JPS62197409A - Block copolymer and composition containing same - Google Patents

Abstract

PURPOSE:To obtain a block copolymer which shows a specified composition distribution in the analysis of a composition by high-performance liquid chromatography and excells in kneadability with a thermoplastic resin, etc., by copolymerizing a vinylaromatic hydrocarbon with a conjugated diene in specified conditions. CONSTITUTION:This block copolymer has a polymer segment based on a vinylaromatic hydrocarbon (e.g., styrene) and a polymer segment based on a conjugated diene (e.g., butadiene), and the weight ratio of the vinylaromatic hydrocarbon to the conjugated diene is 10/90-60/40. It is required that the total amount of component A (a component in which the vinylaromatic hydrocarbon content is higher than that of the main peak and the difference between the both is 5wt% or above) and a component B (a component in which the vinylaromatic hydrocarbon content is lower than that of the main peak by at least 5wt%) be 20-80% when determined from a composition analysis by high-performance liquid chromatography.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent cross-talkability with thermoplastic resins, inorganic/organic fillers, etc., and compositions containing these materials have good processability and mechanical strength. and the composition.

[Conventional technology]

Unlike natural rubber or ordinary synthetic rubber, block copolymers made of conjugated dienes and vinyl aromatic hydrocarbons can be cured at room temperature without using vulcanizing agents, accelerators, or fillers such as carbon blanks. It has strength and elastic properties comparable to those of vulcanized nidistomers, and exhibits processability similar to that of thermoplastic plastics at high temperatures, so it is currently used very widely by taking advantage of these properties. Examples include injection molded products, extrusion molded products, blow molded products such as hoses, footwear, window frames, containers, toys, household goods, etc.

In these various uses, block copolymers are generally used in combination with inorganic fillers, organic fillers, thermoplastic resins, and the like. For example, Tokuko Sho 45-19388, Tokko Sho 51
-36292. JP-A No. 53-96048 describes a composition for footwear containing a block copolymer mixed with a thermoplastic resin such as polystyrene or polyethylene, a softening agent such as a naphthenic oil, and an organic filler such as clay or calcium carbonate. It is stated that it is used. Also special public service 1971-7126
Publication No. 47-43618, Special Publication No. 52-
Publication No. 21012 describes a method of improving impact resistance by blending the above block copolymer with polystyrene or rubber-modified polystyrene. Similarly, % Kosho 42-1
9935, Japanese Patent Publication No. 45-4624, Japanese Patent Publication No. 5067, Japanese Patent Publication No. 46-1867,
JP-A-48-62851 discloses polypropylene, polyethylene, acrylic resin, vinyl chloride resin,
Attempts have been made to improve the properties of polyphenylene ether resins by blending them with the above block copolymers.

[Problem that the invention seeks to solve]

However, these conventional compositions 11C-J6 use block copolymers with sharp molecular weight distribution and uniform composition distribution, which are produced by utilizing the characteristics of living anionic polymerization. When combined, it exhibits excellent properties such as high tensile strength when used alone, but in compositions containing inorganic fillers, thermoplastic resins, etc., mutual kneading properties are insufficient and it is difficult to achieve the desired performance, such as good strength and impact resistance. Problems have arisen, such as difficulty in achieving properties such as clarity and transparency, and reduced processability.

[Means and effects for solving the problem] Under the present circumstances, the present inventors have found that when using inorganic fillers, thermoplastic resins, etc. in combination with block copolymers, they have excellent crosstalk with them, As a result of our research into obtaining a block copolymer that exhibits good processability, mechanical strength, etc., we found that it was possible to use a block copolymer with a specific composition distribution in compositional analysis using high-performance liquid chromatography. The present invention was completed after discovering that the object can be achieved using K.

That is, the present invention has at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and the present invention has a polymer segment mainly composed of a vinyl aromatic hydrocarbon and a conjugated diene. Weight ratio is 10/90 or more,
In a block copolymer or its hydrogenated product having a ratio of less than 60/40, component A (where the vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak) determined from composition analysis by high performance liquid chromatography. , and the difference between them is 5% by weight or more) and component B (the component whose vinyl aromatic hydrocarbon content is lower than the vinyl aromatic hydrocarbon content of the main peak and the difference between them is 5% by weight or more)
A block copolymer having a total amount of from 20 to 80%, or a composition containing the block copolymer.

The present invention will be explained in detail below.

