WO2016047762A1 - Composition de résine contenant un copolymère séquencé et article moulé associé - Google Patents

Composition de résine contenant un copolymère séquencé et article moulé associé Download PDF

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Publication number
WO2016047762A1
WO2016047762A1 PCT/JP2015/077130 JP2015077130W WO2016047762A1 WO 2016047762 A1 WO2016047762 A1 WO 2016047762A1 JP 2015077130 W JP2015077130 W JP 2015077130W WO 2016047762 A1 WO2016047762 A1 WO 2016047762A1
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Prior art keywords
resin composition
block
styrene
tan
block copolymer
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PCT/JP2015/077130
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English (en)
Japanese (ja)
Inventor
真之 大石
吉田　準
佐藤　英次
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電気化学工業株式会社
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Priority to SG11201702410SA priority Critical patent/SG11201702410SA/en
Priority to JP2016550401A priority patent/JP6573621B2/ja
Publication of WO2016047762A1 publication Critical patent/WO2016047762A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a resin composition containing a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene. More specifically, a block copolymer that is useful as a block copolymer-containing resin composition itself or a compound with various thermoplastic resins can be obtained as a molded article such as a sheet or film having excellent impact resistance.
  • the present invention relates to a resin composition containing a coalescence.
  • a resin composition comprising a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene and having a relatively high vinyl aromatic hydrocarbon content, particularly a block copolymer of styrene and butadiene, and the block copolymer.
  • a resin composition in which a polymer is blended with a styrene polymer (GPPS) has excellent properties such as impact resistance, so that the molded product is suitable for injection molding applications and extrusion molding applications such as sheets and films. Widely used.
  • GPPS styrene polymer
  • the present invention provides a vinyl aroma that can obtain a molded article such as a sheet or a film that can achieve particularly high impact resistance without deteriorating other properties such as bending strength, tensile elastic modulus, and sheet impact. It is an object of the present invention to provide a resin composition containing a block copolymer of an aromatic hydrocarbon and a conjugated diene, and a resin composition containing the resin composition and a thermoplastic resin.
  • the present inventors have (A) a conjugated diene content ratio, (B) a vinyl aromatic hydrocarbon block ratio, and (C) a differential refractive index method.
  • E) dynamic viscoelasticity Loss tangent (tan ⁇ ) obtained by measurement has one maximum value (tan ⁇ (max) value) in the temperature range of ⁇ 100 to ⁇ 60 ° C., and is 30 ° C. higher than the maximum temperature (tan ⁇ peak temperature).
  • Tan ⁇ value (tan ⁇ (max + 30 ° C.) value) has a specific range ratio to tan ⁇ value (tan ⁇ (max) value) at the maximum temperature, ie, (tan ⁇ (max + 3)
  • the present inventors have found that the above problems can be achieved by a resin composition having a value of 0 ° C.) / Tan ⁇ (max)) of 0.6 or more, and have reached the present invention.
  • the range of 0.6 or more which is a requirement for the dynamic viscoelasticity of the above (E), achieves the object of the present invention as described later. This is a major cause of the problem.
  • the present invention resides in a resin composition containing a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and satisfying the following (A) to (E).
  • A) The content ratio of the conjugated diene is 22% by mass to 35% by mass with respect to the entire block copolymer.
  • B) The vinyl aromatic hydrocarbon has a block ratio of 98% by mass to 100% by mass.
  • block copolymer resin composition of the vinyl aromatic hydrocarbon of the present invention and a conjugated diene, or a resin composition containing the resin composition and another thermoplastic resin By using the block copolymer resin composition of the vinyl aromatic hydrocarbon of the present invention and a conjugated diene, or a resin composition containing the resin composition and another thermoplastic resin, other elastic modulus such as tensile modulus can be obtained. Without deteriorating the characteristics, it is possible to obtain, for example, extrusion molding or injection molding of a sheet, film, etc. having high impact resistance.
  • the resin composition satisfies the above requirements (A) to (E), particularly, the above (E) dynamic viscoelasticity requirements. Seems to be achieved.
  • the block copolymer of the vinyl aromatic hydrocarbon and the conjugated diene of the present invention in order to make the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value, which is the requirement of the above (E), 0.6 or more. It is necessary to repeat the soft segment block and the hard segment block. Although both blocks are clearly distinguished in the polymer design, the hard segment block sandwiched between the soft segment blocks is taken into the soft segment block and apparently functions as a soft segment. Thereby, the content ratio (mass) of the conjugated diene can be reduced without reducing the proportion of the soft segment block in the block copolymer, and the rigidity is considered to be improved. Compared to the soft segment block alone, the Tg (tan ⁇ peak temperature) on the low temperature side hardly changes, so that the apparently captured hard segment block has good impact resistance without impairing the function of the soft segment. It is thought that sex is obtained.
