thiourea, and a wax. By blending at least seven selected compounds, the durability under outdoor conditions can be further improved. -1-phenylenediamine compounds include diaryl-p-phenylenediamine, N,N'-diphenyl-1)-phenylenediamine, N-phenyl-N'-isopropyl-
p-phenylenediamine, N,N'-diconaphthyl-p-phenylenediamine, N-(3-methacryloyloxy-cohydroxyprobyl)-N'-phenyl-p-phenylenediamine, alkyl IL 74',!
Shizui+, 11+MaS+/N' 1-r-H+
N'-11 octyl p-phenylenediamine, N
-Phenyl-N'-(/,3-dimethylbutyl)-p-
Phenylenediamine, N,N'-bis(/-methylhebutyl)-p-phenylenediamine, mixed diaryl-p
-phenylenediamine, etc. As a quinoline compound, 2.2,4t-)limethyl-/9.2
Examples of -dihydro- include monoethoxyquinoline, poly(2,,2°gutrimethyl/, 2-)limethyl/, 2-dihydroquinoline), and the like. Also, as a dithiocarbamic acid compound, diethylditeoca! Examples include nickel repamate and nickel diptyldithiocarbamate. These are block copolymers 70 as required.
It is generally added in an amount of 2 to 0,007 parts by weight, preferably /-0,007 parts by weight.

Furthermore, the block copolymer composition of the present invention may contain lubricants, antistatic agents, various stabilizers, plasticizers, softeners, etc., as necessary.

The block copolymer composition of the present invention can also be used in combination with other polymers. Such polymers include the above-mentioned vinyl aromatic hydrocarbon-based polymers, the above-mentioned vinyl aromatic hydrocarbon-based polymers and other monomers,
For example, ethylene, propylene, butylene, vinyl chloride,
Vinylidene chloride, vinyl acetate, acrylic esters such as methyl acrylate, methacrylic esters such as methyl methacrylate, copolymers with acrylonitrile, rubber-modified high-impact styrenic resins (HIPS), acrylonitrile-butadiene-styrene copolymers, etc. Polymer (AB8), methyl methacrylate-butadiene-styrene copolymer, polyphenylene ether resin, polyethylene, polypropylene, polycarbonate, polysulfone, polyamide,
Examples include polyester, polyvinyl chloride, polymethacrylate, and the like. .

The block conjugate composition of the present invention can be produced by any conventionally known compounding method.

For example, a method is used in which the bath agent is removed by heating after dissolving or dispersing the mixture in a single agent such as an oven roll, an intensive mixer, an internal mixer, a coney goo, a continuous kneader with a twin-screw rotor, and an extruder.

Examples are shown below to explain the present invention in more detail, but these examples are intended to demonstrate the excellent effects obtained by the present invention, and are not intended to limit the scope of the present invention. .

The block copolymers used in the examples of the present invention are as follows:
It was manufactured as follows.

[Block copolymer (A)]

In a nitrogen gas atmosphere, n-hexane solution containing 20 parts by weight of 3-butadiene/j and 20 parts by weight of styrene was added.
- Added 0.77 parts by weight of butyllithium and
After polymerization for an hour, an n-hechitin solution containing 20 parts by weight of 3-butadiene and 0 parts by weight of styrene was further added and polymerized at 20° C. for an hour. The obtained polymer was a block copolymer having a B-A-B-A structure with a styrene content of 0.

[Block copolymer (B)]

In a nitrogen gas atmosphere, 0.31 parts by weight of n-butyllithium was added to a cyclohexane solution containing 30 parts by weight of styrene, and after polymerization at 70°C for 7 hours, cyclohexane containing 20 parts by weight of 3-butadiene was added. The solution was added and polymerized at 0°C for 2 hours.

Thereafter, tetrachlorosilane was added in an amount equivalent to the n-butyllithium used, and
A-B) A block copolymer having a 48i structure was obtained.

[Block copolymer (C)]

In a nitrogen gas atmosphere, 0.07 parts by weight of n-butyllithium was added to a cyclohexane solution containing 30 parts by weight of styrene and 0.3 parts by weight of tetrahydrofuran, and the mixture was heated at 70°C.
After polymerization for 7 hours, a cyclohexane solution containing 20 parts by weight of 3-butadiene/j and 20 parts by weight of styrene was further added and molding was carried out at 70°C for 2 hours. The obtained polymer is a block copolymer having an A-B-A structure with a styrene content of 25 Ii [Block copolymer (D)] In a nitrogen gas atmosphere, cyclohexane containing part by weight of butadiene/j Add n-butyllithium to the solution θ, θ♂
After adding parts by weight and polymerizing at 70°C for 1 hour, 20 parts by weight of styrene, 1 part by weight of butadiene, and 50 parts by weight of styrene were respectively added and polymerized. The polymerization temperature in each step was 20° C., and the polymerization time was 7 hours. The obtained polymer has a styrene-containing t7θ weight of B
It was a block copolymer with a -A-B-A structure.

In addition, each block copolymer contains BHT and T as stabilizers.
0.5 parts by weight of each NP was added to 700 parts by weight of the block copolymer.

Examples/-1 and Comparative Examples 7-23 Weather resistance and color tone were investigated using compression molded pieces of block copolymer compositions prepared according to the formulation shown in Table 7.
The results are shown in Table/.

Next, as Comparative Examples 9 to 23, Examples /~/! except that higher fatty acids were not used. Comparative samples of compression molded pieces similar to the above have weather resistance in Examples/~/! Although they had the same performance as the above, they all had extremely poor color tone (evaluation rank: poor or poor) and were problematic in practice.

The above results revealed that a composition with excellent weather resistance and color tone can be obtained by blending a higher fatty acid and a hindered amine compound with a block copolymer.

(Margin below) Table 7 (Continuation of table/) (Note 1) The compound number is the number in the above specification.

However, ■ to ■ are the following compounds.

■: f-nor L89 Gugu (Sankyo Co., Ltd.) ■: Palmitic acid ■: Behenic acid (Note 2) The amount added to 10θ parts by weight of the block copolymer is shown.

(Note 3) The tensile elongation at break of each sample after the 700-hour weather meter irradiation test was compared with the tensile elongation at break of each sample before the test, and the quality of weather resistance was determined based on the retention rate.

Equipment used: Atlas Sunshine Weather Meter Judgment criteria: A; Retention rate! θ ratio above; Retention rate Otsu θ Chi - Hi, Less than za θ Chi C; Retention rate 0 Chi or more, less than Otsu θ Chi: Retention rate less than θ ratio (Note 4) Block copolymer composition The color tone was determined by the color of the molded piece.

Judgment criteria: ○; No coloring. Or pale yellow ×; dark yellow. Or red and yellow Examples 72-2/ A higher fatty acid and a hindered amine compound were added to a mixture of a block copolymer and polystyrene, etc. to produce a compression molded piece. The weather resistance and color tone of each sample obtained were examined, and the results are shown in Table 2.

(Margin below)

Claims (1)

[Claims] Based on 700 parts by weight of a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, (a) higher fatty acid θ,
Block copolymer composition containing ~3 parts by weight of a hindered amine compound (o, o or ~3 parts by weight)