JPS62197410A - Block copolymer resin 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-perforamnce liquid chromatography and excells in transparency, impact resistance, 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 60/40-95/5. 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%) is 20-80% when determined from a composition analysis by high-performance liquid chromatography.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a block copolymer resin with excellent transparency and impact resistance, and a transparent block copolymer resin containing the same block copolymer resin.
This invention relates to a resin composition with excellent impact resistance and the like.

[Conventional technology]

A block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon has excellent transparency when the vinyl aromatic hydrocarbon content is relatively high, and a thermoplastic resin with better impact resistance than polystyrene can be obtained. Its usage has been increasing in recent years, mainly in fields such as food packaging containers, daily necessities, toys, and light electrical parts.

Methods for producing such block copolymers are disclosed in Japanese Patent Publications No. 36-19286, Japanese Patent Publication No. 17979-1979, Japanese Patent Publication No. 2423-1973, and Japanese Patent Publication No. 57-495.
Publication No. 67, Japanese Patent Publication No. 11446/1987, and the like.

Furthermore, such block copolymers may be blended with polystyrene for the purpose of improving rigidity, and conversely, block copolymers may be blended for the purpose of improving the impact resistance of monostyrene. Methods for producing darning compositions include Japanese Patent Publication No. 19388/1988, Japanese Patent Publication No. 43618/1982, Japanese Patent Publication No. 27701/1989, and Japanese Patent Publication No. 32/1983.
Publication No. 774 and Japanese Patent Publication No. 53-417 are cited.

[Problem that the invention seeks to solve]

However, the block copolymers disclosed in these methods do not have sufficient dart impact strength for injection molded or extrusion molded products, and when blended with thermoplastic resins such as polystyrene to improve impact resistance. However, the effect of improving dart impact strength is insufficient, and improvements are desired. Furthermore, the block copolymers disclosed in the above-mentioned methods have a relatively large dependence on molding conditions, and have the disadvantage that their physical properties tend to change due to changes in conditions such as molding temperature and shearing force.

[Means and effects for solving the problem] Under the present circumstances, the present inventors have studied the possibility of obtaining a block copolymer that has excellent dart impact strength and is less dependent on molding conditions in injection molding or extrusion molding. As a result of proceeding with
In a compositional analysis method using high performance liquid chromatography (using an ultraviolet absorption photometer as a detector and detecting at a wavelength of 254 nm), the purpose is achieved by using a block copolymer with a specific composition distribution. This discovery led to the completion of the present invention.

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 has at least one polymer segment mainly composed of a conjugated diene such as a vinyl aromatic hydrocarbon. In a block copolymer or its hydrogenated product with a TTI ratio of 60/40 to 9515, the component number determined from composition analysis by high performance liquid chromatography (vinyl aromatic hydrocarbons with a main peak of vinyl aromatic hydrocarbon content) component B (the vinyl aromatic hydrocarbon content is less than the vinyl aromatic hydrocarbon content of the main peak and the difference is 5% by weight or more) The total amount of ingredients (components that are above) is 20 to 80
%, or a composition of the block copolymer resin and a thermoplastic polymer.

The present invention will be explained in detail below.

The block copolymer resin of the present invention has at least one, preferably two or more polymer segments mainly composed of vinyl aromatic hydrocarbons and at least one polymer segment mainly composed of conjugated dienes. The block copolymer has a weight ratio of aromatic hydrocarbon to conjugated diene of 60/40 to 9515, preferably 65/35 to 90/10. The content of vinyl aromatic hydrocarbon is 60/40 in the above ratio value.
If it is less than 9515, the rigidity and surface hardness will be poor, and if it exceeds 9515, the impact resistance will be poor, which is not preferable. In the present invention, a polymer segment mainly containing vinyl aromatic hydrocarbons is a polymer segment containing 50% by weight or more of vinyl aromatic hydrocarbons, and is a polymer segment containing conjugated diene and vinyl aromatic hydrocarbons. It is composed of a combined portion and/or a vinyl aromatic hydrocarbon polymer portion. A polymer segment mainly containing conjugated diene refers to a polymer segment with a vinyl aromatic hydrocarbon content of less than 50% by weight, 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 Chino-like manner. Further, in the copolymer portion, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and/or portions in which vinyl aromatic hydrocarbons are distributed in a Chi-A-like manner may coexist. 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 resin of the present invention is that it uses liquid chromatography (using an ultraviolet absorption photometer as a detector,
Components (components where the vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak and the difference is 5% by weight or more) and components determined from composition analysis using 54 nm wavelength detection) B (the 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) and the total amount is 2
Fi 0 to 80%, preferably Fi 30 to 70X.