  • the resin composition containing the block copolymer of the vinyl aromatic hydrocarbon and conjugated diene of the present invention (hereinafter also simply referred to as “resin composition” or “resin composition of the present invention”) is the above ( It is necessary to satisfy the requirements of A) to (E).
  • the vinyl aromatic hydrocarbon used here include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, ⁇ -methylstyrene. Vinyl naphthalene, vinyl anthracene and the like. Of these, styrene is preferable.
  • One or more vinyl aromatic hydrocarbons may be used.
  • Conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Is mentioned. Of these, 1,3-butadiene or isoprene is preferred. One or more conjugated dienes may be used.
  • the resin composition containing the block copolymer of the present invention comprises a block copolymer of vinyl aromatic hydrocarbon and conjugated diene.
  • the block copolymer of vinyl aromatic hydrocarbon and conjugated diene may be used alone or as a mixture of two or more kinds, and additives and other resins may be used in combination as long as the effects are not hindered.
  • the block copolymer of the present invention preferably has a structure in which a block made of vinyl aromatic hydrocarbon and a block made of conjugated diene are arbitrarily combined.
  • the resin composition must have a conjugated diene content of (A) block copolymer of 22% by mass to 35% by mass. If the content ratio of the conjugated diene is less than 22% by mass, the impact strength of the resin composition is lowered, which is not preferable. On the other hand, when the content ratio of the conjugated diene exceeds 35% by mass, the rigidity is not preferable. Among them, the content ratio of the conjugated diene is preferably 23% by mass to 32% by mass, and more preferably 24% by mass to 31% by mass.
  • the block ratio of the vinyl aromatic hydrocarbon contained in the resin composition (B) is required to be 98 to 100% by mass.
  • the block ratio of the vinyl aromatic hydrocarbon in the resin composition is less than 98%, the impact strength decreases, which is not preferable.
  • the block rate is preferably 99 to 100% by mass.
  • the upper limit of the block ratio is 100% by mass and does not exceed this.
  • the resin composition (C) must have a molecular weight distribution obtained by GPC measurement by the differential refractive index method, that is, a mass average molecular weight (Mw) / number average molecular weight (Mn) of 1.3 to 3.5. It is. If Mw / Mn is less than 1.3, the impact strength decreases, which is not preferable. On the other hand, when Mw / Mn exceeds 3.5, the rigidity is not preferable. In particular, Mw / Mn is preferably 1.3 to 3.0, and more preferably 1.4 to 2.5.
  • the resin composition needs to have an area ratio of high molecular weight components of 30% to 55% in the chromatogram obtained by (D) GPC measurement by the differential refractive index method. If the area ratio of the high molecular weight component is less than 30%, the rigidity is not preferred. On the other hand, if it exceeds 55%, the impact resistance is lowered, which is not preferable.
  • the area ratio of the high molecular weight component is preferably 30 to 54%, and more preferably 30 to 44%.
  • the area ratio of the high molecular weight component means that the peak top molecular weight Mp is the maximum among the peaks whose area ratio to the total peak area is 10% or more in the chromatogram obtained by GPC measurement. A peak having a peak is identified, and the ratio of the peak area to the total peak area is obtained.
  • the resin composition has (E) a maximum value (tan ⁇ (max) value) in which the loss tangent (tan ⁇ ) obtained by dynamic viscoelasticity measurement is in the temperature range of ⁇ 100 ° C. to ⁇ 60 ° C.
  • the tan ⁇ value (tan ⁇ (max + 30 ° C.) value) at 30 ° C. higher than the maximum temperature (tan ⁇ peak temperature) is 0.6 or more with respect to the tan ⁇ value (tan ⁇ (max) value) at the maximum temperature.
  • Ratio that is, (tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value) needs to be 0.6 or more.
  • the above (tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value) is preferably 0.65 or more, more preferably 0.75 or more, whereby the impact resistance of the obtained molded product is improved.
  • the properties and rigidity can be increased in a well-balanced manner without impairing other characteristics.
  • the above (tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value) has no upper limit and is preferably larger, but is usually less than 1.
  • the resin composition is a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene that satisfies the requirements (A) to (E), and contains at least two types of block copolymers having different molecular weights. It is preferable that the number is 3 or more.
  • the chemical structure of such a block copolymer is preferably represented by the following general formula (I) and / or (II), and is a block copolymer of at least two vinyl aromatic hydrocarbons having different molecular weights and a conjugated diene: It is preferable to contain 3 or more types.
  • S is a polymer block having vinyl aromatic hydrocarbon as a monomer unit
  • B is a polymer block having conjugated diene as a monomer unit
  • m represents the number of polymer chains bonded to the coupling agent residue.