The block copolymer of the present invention has at least one, preferably two or more, vinyl aromatic hydrocarbon-based polymer segments and at least one conjugated diene-based polymer segment, and has a vinyl aromatic The block copolymer has a weight ratio of group hydrocarbon to conjugated diene of 10,790 or more and less than 60/40, preferably 15/85 to 55/45. The content of vinyl aromatic hydrocarbon is 1 at the above ratio A value.
If it is less than 0790, the strength and crosstalk will be poor, and if it is less than 60
/40 or more is not preferable because the rubber elasticity decreases and the effect of improving the impact resistance of thermoplastic resins and the like deteriorates. In the present invention, a polymer segment mainly composed of vinyl aromatic hydrocarbons is defined as a polymer segment whose vinyl aromatic hydrocarbon content is 50111j.
% or more, and is composed of a copolymer portion of a conjugated diene and a vinyl aromatic hydrocarbon and/or a vinyl aromatic hydrocarbon polymer portion. In addition, a polymer segment mainly containing a conjugated diene is a polymer segment in which the vinyl aromatic hydrocarbon content is less than 50% by weight, and a copolymer portion of a conjugated diene and a vinyl aromatic hydrocarbon and/or Composed of a conjugated diene polymer portion. The vinyl aromatic hydrocarbon in the copolymer portion of the conjugated diene and the vinyl aromatic hydrocarbon may be uniformly distributed in the polymer chain or may be distributed in a tapered manner.

Further, the copolymer portion may include a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and/or a plurality of portions in which vinyl aromatic hydrocarbons are distributed in a tapered manner.

In such a case, the proportions of conjugated diene and vinyl aromatic hydrocarbon in each copolymerization portion may be the same or different.

The biggest feature of the block copolymer of the present invention is that it uses liquid chromatography (using an ultraviolet absorption photometer as a detector),
Component A (detected at a wavelength of nm) determined from composition analysis by K
greater than the vinyl aromatic hydrocarbon content and the difference is 5
The total amount of component B (component whose vinyl aromatic hydrocarbon content is less than the vinyl aromatic hydrocarbon content of the main peak and whose difference is 531 mass % or more) It is 20-80%, preferably 30-70%. If the total amount of component A and component B is less than 20%, the impact resistance will be poor, and if it exceeds 80%, the transparency and impact resistance will be poor, which is not preferable.

In the present invention, the composition analysis by high performance liquid chromatography refers to the method developed by Professor Naka of the University of Agriculture and Technology (Ma
kranoJ, Chem, Rapid Com
Un, 5, 719-722 (1984) and Proceedings of the Society of Polymer Science, Vol. 32, No. 9, 2227-2230 (1983)
) K description), and acrylonitrile-ethylene glycol dimethacrylate copolymer gel (particle size z5-5
．． This is a method for separating and analyzing polymers based on differences in composition by using an eluent composition gradient method (hexane/chloroform) in a column packed with 0 μm). An ultraviolet absorption photometer is used as a detector, and detection is performed at a wavelength of 254 nm. The composition of the eluted component is determined using a calibration curve prepared using a standard sample prepared by the method described in the above-mentioned literature. In the present invention, the vinyl aromatic hydrocarbon content of the main peak is the vinyl aromatic hydrocarbon content (wt%) corresponding to the portion where the absorbance at a wavelength of 254 nm is maximum in the high performance liquid chromatogram obtained by the above method. . In addition, when there are two or more parts in which the absorbance at a wavelength of 254 nm is maximum in the high performance liquid chromatogram, the part with the highest content of vinyl aromatic hydrocarbon is defined as the main peak.

The proportion of OA in the present invention is calculated by calculating the area of the component corresponding to the component whose vinyl aromatic hydrocarbon content is 5% or more by weight or more than the vinyl aromatic hydrocarbon content of the main peak in a high-performance liquid chromatogram. It is found by dividing K by the area of . Similarly, the proportion of component B is determined by dividing the area of the portion corresponding to the component whose vinyl aromatic hydrocarbon content is 5% or more by weight less than the vinyl aromatic hydrocarbon content of the main peak by the area of all components. It is determined by

In the present invention, when the vinyl aromatic hydrocarbon content of the main peak is equal to or lower than the vinyl aromatic carbon content of the entire block copolymer, the former is preferably smaller than the latter, and the difference is 1% by weight. In the above cases, the impact resistance is excellent, and conversely, when the vinyl aromatic hydrocarbon content of the main peak exceeds the vinyl aromatic hydrocarbon content of the entire block copolymer, the former is preferably larger than the latter, and If the difference is 1% by weight or more, the transparency is excellent.
Depending on the composition distribution IIK, it can be used for various purposes.

The block copolymer of the present invention has a ratio of weight average molecular weight (hereinafter referred to as C) to number average molecular weight (hereinafter referred to as Nn) of the vinyl aromatic hydrocarbon polymer block in the block copolymer of 1.2. ~3. o, preferably in the range of 1.3 to zO, is recommended from the viewpoint of crosstalk and the effect of improving the impact resistance of the thermoplastic resin.

