WO2024048506A1 - Composition de copolymère séquencé, composition de résine contenant une composition de copolymère séquencé, film thermorétractable - Google Patents

Composition de copolymère séquencé, composition de résine contenant une composition de copolymère séquencé, film thermorétractable Download PDF

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WO2024048506A1
WO2024048506A1 PCT/JP2023/030927 JP2023030927W WO2024048506A1 WO 2024048506 A1 WO2024048506 A1 WO 2024048506A1 JP 2023030927 W JP2023030927 W JP 2023030927W WO 2024048506 A1 WO2024048506 A1 WO 2024048506A1
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mass
block copolymer
copolymer composition
heat
vinyl aromatic
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PCT/JP2023/030927
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English (en)
Japanese (ja)
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友哉 中村
正 澤里
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デンカ株式会社
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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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 block copolymer composition, a resin composition containing the block copolymer composition, and a heat-shrinkable film including a layer composed of the resin composition.
  • Heat-shrinkable films using block copolymers made by polymerizing vinyl aromatic compounds and conjugated diene compounds have excellent heat-shrinkability and finish after shrinkage, and are suitable for various shapes and attachment methods of packaged objects. Because of its adaptability, it is widely used for shrink packaging such as labels for PET bottled beverages.
  • Patent Document 1 discloses a method in which a heat-shrinkable film is made into a foamed film to make the specific gravity smaller than that of water, thereby making it possible to easily separate PET bottles by a specific gravity separation method.
  • the foamed film since the foamed film has air bubbles inside the film, it may have poor surface smoothness and transparency, which may cause problems with printing characteristics and appearance when used as a label.
  • the present invention provides a heat-shrinkable film that allows specific gravity separation with water when a heat-shrinkable film is obtained from a resin composition containing a block copolymer composition, even if the heat-shrinkable film is non-foamed.
  • An object of the present invention is to provide a block copolymer composition from which a transparent film can be obtained.
  • a block copolymer composition containing one or more types of block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit contains 52% by mass of the vinyl aromatic monomer unit when the total mass of the vinyl aromatic monomer unit and the conjugated diene monomer unit is 100% by mass.
  • the block copolymer composition has a flexural modulus of 1000 MPa or more as measured in accordance with ISO 178, and the block copolymer composition has a heating rate of 4° C. in accordance with ISO 6721-1.
  • the loss tangent value (tan ⁇ ) when performing dynamic viscoelasticity measurement in a fixed three-point bending mode is at least in the range of 80°C or more and 110°C or less.
  • a block copolymer composition containing one or more block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit contains 52% of the vinyl aromatic monomer units when the total mass of the vinyl aromatic monomer units and the conjugated diene monomer units is 100% by mass.
  • the block copolymer composition has a flexural modulus of 1000 MPa or more as measured according to ISO178, The block copolymer composition was subjected to dynamic viscoelasticity measurement in a fixed three-point bending mode under the conditions of a heating rate of 4°C/min, a frequency of 1Hz, and a strain of 0.02% in accordance with ISO6721-1.
  • the loss tangent value (tan ⁇ ) has at least one peak in the range of 80 ° C. or more and 110 ° C. or less, Block copolymer composition.
  • At least one of the one or more block copolymers contained in the block copolymer composition has a structure represented by any one of the following formulas (i) to (iv). , (i) (S1) n - (B) m (ii) (S1) n - (B) m - (S2) (iii) (S1) n - (B) m -X (iv) (S1) n - (B) m - (S2) -X [In the formula, each of (S1) and (S2) is a polymer block with a vinyl aromatic monomer unit content of 85% by mass or more and 100% by mass or less, and (B) is a conjugated diene monomer unit.
  • Each of the block copolymers having structures represented by formulas (i) to (iv) above contains 40% by mass as the total mass of (S1) 1 to (S1) n in 100% by mass of the block copolymer. Contains not less than 70% by mass,
  • Each of the block copolymers having structures represented by formulas (i) to (iv) above contains 30% by mass as the total mass of (B) 1 to (B) m in 100% by mass of the block copolymer.
  • Each of the block copolymers having structures represented by formulas (i) to (iv) above contains 0% by mass or more and 12% by mass or less as the mass of (S2) in 100% by mass of the block copolymer. , 60% by mass or more as the total mass of block copolymers having a structure represented by any one of formulas (i) to (iv) in 100% by mass of the one or more block copolymers. Contains less than % by mass, The block copolymer composition according to [1] or [2].