  • m is an integer of 1 or more, preferably 2 to 10, more preferably 2 to 5.
  • n represents the number of repeating units and is an integer of 1 or more. From the viewpoint of ease of polymerization operation, n is preferably 1 to 5, and more preferably 1 to 3.
  • X represents a residue of a coupling agent.
  • a block copolymer having a block structure can be obtained by anionic polymerization as described later.
  • the molecular weight of S sandwiched between B is not particularly limited, but is preferably 600 or more, more preferably 600 to 20,000.
  • the molecular weight is 600 or less, it cannot be distinguished from the polybutadiene block at the time of measuring the block ratio, and there is a possibility of affecting the block ratio measurement result. That is, the boundary between B and S must be clearly distinguished, and the degree of polymerization of S sandwiched between B is considered to be preferably 6 or more.
  • the molecular weight exceeds 20,000, the molecular weight (Me) between the entanglement points of general polystyrene is exceeded, so the hard segment block S sandwiched between the soft segment blocks B is not taken into the soft segment block B and is sandwiched between B.
  • the S cannot be regarded as a soft segment block, and physical properties such as impact strength may not be expressed.
  • a block copolymer having a block structure of a vinyl aromatic hydrocarbon represented by the general formula (I) and a conjugated diene and / or a block copolymer having a block structure represented by (II) The coalescence is preferably a resin composition containing all block structures of vinyl aromatic hydrocarbons and conjugated dienes represented by the following general formulas (i) to (iii). That is, in the block copolymer represented by the general formula (I) and / or the block copolymer represented by (II), the terminal polystyrene block S is S1-S2-S3, S2-S3, and It is preferable that it is a resin composition containing S3 and the block polymer which is different block chain length.
  • S1-S2-S3- (BS) nB-S4 i) S2-S3- (BS) n-B-S4 (ii) S3- (BS) n-B-S4 (iii)
  • the block copolymer containing all the block structures represented by the above general formulas (i) to (iii) can be obtained, for example, by adding a polymerization initiator in a plurality of times in a series of anionic polymerization reactions. Can do. When a monomer is added after adding a polymerization initiator in the middle, a new polymer chain is synthesized not only from the terminal of the polymer chain polymerized so far but also from the polymerization initiator added in the middle. Therefore, each time a polymerization initiator is added and a monomer is further added, block structures having different block chains are formed.
  • a block copolymer containing all the block structures represented by the above general formulas (i) to (iii) can be obtained by adding a polymerization initiator (for example, butyllithium, etc.) three times during the polymerization. Can do.
  • a polymerization initiator for example, butyllithium, etc.
  • block copolymer containing all the block structures represented by the general formulas (i) to (iii) is a block copolymer having each of the block structures represented by the general formulas (i) to (iii). It can also be obtained by blending them after polymerization.
  • S, S1, S2, S3, and S4 are polymer blocks having vinyl aromatic hydrocarbon as a monomer unit, and B is a conjugated diene as a monomer unit. It is a polymer block.
  • n represents the number of repeating units and is an integer of 1 or more. From the viewpoint of ease of polymerization operation, n is preferably 1 to 5, and more preferably 1 to 3.
  • the block copolymer has such a chemical structure, the physical property balance such as impact resistance and rigidity obtained by the resin composition of the present invention is excellent.
  • the living active terminal is lost with water or alcohol after all the monomers used have been converted into polymers, that is, after the preparation of the S4 block of the above general formulas (i) to (iii) It is preferable to add a coupling agent before activation to obtain a resin composition in which active ends are coupled. Thereby, the balance of physical properties such as impact resistance and rigidity obtained with the resin composition of the present invention is not affected.
  • the block copolymer can be produced by anionic polymerization of vinyl aromatic hydrocarbon and conjugated diene monomers in an organic solvent using an organic lithium compound as a polymerization initiator.
  • Organic solvents are aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, or ethylbenzene, xylene.
  • Aromatic hydrocarbons such as can be used. From the viewpoint of the solubility of the block copolymer, cyclohexane is preferred.
  • An organolithium compound is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.
  • Monofunctional organolithium compounds, polyfunctional organolithium compounds such as hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium can be used.
  • vinyl aromatic hydrocarbon and conjugated diene used in the present invention those described above can be used, and one or two or more can be selected and used for polymerization.
  • living anionic polymerization using the organolithium compound as a polymerization initiator almost all of the vinyl aromatic hydrocarbon and conjugated diene subjected to the polymerization reaction are converted into a polymer.
  • the molecular weight of the block copolymer in the present invention can be controlled by the addition amount of the polymerization initiator with respect to the total addition amount of the monomer.