MwAJn of the vinyl aromatic hydrocarbon polymer block can be measured as follows. A vinyl aromatic hydrocarbon polymer component (
L・M fist KOLTHOFF, e taJ,, J, P
olym, sci, 1,429 (1946)) by gel permeation chromatography (Gel permeation chromatography)
PC) and calculated using a conventional method (for example, the method described in "Gel Chromatography Basics" published by Kodansha). The calibration curve for GPCK is created using standard polystyrene commercially available for GPC.

The block copolymer of the present invention can be obtained by polymerization in a hydrocarbon solvent using an organolithium compound as an initiator.

Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane, and alicyclic hydrocarbons such as dichloropentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene can be used. Organolithium compounds have VC in the molecule.
An organic lithium compound containing one or more lithium atoms, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ec
-butyllithium, tert-butyllithium, hexamethylene dilithium, butadienyl dilithium, imprenyl dilithium, and the like.

In the present invention, vinyl aromatic hydrocarbons include styrene, 0-methylstyrene, p-methylstyrene, p-
Examples include tcrt-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, and styrene is particularly common. These may be used not only alone, but also as a mixture of two or more. The conjugated diene is a diolefin having a pair of conjugated double bonds, such as 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.

When producing the block copolymer of the present invention, the method for forming a copolymer portion of a vinyl aromatic hydrocarbon and a conjugated diene is as follows: (1) A mixture of a vinyl aromatic hydrocarbon and a conjugated diene is continuously mixed. Methods such as (if) copolymerizing the vinyl aromatic hydrocarbon and the conjugated diene using a polar compound acid or a randomizing agent can be adopted. Polar compounds and randomizing agents include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, potassium and sodium Examples include alkoxides.

The bonding state of the vinyl aromatic hydrocarbon copolymerized into the copolymer portion of the vinyl aromatic hydrocarbon and conjugated diene by the above method was developed by Professor Naka of Agriculture and Technology University et al. Method (Journal of Japan Rubber Association, 54 (91)
, 564 (1981)), it can be known from K that ozone decomposes. The ratio of the component corresponding to styrene monomer to the component corresponding to styrene tetramer measured by this method is 5!5% of the total vinyl aromatic hydrocarbon volume in the block copolymer. If the amount is less than 5% by weight, a block copolymer with relatively good hardness and rigidity will be obtained, and if it is 5 to 40% by weight, a relatively tough block copolymer will be obtained.

The block copolymer of the present invention has a polymer structure having the general formula % formula %) (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. block.The boundary between A block and B block does not necessarily need to be clearly distinguished.n is an integer of 1 or more, and generally an integer of 1 to 5.) A linear block represented by Copolymer or general formula, ni) C (BA 斥 9 iX (e) ((A-B tei 韮iX (he) B+F-A-]hiF1-X
(In 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, epoxidized soybean oil, or a carboxylic acid ester, or a polyfunctional organolithium compound, etc. radial block copolymer represented by the residue of the initiator (indicated by m and n are integers of 1 or more, generally integers of 1 to 5), or any mixture thereof. be. Particularly preferred is a block copolymer in which both ends of the polymer chain are formed of polymer blocks containing mainly vinyl aromatic hydrocarbons.

The method for producing the block copolymer of the present invention includes adding a new catalyst during production, or adding alcohol or alcohol during production.
Do not add a deactivating agent such as carboxylic acid to partially deactivate the active sites, or add a chain transfer agent such as toluene, arenes, vinyl acetylenes, secondary amines to cause a chain transfer reaction. , adjusting the miscibility within the polymerization system, or using these methods in combination, but is not limited thereto. Component A
Any method may be used as long as the ratio of component B is within the range defined by the present invention.

The molecular weight of the block copolymer used in the present invention is 10.0
00 to 1,000,000, preferably 20,000 to
5,000,000. ) In addition, the block copolymer can be modified by hydrogenation, halogenation,...hydrogenation, or chemical reaction to the extent that it does not impair its basic properties, such as the effect of improving impact resistance. ,
Modifications such as introduction of functional groups such as nitrile groups, sulfonic acid groups, and amino groups may also be performed.