If the total amount of component B and component B is less than 20%, impact resistance and moldability will be poor, and if it exceeds 80%, transparency 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 (Mi
kromol, Ohem, Rapid Co
mmun, mutual.

719-722 (1984) and Proceedings of the Society of Polymer Science 3
2, No. 9, 2227-2230 (1983))
Acrylonitrile-ethylene glycol dimethacrylate copolymer gel (particle size 2.5-5.0 μm)
This is a method to separate and analyze two limers based on their compositional differences by using an eluent composition gradient method (hexane/chloroform) in a column filled with . 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. . still,
If there are two or more portions with the highest absorbance at a wavelength of 254 nm in the high-performance liquid chromatogram, the portion with the higher vinyl aromatic hydrocarbon content is determined to be the main peak.

The ratio of components in the present invention is determined by calculating the area of the part corresponding to the component whose vinyl aromatic hydrocarbon content is υ5% by weight or more higher than the vinyl aromatic hydrocarbon content of the main peak in a high-performance liquid chromatogram. It is found by dividing 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.
It can be used for various purposes depending on the state of composition distribution.

The block copolymer resin of the present invention has a weight average molecular weight (hereinafter referred to as Mw) and a number average molecular weight (hereinafter referred to as Mn) of the vinyl aromatic hydrocarbon polymer block in the block copolymer resin.
ratio of 1.2 to 3.0, preferably 1.3 to 2
．． A value in the range of 0 is recommended from the viewpoint of kneading properties and the effect of improving the impact resistance and elegance of the thermoplastic resin.

Mw/Mn of the vinyl aromatic hydrocarbon polymer block can be measured as follows. A vinyl aromatic hydrocarbon polymer component (LM/ KOLTHOFF, et al, ,
J, Polym, sci, 1, 429 (1
946) method described in d) by gel semiation chromatography (GPO), and a conventional method (for example, [
It refers to the value calculated according to the method described in "Gel Chromatography Basics" published by Kodansha). Is the calibration curve for GPOK a commercially available standard for GPO? Use one made using Listyrene.

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

Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, impentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; or benzene. , aromatic hydrocarbons such as toluene, ethylbenzene, and xylene. Organolithium compounds have 1 in the molecule.
It is an organic lithium compound in which two or more lithium atoms are combined, such as ethyllithium, n-prozyllithium,
Isopropyllithium, n-butyllithium, 5ec-
Examples include butyl lithium, tert-butyl lithium, hexamethylene dilithium, tutagenyl dilithium, and imprenyl dilithium.

In the present invention, vinyl aromatic hydrocarbons include styrene, 0-methylstyrene, p-methylstyrene, pte
rt-butylstyrene, 1,3-dimethylstyrene, α
-Methylstyrene, vinylnaphthalene, vinylanthracene, etc., among which 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-
Phtadiene, 2-methyl-1,3-rtadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,
Examples include 3-pentadiene and 1,3-hexadiene, and particularly common ones include 1°3-citadiene and isoprene. These may be used not only in 111 but also in combination of two or more.

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

The bonding state of the vinyl aromatic hydrocarbon copolymerized into the copolymer portion of the vinyl aromatic hydrocarbon and the conjugated die/die by the above method is determined by the method developed by Professor Naka of Agriculture and Technology University et al. (Japan: Journal of the Pmu Association, 54 (9)
, 564 (1981)). If the proportion of the component corresponding to styrene monomer to the component corresponding to styrene tetramer measured by this method is less than 5% by weight of the total vinyl aromatic hydrocarbons in the block copolymer, the comparison will be made. A block copolymer with good hardness and rigidity can be obtained, and
When the amount is 40%, a relatively tough block copolymer can be obtained.