  • the block ratio of vinyl aromatic hydrocarbon depends on the supply rate of vinyl aromatic hydrocarbon and conjugated diene and the amount of randomizing agent added when polymerizing vinyl aromatic hydrocarbon and conjugated diene to produce block copolymer. Can be controlled.
  • the randomizing agent is a compound that acts as a Lewis base in the reaction, and amines, ethers, thioethers, phosphoramides, alkylbenzene sulfonates, and other potassium or sodium alkoxides can be used.
  • amines include tertiary amines such as trimethylamine, triethylamine, and tetramethylethylenediamine; and cyclic tertiary amines.
  • ethers include dimethyl ether, diethyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and tetrahydrofuran (THF).
  • triphenylphosphine; hexamethylphosphoramide; potassium or sodium alkylbenzenesulfonate; butoxides such as potassium and sodium; Tetrahydrofuran (THF) is preferable.
  • the addition concentration is preferably 0.001 to 10 parts by mass per 100 parts by mass of the monomer used as a raw material.
  • the timing of addition may be before the start of the polymerization reaction or before the polymerization of the copolymer chain. Further, it can be added as required.
  • the coupling may be performed by adding a coupling agent before deactivating the living active terminal.
  • the coupling means that a covalent bond is formed between the living active site located at one end of the polymer chain and the reaction site in the coupling agent molecule, whereby two or more polymer chains are coupled into one coupling. This refers to binding through agent molecules.
  • a coupling agent is a compound having two or more reactive sites per molecule that can be attacked by a living active site.
  • the coupling agent is not limited, but chlorosilane compounds such as dimethyldichlorosilane, silicon tetrachloride and 1,2-bis (methyldichlorosilyl) ethane; alkoxysilanes such as dimethyldimethoxysilane, tetramethoxysilane and tetraphenoxysilane Compounds; tin tetrachloride; polyhalogenated hydrocarbons; carboxylic acid esters; polyvinyl compounds; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil; Preferably, epoxidized fats and oils, more preferably epoxidized soybean oil.
  • chlorosilane compounds such as dimethyldichlorosilane, silicon tetrachloride and 1,2-bis (methyldichlorosilyl) ethane
  • alkoxysilanes such as dimethyldimethoxysilane, t
  • Examples of the bifunctional coupling agent having two reaction sites per molecule include dimethyldichlorosilane and dimethyldimethoxysilane.
  • Examples of the trifunctional coupling agent having three reaction sites per molecule include methyltrichlorosilane and methyltrimethoxysilane.
  • Examples of the tetrafunctional coupling agent having four reaction sites per molecule include tetrachlorosilane, tetramethoxysilane, and tetraphenoxysilane.
  • epoxidized oils and fats have 3 ester groups per molecule and 0 to 3 epoxy groups per long chain alkyl group on the side of 3 long chain alkyl groups. It becomes a functional coupling agent.
  • the coupling agent may be used alone or in combination of two or more polyfunctional coupling agents.
  • one or more bifunctional coupling agents and one or more multifunctional coupling agents can be used in combination.
  • the polyfunctional coupling agent is used alone.
  • the reactive site that can be attacked by the living active site in the coupling agent is not necessarily required to react completely, and a part of the reactive site may remain without reacting. Furthermore, it is not necessary that the polymer chain having all living active sites at one end reacts with the reaction site of the coupling agent, and the polymer chain left unreacted remains in the finally generated block copolymer. May be. And even if the block copolymer having a smaller number of branches than the number of branches expected when the reaction site of the coupling agent used is completely reacted, the block copolymer finally produced is mixed.
  • a polymer chain in which only the coupling agent is bonded to one end, in which the coupling agent is replaced in the living active site may be mixed in the final product block copolymer.
  • the final block copolymer has a number of branches equal to the number of branches expected when the reaction site of the coupling agent used is completely reacted, and the reaction site of the coupling agent used is completely
  • the addition amount of the coupling agent may be arbitrary, but is preferably set so that the reaction site of the coupling agent is present in a stoichiometric amount or more with respect to the living active terminal. Specifically, the addition amount of the coupling agent is preferably set so that there are 1 to 2 equivalents of reaction sites relative to the number of moles of living active terminals present in the polymerization solution before the coupling step.
  • the block copolymer thus obtained can be inactivated by adding a sufficient amount of a polymerization terminator such as water, alcohol or carbon dioxide to inactivate the living active terminal.
  • a polymerization terminator such as water, alcohol or carbon dioxide
  • a method of recovering the copolymer from the organic solvent solution of the obtained block copolymer a method of precipitating with a poor solvent such as methanol, a method of precipitating by evaporating the solvent with a heating roll or the like (drum dryer method), A method of removing the solvent with a vent type extruder after concentrating the solution with a concentrator, a method of dispersing the solution in water, blowing water vapor and removing the solvent by heating (steam stripping method), etc. Any method can be adopted.