A 4IK hydrogenated (hydrogenated) block copolymer is a preferred method of improvement because it improves heat aging resistance and weather resistance. The block copolymer before hydrogenation is based on a conjugated diene (1,2-vinyl bond content is recommended to be 20 to 60%, preferably 25 to 50%). The catalysts used include (1) Ni, Pt,
Supporting metals such as Pd and Ru on carriers such as carbon, silica, alumina, and clay? , :m! A so-called Chive 2-type catalyst using a heterogeneous catalyst, an organic acid salt or acetylacetone salt such as Ni, Co, Fe, or Cr, and a reducing agent such as organic At, or an organometallic compound such as Ru or Rh. Homogeneous catalysts such as so-called organic acid catalysts are known.

Specific methods include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Laid-open No. 59-13.
Hydrogenation is performed in the presence of a hydrogenation catalyst in an inert solvent by the method described in Publication No. 3203 to obtain a hydrogenated product,
Hydrogenated block copolymers for use in the present invention can be synthesized. At that time, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is transformed into an olefin. The compound can be converted into a polymer block. In addition, hydrogenation of aromatic double bonds based on the vinyl aromatic compound copolymerized into the polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a conjugated diene compound as necessary. ``4VC is not particularly limited, but it is preferable that the hydrogenation rate is 20% or less.The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer is determined by infrared spectrophotometry. This can be easily determined using a magnetic resonance analyzer, nuclear magnetic resonance apparatus, etc.

The block copolymer of the present invention can be combined with various thermoplastic polymers to improve mutual properties. These thermoplastic polymers include block copolymer resins of vinyl aromatic hydrocarbons and conjugated dienes with a vinyl aromatic hydrocarbon content of 60 to 95% by weight outside the range specified in the present invention, vinyl aromatic A block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene having a group hydrocarbon content of less than 60% by weight, a polymer of the vinyl aromatic hydrocarbon monomer, a polymer of the vinyl aromatic hydrocarbon monomer, and a conjugated diene. Other vinyl monomers, such as ethylene, propylene,
Butylene, vinyl chloride, vinylidene chloride, vinyl acetate,
At least one vinyl aromatic selected from acrylic esters such as methyl acrylate, methacrylic esters such as methyl methacrylate, copolymers with acrylonitrile, methacrylonitrile, etc., rubber-modified styrenic resins (HIPS'), etc. Hydrocarbon resins, polyethylene, copolymers of ethylene containing 50% or more of ethylene and other monomers copolymerizable with it, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and their hydrolysis polyethylene resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene, polypropylene, copolymers of propylene containing 50% or more of propylene and monomers copolymerizable with it, such as propylene-ethylene copolymers, fluoropylene - Polypropylene resins such as ethyl acrylate copolymer and chlorinated polypropylene, polybutene-1, polybutene-based resins that are copolymers of butene-1 and other monomers copolymerizable with it, polyvinyl chloride, Vinylidene chloride, vinyl chloride and/or polyvinyl chloride resin that is a copolymer of vinyl chloride and/or vinylidene chloride containing 50% or more of vinylidene chloride and other monomers that can be copolymerized therewith, containing vinyl acetate Polyvinyl acetate resin which is a copolymer of vinyl acetate and other copolymerizable monomers in an amount of 50% or more, and its hydrolyzate, acrylic acid and its esters and amides, methacrylic acid and its esters and amides. Polymer, polyacrylate resin which is a copolymer with other copolymerizable monomers containing 50% or more of these acrylic acid monomers, a combination of acrylonitrile and/or methacrylonitrile, 50% or more of these acrylonitrile monomers % or more of other copolymerizable monomers, linear polymers in which the constituent units of the polymer are bonded by repeated amide group bonds, such as ε-aminocaprolactam and ω-amino Polyamide resins such as ring-opening polymers of laurolactam, condensation polymers of ε-aminoundecanoic acid, condensation polymers of hexamethylene diamine and dibasic acids such as adipic acid and sepacic acid, and polymers whose constituent units are esters. Linear polymers bonded by repeated bonds K, such as dibasic acids such as phthalic acid and inphthalic acid, or derivatives thereof, and ethylene glycol, propylene glycol, butylene glycol, etc. (1) IJ: 1-AJ[ ), polyester resins, polyphenylene ether resins, or grafted polyphenylene ethers obtained by graft polymerization of vinyl-substituted aromatic hydrocarbons to these resins. Polyacetal resins such as copolymers with and linear polymers in which the constituent units of the polymer are bonded by repeating K of carbonate type bonds, Example t C 4.4 Ni-dihydroxydiphenylalkane, 4.4'
- Polycarbonate resins such as polymers obtained by reaction of dihydroxy compounds such as dihydroxy diphenyl sulfirad and phosgene, or polymers obtained by transesterification of the dihydroxy compounds and diphenyl carbonate, polyether sulfones, polyallyl Consisting of polysulfone resins such as sulfone, thermoplastic polyurethane resins obtained by polyaddition reaction of diisocyanate components and glycol components, polybutadiene resins such as transpolybutadiene and 1,2-polybutadiene, bisphenol A and heptal acidity. Polyarylate resins that are polycondensation polymers, fluororesins with a structure in which part or all of the hydrogen in a chain hydrocarbon polymer compound is replaced with fluorine, polyoxybenzoyl resins, polyimide resins, polyimide resins, etc. It is.