  • (S1) is a homoblock composed of vinyl aromatic monomer units, or a random copolymer composed of vinyl aromatic monomer units and conjugated diene monomer units block
  • (B) is a homoblock composed of conjugated diene monomer units
  • (S2) is a homoblock composed of vinyl aromatic monomer units
  • [5] Any one of [1] to [4], wherein the vinyl aromatic monomer unit is a styrene monomer unit, and the conjugated diene monomer unit is a butadiene monomer unit.
  • a heat-shrinkable film comprising a layer made of the resin composition according to [6].
  • the heat-shrinkable film obtained from the resin composition containing the block copolymer composition of the present invention can be separated by specific gravity with water even if it is not foamed.
  • the block copolymer composition according to one embodiment of the present invention contains one or more block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit. In one embodiment, the block copolymer composition contains only a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit. Furthermore, the block copolymer composition may contain various additives within the range that does not impede the effects of the present invention.
  • a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit according to an embodiment of the present invention is obtained by block copolymerizing a vinyl aromatic monomer and a conjugated diene monomer. It is a block copolymer synthesized by The block copolymer is a block copolymer having one or more types of block chains composed of vinyl aromatic monomer units and/or conjugated diene monomer units.
  • the vinyl aromatic monomer unit is a constituent unit of a block copolymer derived from a vinyl aromatic monomer used in copolymerization of the block copolymer.
  • vinyl aromatic monomers include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, and ⁇ -methylstyrene.
  • examples include styrenic monomers such as, vinylnaphthalene, vinylanthracene, etc.
  • the vinyl aromatic monomer is preferably styrene. These monomers may be used alone or in combination of two or more.
  • the conjugated diene monomer unit is a constituent unit of a block copolymer derived from a conjugated diene monomer used in copolymerization of the block copolymer.
  • the conjugated diene monomer include butadiene monomers such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-dimethyl-1,3-butadiene; Examples include 1,3-pentadiene and 1,3-hexadiene.
  • the conjugated diene monomer is preferably 1,3-butadiene or isoprene. These monomers may be used alone or in combination of two or more.
  • the content of vinyl aromatic monomer units and conjugated diene monomer units in the block copolymer according to one embodiment of the present invention is not particularly limited, but the content of the block copolymer is 100% by mass.
  • the vinyl aromatic monomer unit is 50 to 80% by mass
  • the conjugated diene monomer unit is 20 to 50% by mass
  • the vinyl aromatic monomer unit is 52% by mass. It is more preferable that the amount of conjugated diene monomer units is 31 to 48% by weight.
  • the preferred content of vinyl aromatic monomer units in the block copolymer is, for example, 50, 55, 60, 65, 70, 75, or 80% by mass when the block copolymer is 100% by mass. %, and may be within a range between any two of the numerical values exemplified here.
  • the preferable content of the conjugated diene monomer unit in the block copolymer is, for example, 20, 25, 30, 35, 40, 45, or 50% by mass when the block copolymer is 100% by mass. and may be within the range between any two of the numerical values exemplified here.
  • the block copolymer is more likely to be uniformly compatible with each other, making it difficult for gel formation and reduction in transparency to occur.
  • the content of the vinyl aromatic monomer unit means the total content of the vinyl aromatic monomer units used together.
  • the content of the conjugated diene monomer units means the total content of the conjugated diene monomer units used together.
  • the weight average molecular weight of the block copolymer is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, and even more preferably 70,000 to 200,000.
  • a value of 40,000 or more provides the block copolymer composition with sufficient rigidity and impact resistance, and a value of 500,000 or less provides a block copolymer composition with good processability, which is preferable.
  • the weight average molecular weight of the block copolymer can be measured using gel permeation chromatography (hereinafter abbreviated as GPC).
  • At least one block copolymer containing one or more vinyl aromatic monomer units and a conjugated diene monomer unit contained in the block copolymer composition according to an embodiment of the present invention preferably has a structure represented by any one of the following formulas (i) to (iv).
  • each of (S1) and (S2) is a polymer block with a vinyl aromatic monomer unit content of 85% by mass or more and 100% by mass or less, and (B) is a conjugated diene monomer unit.
  • each of the block copolymers having structures represented by formulas (i) to (iv) above contains 40% by mass as the total mass of (S1) 1 to (S1) n in 100% by mass of the block copolymer.
  • Each of the block copolymers containing at least 70% by mass and having a structure represented by the formulas (i) to (iv) contains (B) 1 to (B) in 100% by mass of the block copolymer. ) Contains 30% by mass or more and 48% by mass or less as the total mass of m .
  • each of the block copolymers having structures represented by formulas (i) to (iv) above contains (S2) in 0% by mass or more and 12% by mass or less in 100% by mass of the block copolymer.