  • thermoplastic resin composition The resin composition can be used in the form of a resin composition blended with another thermoplastic resin.
  • thermoplastic resins include polystyrene polymers, polyphenylene ether polymers, polyethylene polymers, polypropylene polymers, polybutene polymers, polyvinyl chloride polymers, polyvinyl acetate polymers, polyamide polymers.
  • thermoplastic resins are polystyrene-based polymers, such as general-purpose polystyrene (GPPS), impact-resistant polystyrene (HIPS), methyl methacrylate-styrene copolymer, methacrylic acid-styrene copolymer, acrylonitrile-styrene copolymer, Examples include acrylonitrile-butadiene-styrene copolymer, and general-purpose polystyrene (GPPS) is particularly preferable.
  • GPPS general-purpose polystyrene
  • HIPS impact-resistant polystyrene
  • methyl methacrylate-styrene copolymer methacrylic acid-styrene copolymer
  • GPPS general-purpose polystyrene
  • GPPS General purpose polystyrene
  • the blending mass ratio of the block copolymer composition is less than 10, it is not preferable because the impact strength of the resin composition decreases. When it exceeds 80, the rigidity of the resin composition decreases, which is not preferable. .
  • the resin composition or the resin composition containing the resin composition and the thermoplastic resin may further contain various additives as necessary.
  • various additives for example, stabilizers, lubricants, processing aids, antiblocking agents, antistatic agents, antifogging agents, weathering improvers, softeners, plasticizers, pigments, mineral oil, fillers, flame retardants Additives such as can be added.
  • the stabilizer examples include 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6- Phenolic antioxidants such as di-tert-butyl-4-methylphenol, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, trisnonylphenyl phosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, etc. And phosphorus-
  • saturated fatty acids such as palmitic acid, stearic acid and behenic acid, fatty acid esters such as octyl palmitate and octyl stearate; pentaerythritol fatty acid Esters; fatty acid amides such as erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide; ethylene bisstearic acid amide; glycerin-mono-fatty acid ester; glycerin-di-fatty acid ester; and sorbitan-mono -Sorbitan fatty acid esters such as palmitic acid ester, sorbitan mono-stearic acid ester; higher alcohols typified by myristyl alcohol, cetyl alcohol, stearyl alcohol: high impact polystyrene (HIPS) Etc., and the
  • benzotriazole ultraviolet absorbers such as 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole; 2,4-di- salicylate UV absorbers such as tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate; benzophenone UV absorbers such as 2-hydroxy-4-n-octoxybenzophenone; Hindered amine type weather resistance improvers such as tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate; Furthermore, liquid paraffin such as white oil and mineral oil, silicone oil, microcrystalline wax and the like can be added. These additives are preferably used in the resin composition in an amount of preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 0 to 3% by mass.
  • each component in the case of obtaining this resin composition is not particularly limited.
  • it may be dry blended with a Henschel mixer, a ribbon blender, a V blender or the like, and further melted with an extruder to be pelletized. Good.
  • it may be added at the stage of production of each polymer, before the start of polymerization, in the middle of the polymerization reaction, or after treatment of the polymer.
  • the above-described resin composition can be formed by any conventionally known molding method, for example, extrusion molding, injection molding, hollow molding, etc., and various shapes of extrusion molded products including sheets and films, injection molded products, hollow molded products, and pneumatic molding. It can be easily molded into practically useful products such as products, vacuum molded products, biaxially stretched molded products, and the like.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (15).
  • (1) 500.0 kg of cyclohexane and 75.0 g of tetrahydrofuran (THF) were placed in a reaction vessel.
  • (2) 780 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution and kept at 30 ° C.
  • the conjugated diene-containing mass ratio was 22.0%, and the block ratio of the vinyl aromatic hydrocarbon was 100%.
  • the tan ⁇ peak temperature was ⁇ 78 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.84.
  • the main points of the above polymerization example 1 are summarized in Table 1.
  • the composition of the block copolymer can be determined by adjusting the amount of the monomer used in the above (3), (5), (7) to (13), and the above (2)
  • the molecular weight can be determined by adjusting the amount of n-butyllithium used in (4) and (6). Accordingly, block copolymer resin compositions of Polymerization Examples 2 to 14 were obtained in the same manner as in Polymerization Example 1 except for the conditions shown in Table 1 below.
  • the main points of the above polymerization examples 2 to 14 are summarized in Table 1.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (13).
  • the conjugated diene-containing mass ratio was 24.0%, and the vinyl aromatic hydrocarbon block ratio was 89%.