The block copolymer resin of the present invention has a tellimer structure of the general formula % (%) (In the above formula, LB is a polymer block mainly composed of vinyl aromatic hydrocarbons, and LB is a polymer block mainly composed of conjugated dienes. It is a combined block. The boundary between A block and B block does not necessarily have to be clearly distinguished. n is an integer of 1 or more, and is generally an integer of 1 to 5.) Block copolymer, or general formula, to) ((B-person→-→-X am+2) )((Person-B→-Person+-X n m+4 (In the above formula, A and B are the same as above, and x is, for example, silicon tetrachloride, tin tetrachloride, polyoxygenated soybean oil, calzeta. It represents the residue of a coupling agent such as an ester of phosphoric acid or the residue of an initiator such as a polyfunctional organolithium compound. m and n are integers of 1 or more. Generally, they are integers of 1 to 5.) A radial block copolymer represented by the above formula, or any mixture thereof.Particularly preferred is a radial block copolymer represented by It is a polymer.

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.
Some of the active sites can be deactivated by adding a deactivating agent such as cal-I acid, or a chain transfer reaction can be initiated by adding a chain transfer agent such as toluene, arenes, vinyl acetylenes, or secondary amines. Examples include, but are not limited to, methods for causing the polymerization to occur, adjusting the miscibility within the polymerization system, or using these methods in combination. Any method may be used as long as the ratio of component B and component B falls within the range defined by the present invention.

The molecular weight of the block copolymer used in the present invention is 1G, 0
00~i, ooo, ooo, preferably 20,000~
s, oooρ00. In addition, block copolymers can be treated with hydroxyl groups, thiol groups, and nitrile groups by hydrogenation, halogenation, no-hydrogenation, or chemical reaction within a range that does not impair their basic properties, such as the effect of improving impact resistance. Modifications such as introduction of functional groups such as sulfonic acid groups, sulfonic acid groups, and amino groups may also be performed.

In particular, a hydrogenated block copolymer is a preferable improvement method because it improves heat aging resistance and weather resistance. It is recommended that the block copolymer before hydrogenation has a 1,2-vinyl bond content based on the conjugated diene of 20 to 60%, preferably 25 to 50%. Catalysts used in the hydrogenation reaction include (1) Ni, Pt
, Pd, Ru, etc. supported on a carrier such as Car/7, silica, alumina, diatomaceous material, etc.; and (2) organic acid salts such as Ni, Co, Fe, Or, etc., or acetylacetone. A so-called Ziegler type catalyst using a salt and a reducing agent such as organic B, or Ru
Homogeneous catalysts such as so-called organic complex catalysts such as organometallic compounds such as , Rh, etc. are known. Specifically, the method described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Laid-open No. 59-133203 is used in the presence of a hydrogenation catalyst in an inert solvent. By hydrogenating, a hydrogenated product can be obtained, and the hydrogenated block copolymer used in the present invention can be synthesized. At that time, the number of aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 8.
By hydrogenating 0%, a polymer block mainly composed of a conjugated diene compound can be morphologically converted into an olefinic compound polymer block. In addition, hydrogenation of aromatic double bonds based on a vinyl aromatic compound copolymerized into a polymer block B mainly consisting of a vinyl aromatic compound and, if necessary, a polymer block B mainly consisting of a conjugated diene compound. Although there is no particular restriction on the hydrogenation rate, it is preferable that the hydrogenation rate is 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.

The block copolymer resin of the present invention can be combined with various thermoplastic polymers to improve mutual properties.