Suitable thermoplastic polymers to be combined with the block copolymer of the present invention include styrene resins, polyethylene resins, polypropylene resins, polycarbonate resins,
It is a polyphenylene ether resin. Styrenic resins are particularly preferred, and examples of such resins include non-rubber-modified styrenic polymers and rubber-modified styrenic polymers.

The non-rubber-modified styrenic polymer is obtained by polymerizing the above-mentioned vinyl aromatic hydrocarbon compound or a monomer copolymerizable therewith. Monomers copolymerizable with vinyl aromatic hydrocarbon compounds include α-methylstyrene, acrylonitrile, acrylic ester,
Examples include methacrylic acid ester and maleic anhydride.

Particularly preferred non-rubber modified styrenic polymers include polystyrene, styrene-α-methylstyrene copolymer,
Examples include acrylonitrile-styrene copolymer, styrene-methacrylic acid ester copolymer, and styrene-maleic anhydride copolymer, and these can be used alone or in a mixture of two or more.

The rubber-modified styrenic polymer is obtained by polymerizing a mixture of a vinyl aromatic hydrocarbon compound or a monomer copolymerizable therewith with an elastomer, and polymerization methods include suspension polymerization, emulsion polymerization, bulk polymerization, Bulk-suspension polymerization and the like are commonly carried out. Examples of monomers copolymerizable with vinyl aromatic hydrocarbon compounds include α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, and maleic anhydride.

Examples of elastomers include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, high styrene rubber, polybutadiene rubber, chloroprene rubber, polybutene rubber, rubbery ethylene-propylene copolymer, and rubbery butadiene-acrylonitrile copolymer. polymer,
Butyl rubber, various nitrile rubbers, rubbery ethylene-vinyl acetate copolymers, rubbery ethylene-acrylic acid ester copolymers, rubbery atactic polypropylene resins,
A rubbery ethylene-acrylic acid ionomer or the like is used.

These distomers are generally dissolved in an amount of 2 to 70 parts by weight, more generally 3 to 50 parts by weight, per 100 parts by weight of a vinyl aromatic hydrocarbon compound or a monomer copolymerizable therewith. Alternatively, it is subjected to bulk polymerization, bulk-suspension polymerization, emulsion polymerization, etc. in the form of latex.

Particularly preferred rubber-modified styrenic polymers include impact-resistant rubber-modified styrene polymers, acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and methacrylic ester-butadiene-styrene copolymers. , impact-resistant rubber-modified styrene-maleic anhydride copolymer, etc., and these can be used alone or in a mixture of two or more.

When the block copolymer of the present invention is used in combination with the above-mentioned thermoplastic polymer, the blending amount can be varied depending on the properties of the desired composition, and generally the block copolymer and the thermoplastic polymer are combined. It can be used at a weight ratio of 99/1 to 1/99, preferably 9515-5/95. Two or more thermoplastic polymers may be used in combination in any proportion.

Specifically, when using a block copolymer as a modifier for a thermoplastic resin, the weight ratio of the block copolymer and the thermoplastic polymer is 2/9 to 50150, preferably 5/9. 40/60 is common. When improving the hardness of the block copolymer, the weight ratio of the block copolymer to the thermoplastic polymer is 40/6 to 97/3. Preferably, 90/10 is common.

The block copolymer of the present invention can be used by blending an inorganic filler and/or an organic filler. Specific examples include calcium carbonate, clay, silica, zinc oxide, magnesium carbonate, magnesium silicate, talc,
Diatomaceous earth, dolomite, mica powder, aluminum sulfate, barium sulfate, graphite, glass fiber, carbon black, high styrene resin, coumaron, indene resin, phenol/formaldehyde resin, modified melamine resin,
Examples include petroleum resin, lignin, wood flour, and carbon fiber. These are block copolymers 10 to 10 per GX Kabe
200 parts by weight, preferably 30 to 150 parts by weight are used.

Further, a softening agent can be blended into the block copolymer of the present invention, and specific examples thereof include lubricating oil, halaffinic process oil, naphthenic process oil, aromatic process oil, paraffin, petrolatum, and asphalt. , vegetable oils (castor oil, cottonseed oil, rapeseed oil, soybean oil, etc.), submersible oils, rosin, fatty acids, etc., and these include 200 parts by weight or less, generally 2G to 100 parts by weight, preferably 2G to 100 parts by weight, per 100 parts by weight of the block copolymer. 80 parts by weight is used in 4o.