  • the tan ⁇ peak temperature was ⁇ 52 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.47.
  • the main points of Polymerization Example 15 are summarized in Table 2.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (16).
  • (1) 500.0 kg of cyclohexane and 75.0 g of tetrahydrofuran (THF) were placed in a reaction vessel.
  • (2) 1,450 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution, and the temperature was kept at 30 ° C.
  • a block copolymer of styrene and 1,3-butadiene was produced by the following operations (1) to (12).
  • (1) 500.0 kg of cyclohexane and 75.0 g of tetrahydrofuran (THF) were placed in a reaction vessel.
  • (2) 760 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution and kept at 30 ° C.
  • the composition of the block copolymer can be determined by adjusting the amount of the monomer used in the above (3) to (10), and the n-butyllithium used in the above (2) The molecular weight can be determined by adjusting the amount. Accordingly, block copolymers of Polymerization Examples 18 and 19 were obtained by carrying out in the same manner as Polymerization Example 17 except for the conditions shown in Table 4 below. The main points of the above polymerization examples 18 and 19 are summarized in Table 4.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (15).
  • 890 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution and kept at 30 ° C.
  • 33.8 kg of styrene was added, and styrene was anionically polymerized. The internal temperature rose to 45 ° C.
  • the peak top molecular weight (Mp) was 191,000 / 123,000 / 107,000, the area ratio was 32.6 / 20.8 / 46.6 (%), and Mw / Mn was 1.30. It was.
  • the conjugated diene-containing mass ratio was 24.9%, and the vinyl aromatic hydrocarbon block ratio was 95%.
  • the tan ⁇ peak temperature was ⁇ 65 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.74.
  • Table 5 summarizes the main points of the above Polymerization Example 20.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (11).
  • a total amount of 12.2 kg of styrene and a total amount of 48.8 kg of 1,3-butadiene were maintained at 25 kg / h and 100 kg while maintaining the internal temperature of the reaction system at 80 ° C. Both were added simultaneously at a constant addition rate of / h.
  • the internal temperature of the reaction system was lowered to 75 ° C., and 26.5 kg of styrene was added all at once to complete the polymerization.
  • the conjugated diene-containing mass ratio was 24.4%, and the vinyl aromatic hydrocarbon block ratio was 95%.
  • the tan ⁇ peak temperature was ⁇ 65 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.47.
  • Table 6 summarizes the main points of the above Polymerization Example 21.
  • the composition of the block copolymer can be determined by adjusting the amount of the monomer used in the above (3), (5), (7) to (9).
  • the molecular weight can be determined by adjusting the amount of n-butyllithium used in (4) and (6). Therefore, the block copolymer resin compositions of Polymerization Examples 22 and 23 were obtained by carrying out in the same manner as in Polymerization Example 21 except for the conditions shown in Table 6 below.
  • Polymerization Examples 22 and 23 are block copolymers having an SBS structure having a polystyrene block and a polybutadiene block. In the above formula, S represents a polystyrene block, and B represents a polybutadiene block. Table 6 summarizes the main points of the above Polymerization Examples 22 and 23.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (13).
  • (1) 500.0 kg of cyclohexane and 75.0 g of tetrahydrofuran (THF) were placed in a reaction vessel.
  • (2) 780 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution and kept at 30 ° C.
  • the conjugated diene-containing mass ratio was 24.0%, and the vinyl aromatic hydrocarbon block rate was 100%.
  • the tan ⁇ peak temperature was ⁇ 75 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.79.
  • Table 7 summarizes the main points of the above Polymerization Example 24.
  • a block copolymer resin composition of styrene and 1,3-butadiene was produced by the following operations (1) to (17).
  • (1) 500.0 kg of cyclohexane and 75.0 g of tetrahydrofuran (THF) were placed in a reaction vessel.
  • (2) 780 mL of a 10% by mass cyclohexane solution of n-butyllithium was added as a polymerization initiator solution and kept at 30 ° C.
  • the conjugated diene-containing mass ratio was 24.0%, and the vinyl aromatic hydrocarbon block rate was 100%.
  • the tan ⁇ peak temperature was ⁇ 72 ° C., and the tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value was 0.88.
  • Table 8 summarizes the main points of Polymerization Example 25.
  • ⁇ Formulation example> The block copolymers obtained in Polymerization Examples 17 to 19 were mixed at the blending ratios (mass%) shown in Table 9 to produce block copolymer resin compositions.
  • the block copolymer resin composition is melt kneaded at a extrusion temperature of 200 ° C. and a screw rotation speed of 100 rpm using a single-screw extruder (manufactured by Tabata Machinery Co., Ltd., HV-40-30, ⁇ 40 mm), and extruded into a strand shape. After cooling, it was pelletized with a pelletizer.