These thermoplastic polymers have a vinyl aromatic hydrocarbon content of 60 to 95% by weight, which is outside the range specified in the present invention.
A block copolymer resin of a vinyl aromatic hydrocarbon and a conjugated diene, a block copolymer resin of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of less than 60% by weight, a vinyl aromatic as described above Polymers of group hydrocarbon monomers, the above-mentioned vinyl aromatic hydrocarbon monomers and other vinyl monomers, such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic esters such as methyl acrylate, and methacrylate. At least one selected from methacrylic acid esters such as methyl acid, acrylonitrile, copolymers with methacrylonitrile, etc., TM-modified styrene resin (HfF4), etc.
Vinyl aromatic hydrocarbon resins, polyethylene, copolymers of ethylene containing 50% or more of ethylene and other monomers that can be co-electrified with it, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers Coalescence and its hydrolyzate, monoethylene resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene, polypropylene, copolymers of propylene containing 50X or more of propylene and monomers copolymerizable with it, such as propylene- Polypropylene resins such as ethylene copolymer, propylene-ethyl acrylate copolymer and chlorinated polypropylene, monobutene-1, which is a copolymer of butene-1 and other monomers that can be copolymerized with it Resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride which is a copolymer of vinyl chloride and/or vinylidene chloride containing 50% or more of vinyl chloride and/or vinylidene chloride and other monomers copolymerizable with it. polyvinyl acetate resin, which is a copolymer of vinyl acetate with a vinyl acetate content of 50 Y or more and other copolymerizable monomers, and its hydrolyzate, acrylic acid and its ester, and ami-P1 methacrylate. Polymers of acids and their esters and Ami-P, polyacrylate resins that are copolymers with other copolymerizable monomers containing 50% or more of these acrylic acid monomers, polymers of acrylonitrile and/or methacrylonitrile. Nitrile resins that are copolymers with other copolymerizable monomers containing 50% or more of these acrylonitrile monomers, linear polymers in which the constituent units of the polymer are bonded by repeating amide group bonds, e.g. Ring-opening polymers of ε-aminocaprolactam and ω-aminolaurolactam, condensation polymers of C-aminoundecanoic acid, condensation polymers of hexamethylene diamine and dibasic acids such as adigic acid and henananosic acid. diaryamide resins such as, linear polymers in which the constituent units of the polymer are bonded by repeating ester bonds, dibasic acids such as 7-thalic acid and isophthalic acid, or derivatives thereof, ethylene glycol, propylene glycol, etc. , a polyester resin that is a condensate with a glycol component such as zotylene glycol. Riphenylene ether resin or grafted Irifenylene ether resin obtained by graft polymerizing a vinyl-substituted aromatic hydrocarbon to the resin, polyphenylene sulfy P resin, I lyoxymethylene, copolymer of trioxane and alkylene oxy-P, etc. of? Reacetal resin,
Linear polymers in which the constituent units of the polymer are linked by repeating carbonate-type bonds, such as 4,4'-dihyroxydiphenylalkane, 4,4'--, ,7-hyP
Polycarbonate resins such as polymers obtained by the reaction of dihydroxy compounds such as Roxy) phenylsulfide P with phosgene, or polymers obtained by transesterification of the dihydroxy compounds and diphenyl carzenate, polyether sulfones, Polysulfone resins such as polyallylsulfone, thermoplastic polyurethane resins obtained by polyaddition reaction of diincyanate components and glycol components, trans-liptadiene, 1
, polybutadiene resins such as 2-polybutadiene, polyarylate resins which are polycondensation polymers consisting of bisphenol and 7-talol components, and structures in which part or all of the hydrogen in a chain hydrocarbon polymer compound is replaced with fluorine. These include fluororesins, polyoxybenzoyl resins, polyimide resins, etc.

Suitable thermoplastic polymers to be combined with the block copolymer resin of the present invention include styrene resin, polyethylene resin, and polypropylene resin. T? Polycarbonate resin is a polyphenylene tityl resin. Particularly preferred are styrenic resins, 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-Zam modified styrenic polymers include Id,
1. i! I) Styrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, styrene-methacrylic acid ester copolymer, styrene-maleic anhydride copolymer, etc., these may be used alone or in combination of two or more. It can be used as a mixture of

BIM-modified styrenic polymers are obtained by polymerizing a mixture of a vinyl aromatic hydrocarbon compound or a monomer copolymerizable therewith with a distoner, and polymerization methods include suspension polymerization, emulsion polymerization, bulk polymerization, and block polymerization. -Suspension polymerization etc. are commonly carried out. Examples of monomers copolymerizable with vinyl aromatic hydrocarbon compounds include α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, and maleic anhydride.