Furthermore, the block copolymer of the present invention may contain crosslinking agents such as organic peroxides and inorganic peroxides, pigments such as titanium white, carbon black, and iron oxide, twist retardants, antioxidants, ultraviolet absorbers, and antiblocking agents. , antistatic agents, lubricants, lubricants, other bulking agents, or mixtures thereof.

Specifically, compounds described in "Practical Handbook of Additives for Plastics and Rubber" (Kagaku Kogyo Co., Ltd.) can be used.

In the present invention, the composition containing the block copolymer of the present invention can be produced by any conventionally known compounding method. For example, melt mixing method using general mixing machines such as open rolls, intensive mixers, internal mixers, co-kneaders, continuous kneaders with twin rotors, extruders, etc., and bathing after dissolving or dispersing each component in a solvent and mixing. A method of removing the agent by heating, etc. is used.

〔Effect of the invention〕

The block copolymer of the present invention can be used in combination with various materials by taking advantage of its excellent cross-crossability with thermoplastic resins, inorganic/organic fillers, etc. It is possible to easily produce a composition that has excellent properties such as properties, paintability, printability, adhesion properties, rubber elasticity, tensile strength, and tear strength. Therefore, the block copolymer of the present invention can be used as a modifying material for various thermoplastic resins and thermosetting resins, as a material for footwear, as a material for adhesives and adhesives, as a modifying material for asphalt, as a material for electric wires and cables, and as a material for vulcanized rubber. Can be used as a modification material, etc. for example,
The thermoplastic resin modified with the block copolymer of the present invention is
Extrusion molding, injection molding, blow molding, etc. are used to produce sheets, films, foams, injection molded products of various shapes, blow molded products, etc.
It can be molded into pressure-formed products, vacuum-formed products, etc., and can be used for food packaging containers, home appliances, automobile parts, industrial products, toys, etc. In addition, the composition for soles can be used for various shoes,
Can be used with sandals etc.

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. isn't it.

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

[Block copolymer prisoner]

After the autoclave was internally purged with nitrogen gas, a cyclohexane solution containing 3 parts by weight of purified and dried styrene and an n-butyl lithium solution containing 0.026 parts by weight were added.
A hexane solution was added and polymerization was carried out at 70°C for 1 hour. Next, a cyclohexane solution containing 61 rt parts of styrene and an n-hexane solution containing 0.026 parts by weight of n-butyllithium were added to the polymerization solution, and polymerization was carried out at 70° C. for 1 hour. Furthermore, a cyclohexane solution containing 16 parts by weight of styrene and 0.053 parts by weight of n-butyllithium were added to the polymerization solution.
A n-hexane solution containing parts by weight was added and polymerized at 70°C for 1 hour. Then add butadiene 60 to the polymerization solution.
．． ii Add the cyclohexane solution containing the measuring part to 7
After polymerization at 0°C for 2 hours, a cyclohexane solution containing 15 parts by weight of styrene was further added and polymerization was performed at 70°C for 1 hour. The styrene content of the obtained block copolymer was 40% by weight.

[Block copolymer (B)]

In an autoclave similar to the above, a cyclohexane solution containing 101 parts of styrene and 0.0 parts of n-butyllithium was added.
70 by adding n-hexane solution containing 0.7 parts by weight.
Polymerization was carried out at ℃ for 1 hour. Next, add styrene 15 to the polymerization solution.
A cyclohexane solution containing 0.035 parts by weight of n-butyllithium and an n-hexane solution containing 0.035 parts by weight of n-butyllithium were added and polymerized at 7G"C for 1 hour. Thereafter, 60 parts by weight of butadiene and 3 parts by weight of styrene were added to the polymerization solution. After adding a cyclohexane solution containing 15 parts by weight of styrene and polymerizing at 70°C for 2 hours, a cyclohexane solution containing 15 parts by weight of styrene was further added and polymerizing at 70°C for 1 hour.

The styrene content of the obtained block copolymer was 40% by weight.