  • S2 0% by mass or more and 12% by mass or less in 100% by mass of the block copolymer.
  • Each of the polymer blocks (S1) and (S2) has a content of vinyl aromatic monomer units of 85% by mass or more and 100% by mass or less, and a content of conjugated diene monomer units of 0% by mass or more and 15% by mass or less.
  • the polymer block preferably has a content of vinyl aromatic monomer units of 90% by mass or more and 100% by mass or less, and a content of conjugated diene monomer units of 0% by mass.
  • the content of the polymer block is 10% by mass or less.
  • the polymerized block (B) is a polymerized block in which the content of conjugated diene monomer units is 60% by mass or more and 100% by mass or less, and the content of vinyl aromatic monomer units is 0% by mass or more and 40% by mass or less. It is preferable that the content of conjugated diene monomer units is 70% by mass or more and 100% by mass or less, and the content of vinyl aromatic monomer units is 0% by mass or more and 30% by mass or less. It is a polymer block.
  • Each of the block copolymers having structures represented by formulas (i) to (iv) contains 40% by mass or more as the total mass of (S1) 1 to (S1) n in 100% by mass of the block copolymer.
  • the content is 45% by mass or more and 66% by mass or less, more preferably 45% by mass or more and 60% by mass or less.
  • Each of the block copolymers having structures represented by formulas (i) to (iv) contains 30% by mass or more as the total mass of (B) 1 to (B) m in 100% by mass of the block copolymer.
  • the content is 32% by mass or more and 48% by mass or less, preferably 32% by mass or more and 48% by mass or less.
  • Each of the block copolymers having structures represented by formulas (i) to (iv) contains (S2) in 100% by mass of 0% by mass or more and 12% by mass or less, preferably 0% by mass or less. Contains from 10% by mass to 10% by mass.
  • the block copolymer having the structure represented by formula (iii) or (iv) is a polymer block of (S1) n - (B) m or a polymer block of (S1) n - (B) m - (S2). It can be obtained by polymerizing and then coupling with a coupling agent.
  • Coupling agents include dimethyldichlorosilane, silicon tetrachloride, chlorosilane compounds such as 1,2-bis(methyldichlorosilyl)ethane, methyltrichlorosilane, and tetrachlorosilane; dimethyldimethoxysilane, tetramethoxysilane, tetraphenoxysilane, Examples include alkoxysilane compounds such as methyltrimethoxysilane and tetraphenoxysilane; tin tetrachloride; polyhalogenated hydrocarbons; carboxylic acid esters; polyvinyl compounds; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil. . Furthermore, two or more types of coupling agents may be used in combination. A particularly preferred polyfunctional coupling agent is epoxidized soybean oil.
  • ⁇ Content ratio of block copolymer having a structure represented by any one of formulas (i) to (iv)> Preferably, a total of 100 block copolymers containing one or more types of vinyl aromatic monomer units and conjugated diene monomer units contained in the block copolymer composition according to one embodiment of the present invention
  • the total mass of the block copolymer having a structure represented by any one of formulas (i) to (iv) in the mass% is 60% by mass or more and 100% by mass or less, more preferably 70% by mass or less. It contains at least 100% by mass.
  • the total mass of block copolymers having a structure represented by any one of formulas (i) to (iv) is contained in 60% by mass or more and 100% by mass or less in a total of 100% by mass of block copolymers.
  • the polymer block (S1) is preferably a homoblock composed of vinyl aromatic monomer units, or a random block composed of vinyl aromatic monomer units and conjugated diene monomer units.
  • the polymer block (B) is preferably a homoblock composed of conjugated diene monomer units, and the polymer block (S2) is preferably composed of vinyl aromatic monomer units. It is a homoblock composed of
  • (S1) may be a random copolymer block composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit.
  • (S1) as a random copolymer block, it is possible to control the Tg of the block copolymer composition, that is, the peak temperature of the loss tangent value (tan ⁇ ) in dynamic viscoelasticity measurement, and it is possible to control the peak temperature of the loss tangent value (tan ⁇ ) in the dynamic viscoelasticity measurement.
  • Good shrinkage characteristics can be easily obtained when
  • the random copolymer block can be obtained, for example, by adding and polymerizing a vinyl aromatic monomer and a conjugated diene monomer at a constant flow rate ratio.
  • (S1) is a polystyrene block or a random copolymer block composed of styrene monomer and butadiene monomer
  • (B) is a polybutadiene block
  • (S2) may be a polystyrene block.
  • Method for producing a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit is not particularly limited, for example, the above-mentioned vinyl aromatic monomer and conjugated diene monomer are used in an organic solvent using an organolithium compound as an initiator. Examples include a method of polymerizing.