In addition, natural ZAM, synthetic isoprenzam, butadienzam, and styrene-butadiene! Mu,
Hystyrene t, polybutadienzam, chloroprenzam, polybutenzam, diam-like ethylene-propylene copolymer, diam-like butadiene-acrylonitrile copolymer, butylzam, various nitrile-based diams, diam-like ethylene-vinyl acetate copolymer, A mu-like ethylene-acrylic acid ester copolymer, a mu-like atactic polypropylene resin, a mu-like ethylene-acrylic acid ionomer, etc. are used.

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

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

When the block copolymer resin 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. 1i fake ratio with union is 99/1~1/9
9, preferably 9515 to 5/95. Two or more thermoplastic polymers may be used in combination in any proportion.

The block copolymer resin of the present invention and the composition containing the block copolymer resin can contain arbitrary additives, if necessary. There is no particular restriction on the type of additive as long as it is commonly used in the formulation of glass sticks, but examples include glass fiber, glass peas, inorganic reinforcing agents such as silica, charcoal, and talc, organic fibers, and coumaron indene resin. organic reinforcing agents such as organic ξ-oxy-P, cross-linking agents such as Kayakaki A-oxy-P, titanium white, casen black,
Examples include pigments such as iron oxide, dyes, twist retardants, antioxidants, ultraviolet absorbers, antiblocking agents, antistatic agents, lubricants, plasticizers, other fillers, and mixtures thereof. Specifically, compounds described in "Practical Handbook of Additives for Plastics and Plastics" (Kagaku Kogyo Co., Ltd.) can be used.

In the present invention, the composition containing the block copolymer resin 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 resin of the present invention and the composition containing the block copolymer resin are transparent and have excellent impact resistance, so they can be used for various purposes by taking advantage of these characteristics. The block copolymer resin of the present invention and the composition containing the block copolymer resin can be molded into various shapes of injection molded products, sheets, and films by conventionally known molding methods such as injection molding, extrusion molding, and blow molding. It can be easily molded into a wide variety of practically useful products such as foams, hollow molded products of various shapes, pressure molded products, vacuum molded products, -axially stretched molded products, biaxially stretched molded products, etc. It can be used for injection molded products such as toys, daily necessities, food containers, miscellaneous goods, light electrical parts, food containers/packaging materials, blister packaging materials, packaging films for fruits and vegetables, confectionery, industrial parts, etc.

Examples of the present invention will be 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 as follows.

[Block copolymer prisoner]

After internally purging the autoclave with nitrogen gas, a cyclohexane solution containing 9 parts by weight of purified and dried butadiene and an n-containing part by weight of n-butyllithium o,ios were added.
- A hexane solution was added and polymerization was carried out at 70°C for 1 hour. Next, a cyclohexane solution containing 15 parts by weight of styrene was added to the polymerization solution, and polymerization was carried out at 70° C. for 30 minutes. After that, a cyclohexane solution containing 21 parts by weight of butadiene was added and polymerization was carried out at 70°C for 1 hour, and then a cyclohexane solution containing 30 parts by weight of styrene was added.
Polymerization was carried out at 0°C for 30 minutes. After that, 0.0175 parts by weight of methanol was added to the polymerization solution, and then a cyclohexane solution containing 20 parts by weight of styrene was added and
Polymerization was carried out for 0 minutes. Thereafter, 0.0175 parts by weight of methanol was added, and further a cyclohexane solution containing 5 parts by weight of styrene was added, followed by polymerization at 70° C. for 1 hour. The styrene content of the obtained block copolymer was 700 weight.

[Block copolymer]

A cyclohexane solution containing 9 parts by weight of butadiene and 0.10 parts by weight of n-butyllithium were placed in the same autoclave as above.
Add a n-hexane solution containing 5 parts by weight and heat to 70°C.
Polymerization was carried out for 1 hour. Next, a cyclohexane solution containing 15 parts by weight of styrene was added to the polymerization solution, and polymerization was carried out at 70° C. for 30 minutes.