[Block copolymer (C)]

A cyclohexane solution containing 5 parts by weight of styrene and 0.08 parts by weight of n-butyllithium were placed in the same autoclave as above.
A n-hexane solution containing parts by weight was added and polymerized at 70°C for 1 hour. Next, a cyclohexane solution containing 20 parts by weight of styrene and an n-hexane solution containing parts by weight of n-butyllithium O,OS were added to the polymerization solution, and polymerization was carried out at 70'C for 1 hour. Thereafter, 35 parts by weight of butadiene and 25 parts by weight of styrene were added to the polymerization solution.
After polymerizing for 1 hour at 0°C, 35 parts by weight of butadiene and 25 parts by weight of styrene were further added and polymerization was carried out at 70"C for 1 hour. Thereafter, 0.07 parts of silicon tetrachloride was added to the polymer solution.
4 parts by weight were added and reacted at 70°C for 30 minutes. The styrene content of the obtained block copolymer was 30% by weight.

[Block copolymer D]

A cyclohexane solution containing 15 parts by weight of styrene and 5 parts by weight of butadiene was placed in the same autoclave as above.
An n-hexane solution containing 0.2 parts by weight of butyllithium was added and polymerization was carried out at 70"C for 1 hour. Next, a cyclohexane solution containing 2-5 parts by weight of styrene and 20 parts by weight of butadiene was added to the polymerization solution. After adding and polymerizing at 70°C for 1 hour, a cyclohexane solution containing 25 parts by weight of styrene and 20 parts by weight of butadiene was added and polymerized at 70°C for 1 hour.
Polymerized for hours. Then, a cyclohexane solution containing 10 parts by weight of styrene and 5 parts by weight of Butashev was added.
After polymerizing for 1 hour at 0°C, 0.025 parts by weight of methanol was added. Furthermore, after adding a cyclohexane solution containing 9 parts by weight of styrene and polymerizing at 70°C for 30 minutes, 0.025 parts by weight of methanol was added.

Thereafter, a cyclohexane solution containing 61 parts of styrene was added and polymerized at 70° C. for 30 minutes, and then 0.025 parts by weight of methanol was added. Finally, a cyclohexane solution containing 5 parts by weight of styrene was added and
Polymerization was carried out for 0 minutes. The resulting block copolymer had a styrene content of 50% by weight.

[Comparative example block copolymer E]

A cyclohexane solution containing 25 parts by weight of styrene and 0.1 part of n-butyllithium were placed in the same autoclave as above.
70 by adding n-hexane solution containing 0.5 parts by weight.
Polymerization was carried out at ℃ for 1 hour. Next, add butadiene 6 to the polymerization solution.
70 by adding a cyclohexane solution containing 0 parts by weight.
Polymerization was carried out at ℃ for 2 hours. Furthermore, a cyclohexane solution containing 15 parts by weight of styrene was added thereto, and polymerization was carried out at 70° C. for 1 hour. The styrene content of the obtained block copolymer was 40% by weight.

[Comparative example block copolymer F]

A cyclohexane solution containing 70 parts by weight of styrene and 0.1 part of n-butyllithium were placed in the same autoclave as above.
Add a n-hexane solution containing 6 parts by weight and heat to 70°C.
Polymerization was carried out for 1 hour. Next, add 30 ml of butadiene to the polymerization solution.
'T! A cyclohexane solution containing L parts was added and polymerized at 70°C for 2 hours. Thereafter, 0.106 parts by weight of silicon tetrachloride was added to this polymer solution, and
Allowed to react for minutes. The styrene content of the obtained block copolymer was 30% by weight.

Each of the block copolymers obtained as described above and 4-methyl-2,6-di-tert-butylphenol doris-nonylphenyl 7-osphite as a stabilizer were used as a block copolymer 100! 0.0 for each tIlsK.
5] After adding iJi parts, the solvent was distilled off under heating.

Next, the composition of each block copolymer was analyzed based on the above-mentioned method developed by Professor Naka of the University of Agriculture and Technology. The analyzed high performance liquid chromatogram generally has 254n on the vertical axis.
The absorbance detected at a wavelength of m is displayed, and the horizontal axis represents the vinyl aromatic hydrocarbon content of the eluted component (obtained using a calibration curve prepared in advance according to the elution amount). An example of this is shown in Figure 1.

In Figure 1 and 1, 1 and 2 represent the block copolymer of the present invention (A1.(B)), and 3 represents the block copolymer of the comparative example (G).

Examples 1 to 3 and Comparative Examples 1 to 4 13 parts by weight of block copolymer, 80 parts by weight of polystyrene (using Stylon 685 manufactured by Asahi Kasei Corporation), impact-resistant rubber-modified polystyrene (polybutadiene dissolved in about 5 parts by weight of Tsuru styrene monomer) After mixing 7 parts by weight (prepared by bulk polymerization method) in a Henschel mixer, a sheet with a thickness of 0.3511 mm was formed using a 4011 φ sheet extruder. The properties of the obtained sheet are shown in Table 1, and it can be seen that the composition containing the block copolymer of the present invention has excellent impact resistance and transparency.