  • Formulation composition of block copolymer resin composition in Formulation Example 1 peak top molecular weight (Mp), area ratio, Mw / Mn, conjugated diene-containing mass ratio of block copolymer resin composition, block of vinyl aromatic hydrocarbon Table 9 summarizes the rate, tan ⁇ peak temperature, and tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value.
  • the molecular weight is the peak top molecular weight Mp, and when coupling is performed, it is Mp before coupling.
  • the dispersity is weight average molecular weight Mw / number average molecular weight Mn, and is Mw / Mn after coupling when coupling is performed.
  • the conjugated diene content ratio of the block copolymer resin composition was calculated from the use ratio and blending ratio of the 1,3-butadiene amount with respect to the total monomer amount used in the above polymerization examples.
  • ⁇ Block ratio of styrene in resin composition> 1 H-NMR was measured and calculated using nuclear magnetic resonance (NMR).
  • NMR nuclear magnetic resonance
  • the value converted to five protons from the peak intensity integrated value of 6.2 to 6.8 ppm assigned as two protons attached to the ortho position is converted into block styrene.
  • the amount was W.
  • a value obtained by dividing the integral value of the peak intensity was defined as a total styrene amount (total vinyl aromatic hydrocarbon amount) W0.
  • the block ratio was calculated by substituting W and W0 into the following defining formula.
  • the amount of block styrene (the amount of block vinyl aromatic hydrocarbon) W is a chain composed of 5 or more monomer units for the sensitivity of the apparatus.
  • Block ratio of styrene (%) (W / W0) ⁇ 100
  • the loss tangent (tan ⁇ ) was determined from the measurement, and the maximum value among the tan ⁇ maximum values in the temperature range of ⁇ 100 ° C. to ⁇ 60 ° C. was defined as “tan ⁇ (max) value”, and the temperature was defined as “tan ⁇ peak temperature”.
  • the tan ⁇ value at a temperature 30 ° C. higher than the tan ⁇ peak temperature was defined as “tan ⁇ (max + 30 ° C.) value”, and (tan ⁇ (max + 30 ° C.) value / tan ⁇ (max) value) was calculated.
  • a sample of a resin composition for dynamic viscoelasticity measurement was subjected to pressure holding at 200 ° C. to 220 ° C. for 2 minutes with a heating press to relax the orientation, and then rapidly cooled to obtain 0 in an unoriented state. A 6 mm thick sheet was used.
  • Dynamic viscoelasticity measuring apparatus RSA3 manufactured by TA Instruments, Setting temperature range: -120 to 130 ° C, Setting temperature rising rate: 4 ° C / min, Measurement frequency: 1Hz
  • Examples 1 to 16 and Comparative Examples 1 to 11 -Production of GPPS Blend Sheet
  • the block copolymer resin composition and GPPS were mixed at the blending ratios (mass%) shown in Tables 10 and 11, and the sheet was molded by the following procedure.
  • a Tanabe Plastics ⁇ 40mm single screw extruder VS40-26 with a T-die with a width of 40 cm at the tip using the resin of the compounding example at an extrusion temperature of 200 ° C., a T-die temperature of 200 ° C., and a screw speed of 60 rpm.
  • Sheet extrusion was performed, and a single-layer sheet having a sheet thickness of 0.6 mm was produced at a cooling roll temperature of 50 ° C.
  • GPPS used a general-purpose polystyrene resin (manufactured by Toyo Styrene Co., Ltd., Toyo Styrol GP G200C, peak top molecular weight (Mp) 286,000, Mw / Mn 2.53).
  • ⁇ DuPont impact strength> Using a DuPont impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), 20 test pieces of 60 mm square cut out from the sheet were placed on a cradle, and a striker with a tip diameter of 6.35 mm was placed on the test piece. A weight of 100 g was dropped on the upper end of the strike core, and the presence or absence of a crack generated in the sheet was examined by visual observation, and converted into an energy value. Before this measurement, use 2 to 3 separate preliminary test specimens to determine the approximate drop weight height at which the sheet breaks, and the first sheet is measured at the drop weight height determined from the preliminary measurement results.
  • ⁇ Tensile modulus> Using a Tensilon universal testing machine (manufactured by A & D, RTC-1210A), a dumbbell-shaped test piece conforming to JISK6732 is cut from the sheet so that the MD direction is the longitudinal direction, the initial chuck interval is 50 mm, and the tensile speed is 10 mm.
  • the tensile elastic modulus (rigidity) in the MD direction was measured under an environment of 23 ° C./min.