Thereafter, a cyclohexane solution containing 21 parts by weight of butadiene was added and polymerized at 70°C for 1 hour, and then a cyclohexane solution containing 40 parts by weight of styrene was further added and polymerized at 70°C for 30 minutes. Thereafter, 0.039 parts by weight of methanol was added to the polymerization solution, followed by 15 parts by weight of styrene, and polymerization was carried out at 70° C. for 1 hour. The styrene content of the obtained block copolymer was 70% by weight.

[For block copolymers]

A cyclohexane solution containing 6 parts by weight of styrene and 0.01 n-butyllithium were placed in the same autoclave as above.
Add a n-hexane solution containing 8 parts by weight and heat to 70°C.
Polymerization was carried out for 30 minutes. Next, add styrene 10 to the polymerization solution.
A cyclohexane solution containing 0.018 parts by weight of n-butyllithium and an n-hexane solution containing 0.018 parts by weight were added and polymerized at 70° C. for 30 minutes. Then styrene 32
A cyclohexane solution containing 0.036 parts by weight of n-butyllithium and an n-hexane solution containing 0.036 parts by weight were added and polymerized at 70° C. for 30 minutes. Then butadiene 4
After repeating four times the operation of adding a cyclohexane solution containing 3 parts by weight of styrene and 3 parts by weight of styrene and polymerizing at 70°C for 30 minutes, a cyclohexane solution containing 24 parts by weight of styrene was further added and the mixture was heated at 70°C for 1 hour. Polymerized. The styrene content of the obtained block copolymer was 84% by weight.

[Block copolymer Φ)]

A cyclohexane solution containing 25 parts by weight of styrene and 0.0 part of n-butyllithium were placed in the same autoclave as above.
Add a n-hexane solution containing 8 parts by weight and heat to 70°C.
Polymerization was carried out for 1 hour. Next, a cyclohexane solution containing 40 parts by weight of styrene and an n-hexane solution containing 0.08 parts by weight of n-butyllithium were added to the polymerization solution, and polymerization was carried out at 70°C for 1 hour. After that, a cyclohexane solution containing 10 parts by weight of styrene and 1 part by weight of 25 butadiene was added and polymerized at 70°C for 1 hour.
．． 085 parts by weight was added and reacted at 70°C for 30 minutes. The styrene content of the obtained block copolymer was 75% by weight.

[Comparative example block copolymer @)]

In the polymerization of the block copolymer described above, polymerization was carried out in the same manner as for the block copolymer (g) except that methanol was not added during the polymerization. The styrene content of the obtained block copolymer was 70% by weight.

[Comparative example block copolymer (b)]

In the polymerization of the block copolymer (0), the polymerization was carried out in the same manner as for the block copolymer (Cl) except that the entire amount of n-butyllithium used in the polymerization was added at the beginning of the polymerization. The styrene content of the obtained block copolymer was 84% by weight.

[Comparative example block copolymer (G)]

In the polymerization of the block copolymer described above, the block copolymer was used except that the entire amount of n-butyllithium used in the polymerization was added at the beginning of the polymerization, and the amount of silicon tetrachloride added was 0.106 parts by weight. Polymerization was carried out in the same manner as in coalescence (b). The styrene content of the obtained block copolymer was 75% by weight.

Each of the block copolymers obtained as described above contained 4-methyl-2,6-tert-butylphenol doris-nonylphenyl phosphite as a stabilizer at 0% to 100 parts by weight of the block copolymer. After adding .5 parts by weight, 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 254 on the vertical axis.
The absorbance detected at a wavelength of nm is displayed, and the vinyl aromatic hydrocarbon content of the eluted component (obtained using a calibration curve prepared in advance according to the elution amount) is displayed on the horizontal axis. An example of this is shown in FIG.

In FIG. 1, 1 and 2 represent the block copolymers (1) and (C) of the present invention, respectively, and 3 represents the block copolymer of the comparative example (@).

Examples 1 and 2 and Comparative Examples 1 and 2 60 parts by weight of each of the block copolymers shown in Table 1 and 40 parts by weight of polystyrene (Stylon 685, manufactured by Asahi Kasei) were mixed and formed into a sheet extruder to a thickness of 0.5 mm. I got 7 seats. The properties of each 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.

In addition, the block copolymer H of the comparative example was created by mixing block copolymers with different styrene contents produced in the same manner as the block copolymerizer.