In addition, block copolymers G and H of comparative examples were produced in the same manner as block copolymer A except that the amount of styrene used was changed. Moreover, block copolymer I of a comparative example was created by mixing block copolymers having different styrene contents produced in the same manner as block copolymer A.

21 Table C) Compliant with J Engineering S K6714 Example 4 and Comparative Example 5 100 parts by weight of the block copolymer shown in Table JP2, 50 parts by weight of naphthenic process oil, 50 parts by weight of polystyrene (Styron 679 manufactured by Seikasei Co., Ltd.) A composition was prepared by kneading 55 parts by weight of heavy calcium carbonate, 5 parts by weight of titanium oxide, and 0.5 parts by weight of zinc stearate in a heated kneader, and then injection molded at 190°C using a 5-ounce injection molding machine. Molded at ℃. The performance of the molded product obtained is shown in Table 2.

(hereinafter referred to as θ) Table 2 (Note 3) Based on JIS K-6301 (Note 4)
Dunlop repellent. Compliant with BS 903 Example 5~
13 and Comparative Examples 6 to 14 Compositions (Examples 5 to 13) or block copolymers containing 85 parts by weight of each thermosetting resin shown in Table 3 and 15 parts by weight of each block copolymer A 15 E each
Compositions containing parts by weight (Comparative Examples 6 to 14) were prepared, and test pieces were molded under injection molding pressure. Table 3 shows the Izot impact strength & (according to JIS K-6871. The unit is the ball value, with a notch) of each composition, but the composition containing the block copolymer of the present invention is a comparative example. It has better impact resistance than a composition containing a block copolymer.

Table 3 Example 14.15 Low density polyethylene, linear low density polyethylene (LL
DPE) 101 parts of block copolymer C was added to each 101 parts, and the mixture was kneaded in a 30 mm diameter extruder to form pellets. Next, each pellet is extruded with Sakaki to a height of about 100cm.
A μ film was molded. Each film had good impact resistance.

Example 16 In the method for producing a block copolymer, the total amount of styrene was 30% by weight, and tetrahydrofuran was used as the vinylizing agent. A block copolymer having a content of 30% by weight and a 1,2-bond content of the polybutadiene moiety of 35% was obtained.

This block copolymer was hydrogenated by the method described in JP-A-59-133203 to obtain a block copolymer (Jl) with a hydrogenation rate of 98%. The total amount of A and component B was 55%.

Next, 70 parts by weight of block copolymer J, 10 parts by weight of ethylene propylene random copolymer, and 20 parts by weight of component ascus polypropylene! A certain amount was kneaded in a 30utφ extruder to form pellets, and then injection molded. The resulting composition was a highly transparent composition with a total light transmittance of 90%, a tensile strength of 300' to 9/an'', and an elongation of 600%.

[Brief explanation of drawings]

In Figure 1, 1 and 2 are the blocks 1 and 2 of the present invention, respectively.
3 is the block copolymer of the comparative example (
Hail D. Enemy applicant: Asahi Kasei Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] 1. At least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, wherein the vinyl aromatic hydrocarbon and the conjugated diene In a block copolymer or its hydrogenated product in which the weight ratio of vinyl aromatic hydrocarbon content, and the difference is 5% by weight
or more) and component B (component whose vinyl aromatic hydrocarbon content is less than the vinyl aromatic hydrocarbon content of the main peak and the difference between them is 5% by weight or more) is 20 to 80%. % block copolymer. 2. (1) It has at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and the weight of the vinyl aromatic hydrocarbon and the conjugated diene Ratio is 10/90 or more, 60/
In the block copolymer or its hydrogenated product having a molecular weight of less than 40%, component A (the vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak, and The difference is 5
Block copolymers 1 to 1 in which the total amount of component B (component which is less than the vinyl aromatic hydrocarbon content and whose difference is 5% by weight or more) is 20 to 80% 99 parts by weight (2) A composition comprising 99 to 1 part by weight of a thermoplastic resin. 3. (1) It has at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and the weight of the vinyl aromatic hydrocarbon and the conjugated diene Ratio is 10/90 or more, 60/
In the block copolymer or its hydrogenated product having a molecular weight of less than 40%, component A (the vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak, and The difference is 5
The total amount of component B (component whose vinyl aromatic hydrocarbon content is less than the vinyl aromatic hydrocarbon content of the main peak and whose difference is 5% by weight or more) is 20% by weight or more. ~80% block copolymer (2) 5 to 150 parts by weight of thermoplastic resin (3) 10 to 200 parts by weight of inorganic filler and/or organic filler (4) 0 to 200 parts by weight of softener A composition consisting of