  • the block copolymer in the resin composition does not affect the physical properties with or without coupling. From Examples 2 and 10, the block copolymer in the resin composition does not affect the physical properties even when polymerized simultaneously in the reaction vessel or when blended after separately polymerized.
  • Example 8 and Comparative Example 3 as compared with the case where the polybutadiene block and the polystyrene block are repeated and the case where the random block and the polystyrene block are repeated as the soft segment of the block copolymer in the resin composition, the impact strength decreases in the latter. did. That is, the soft segment of the block copolymer in the resin composition must be a polybutadiene block.
  • Example 2 and Comparative Example 10 the conjugated diene mass ratio of each block copolymer resin composition is fixed, and the case where the polybutadiene block and the polystyrene block are repeated is compared with the case where the tapered block is repeated. Declined. In other words, when the polybutadiene block and the polystyrene block are repeated, the boundary between them must be clearly distinguished.
  • the resin composition of the present invention and a composition obtained by blending the resin composition with various thermoplastic resins are effective as a material for sheets and films, and are used for food packaging by taking advantage of excellent impact resistance and mechanical properties. In addition to containers, etc., it can be widely used for daily miscellaneous goods packaging, laminated sheets and films.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Le problème décrit par la présente invention est de fournir une composition de résine contenant un copolymère séquencé d'un hydrocarbure aromatique vinylique et d'un diène conjugué, qui permette d'obtenir un article moulé tel qu'une feuille ou un film présentant une résistance aux chocs exceptionnelle. La solution proposée par l'invention consiste en une composition de résine contenant un copolymère séquencé d'un hydrocarbure aromatique vinylique et d'un diène conjugué, la composition de résine satisfaisant les points (A) à (E) ci-dessous. (A) La teneur en diène conjugué va de 22 % en masse à 35 % en masse. (B) Le rapport de blocs de l'hydrocarbure aromatique vinylique va de 98 à 100 %. (C) Le rapport Mw/Mn obtenu par chromatographie de perméation sur gel va de 1,3 à 3,5. (D) Le rapport de surface des composants polymères représente de 30 à 55 % de la globalité dans un chromatogramme obtenu par chromatographie de perméation sur gel. (E) La tangente de perte obtenue par un mesurage de la viscoélasticité dynamique présente une seule valeur maximale sur une plage de température allant de -100 à -60 °C, et la valeur tan δ lorsque la température est supérieure de 30 °C à la température de la valeur maximale est supérieure de 0,6 ou plus à la valeur tan δ à la température de la valeur maximale.
PCT/JP2015/077130 2014-09-25 2015-09-25 Composition de résine contenant un copolymère séquencé et article moulé associé WO2016047762A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2019074013A1 (ja) * 2017-10-11 2020-08-06 デンカ株式会社 樹脂組成物、熱収縮性フィルムおよび容器

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6361A (ja) * 1987-03-02 1988-01-05 グンゼ株式会社 熱収縮包装された容器
JPH0249015A (ja) * 1989-07-17 1990-02-19 Asahi Chem Ind Co Ltd ブロック共重合体樹脂の製造方法
JPH04255707A (ja) * 1991-02-07 1992-09-10 Asahi Chem Ind Co Ltd ブロック共重合体樹脂の製造方法
JPH09324084A (ja) * 1996-06-05 1997-12-16 Denki Kagaku Kogyo Kk ブロック共重合体樹脂組成物、成形体及びその製造方法
JP2000026698A (ja) * 1998-07-13 2000-01-25 Denki Kagaku Kogyo Kk ブロック共重合体組成物、及びその製造方法
JP2002540230A (ja) * 1999-03-19 2002-11-26 ザ ダウ ケミカル カンパニー 水素化ブッロクコポリマー

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6361A (ja) * 1987-03-02 1988-01-05 グンゼ株式会社 熱収縮包装された容器
JPH0249015A (ja) * 1989-07-17 1990-02-19 Asahi Chem Ind Co Ltd ブロック共重合体樹脂の製造方法
JPH04255707A (ja) * 1991-02-07 1992-09-10 Asahi Chem Ind Co Ltd ブロック共重合体樹脂の製造方法
JPH09324084A (ja) * 1996-06-05 1997-12-16 Denki Kagaku Kogyo Kk ブロック共重合体樹脂組成物、成形体及びその製造方法
JP2000026698A (ja) * 1998-07-13 2000-01-25 Denki Kagaku Kogyo Kk ブロック共重合体組成物、及びその製造方法
JP2002540230A (ja) * 1999-03-19 2002-11-26 ザ ダウ ケミカル カンパニー 水素化ブッロクコポリマー

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2019074013A1 (ja) * 2017-10-11 2020-08-06 デンカ株式会社 樹脂組成物、熱収縮性フィルムおよび容器

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