Example 3 and Comparative Examples 3 to 5 The block copolymers shown in Table 2 were mixed with l8 manufactured by Toshiba Machine Corporation.
A flat plate having a thickness of 3 mm was injection molded at 200°C using a -8OA (5 oz. injection molding machine). The block copolymer of the present invention was transparent and had good impact resistance.

Note that block copolymers H and I of comparative examples were produced in the same manner as block copolymer (0) except that the amount of styrene used was changed.

Table 2 (Note 4) Based on JIS K-6714 Example 4 35 parts by weight of block copolymer (A) and 55 parts by weight of polystyrene
and 10 parts by weight of impact-resistant rubber-modified polystyrene (Stylon 475, manufactured by Asahi Kasei) were kneaded and pelletized using an extruder, and then a sheet having a thickness of 0.3 trrm was formed using an extruder. The resulting sheet had a dart impact value of 40.
kg·bi, and the total light transmittance was 88%.

Example 5 and Comparative Example 6 60 parts by weight of each block copolymer shown in Table 3 and 40 parts by weight of methyl methacrylic acid-styrene copolymer (Cepian MS-200, manufactured by Issel) were mixed and the An injection molded piece was made using an injection molding machine. Compositions containing the block copolymers of the present invention exhibited good impact resistance.

Table 3 Examples 6 to 10 and Comparative Examples 7 to 11 The block copolymers and thermoplastic resins were kneaded and pelletized using an extruder according to the compounding procedure shown in Table 4, and then subjected to the injection process described above. An injection molded piece is made using a molding machine, and its Izot impact strength (based on JI8 K-7110.Unit layer/α
/ cut, notched) were measured.

The results are shown in Table 4.

Example 11 and Comparative Example 12 Block copolymer (4) was polymerized in the same manner as block copolymer (g) except that tetrahydrofuran was used as the vinylizing agent, and styrene-containing fjk70
A block copolymer was obtained in which the amount of 1,2-bonds in the polybutadiene moiety was 35% by weight. This block copolymer was washed with water by the method described in JP-A-59-13320 to obtain a block copolymer g) with a hydrogenation rate of 95X. In the compositional analysis of the block copolymer, the total ratio of component A and component B was 59%, and the Izot impact strength was 10.2 (
kg・CWI/eWr (with N notch).

Next, as a comparative example, a comparative example hydrogenated block copolymer obtained by the same procedure as above in the manufacturing method of the comparative example block copolymer The total amount is 18%, and the Izotsu impact strength is 6
．． 5 (y·an/cm, with a notch).

[Brief explanation of drawings]

In FIG. 1, 1 and 2 are the block copolymers of the present invention) and (C), respectively, and 3 is the block copolymer of the comparative example @).

Claims (1)

[Scope of Claims] 1. At least one polymer segment mainly composed of vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of conjugated diene; In a block copolymer or its hydrogenated product having a weight ratio of 60/40 to 95/5, component A (where the vinyl aromatic hydrocarbon content is the main peak) determined from composition analysis by high performance liquid chromatography. Component B (component whose vinyl aromatic hydrocarbon content is lower than the vinyl aromatic hydrocarbon content of the main peak and whose difference is 5% or more by weight) (components in which the amount is 5% by weight or more) and the total amount is 20 to 80%
% block copolymer resin 2, (1) having at least one vinyl aromatic hydrocarbon-based polymer segment and at least one conjugated diene-based polymer segment; In a block copolymer or its hydrogenated product in which the weight ratio of hydrocarbon and conjugated diene is 60/40 to 95/5, component A determined from composition analysis by high performance liquid chromatography.
(component whose vinyl aromatic hydrocarbon content is higher than the vinyl aromatic hydrocarbon content of the main peak and the difference is 5% by weight or more) and component B (component whose vinyl aromatic hydrocarbon content is the main peak of the vinyl aromatic hydrocarbon content) (components whose content is less than the aromatic hydrocarbon content and whose difference is 5% by weight or more) is 20% in total.
~80% block copolymer resin 99 to 1 part by weight (2) a composition consisting of 1 to 99 parts by weight of a thermoplastic polymer