  • organic solvents examples include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; Examples include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene.
  • aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane
  • alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane
  • An organolithium compound is a compound in which one or more lithium atoms are bonded in the molecule.
  • the organic lithium compound include monofunctional organic lithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium, hexamethylene dilithium, and butadienyl.
  • Examples include polyfunctional organic lithium compounds such as dilithium and isoprenyl dilithium.
  • a randomizing agent may be added to control the polymerization state.
  • Tetrahydrofuran THF is mainly used as the randomizing agent, but other ethers, amines, thioethers, phosphoramides, alkylbenzene sulfonates, potassium or sodium alkoxides, etc. can also be used.
  • Suitable ethers include, in addition to THF, dimethyl ether, diethyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and the like.
  • amines such as trimethylamine, triethylamine, tetramethylethylenediamine, and cyclic amines can also be used.
  • triphenylphosphine, hexamethylphosphoramide, potassium or sodium alkylbenzenesulfonate, potassium or sodium butoxide, and the like can also be used as randomizing agents.
  • the amount of the randomizing agent added for example, 0.001 to 10 parts by mass can be added to 100 parts by mass of the total monomers charged.
  • the timing of addition is preferably before the start of the polymerization reaction. Additionally, it can be added as necessary.
  • the block copolymer thus obtained is inactivated by adding a polymerization terminator such as water, alcohol, carbon dioxide, etc. in an amount sufficient to inactivate the active ends.
  • a polymerization terminator such as water, alcohol, carbon dioxide, etc.
  • Methods for recovering the copolymer from the obtained block copolymer solution include (1) a method of precipitating with a poor solvent such as methanol, and (2) a method of precipitating by evaporating the solvent with a heated roll etc. (drum dryer). method), (3) method of concentrating the solution using a concentrator and then removing the solvent using a vented extruder, (4) recovering the copolymer by dispersing the solution in water and removing the solvent by heating by blowing in steam. Any method can be used, such as a steam stripping method.
  • the block copolymer composition according to one embodiment of the present invention may contain additives within a range that does not impede the effects of the present invention.
  • additives include various stabilizers, lubricants, processing aids, antiblocking agents, antistatic agents, antifogging agents, light resistance improvers, softeners, plasticizers, pigments, etc. can be mentioned.
  • Each additive may be added to the block copolymer solution, or may be blended and melt-mixed with the recovered block copolymer.
  • the stabilizer examples include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy-3, 5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2,6- Examples include phenolic antioxidants such as di-tert-butyl-4-methylphenol, phosphorus antioxidants such as trisnonylphenyl phosphite, and the like.
  • antiblocking agent examples include high impact polystyrene, organic fillers such as crosslinked beads of vinyl aromatic hydrocarbon copolymer, silica beads, quartz beads, and the like.
  • additives include fatty acid amide, ethylene bisstearamide, sorbitan monostearate, saturated fatty acid ester of aliphatic alcohol, and pentaerythritol fatty acid ester. These additives are preferably used in an amount of 5% by mass or less based on 100% by mass of the block copolymer composition.
  • the vinyl aromatic monomer unit and the conjugated diene monomer unit have a total mass of 100% by mass. It contains 52% by mass or more and 69% by mass or less of mer units, more preferably 55% by mass or more and 66% by mass or less, and even more preferably 57% by mass or more and 64% by mass or less.
  • the preferable content of the vinyl aromatic monomer unit in 100% by mass of the vinyl aromatic monomer unit and the conjugated diene monomer unit is 52, 53, 55, 60 , 65, 68, or 69% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the content of vinyl aromatic monomer units is the total content of vinyl aromatic monomer units contained in the block copolymers used together. means.
  • the rigidity of the heat-shrinkable film obtained from the resin composition containing the block copolymer composition is reduced to a level suitable for the heat-shrinkable film. If the amount is 69% by mass or less, the specific gravity separability with water of the heat-shrinkable film obtained from the resin composition containing the block copolymer composition can be further improved.
  • the content of the vinyl aromatic monomer unit in the total 100% by mass of the vinyl aromatic monomer unit and the conjugated diene monomer unit can be measured by a halogen addition method.
  • the block copolymer composition according to one embodiment of the present invention has a flexural modulus of elasticity measured according to ISO 178 of 1000 MPa or more, preferably 1050 MPa or more, and more preferably 1100 MPa or more.
  • the preferable flexural modulus of the block copolymer composition is 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, or 1800 MPa, and is between any two of the numerical values exemplified here. may be within the range of
  • the rigidity of the heat-shrinkable film obtained from the resin composition containing the block copolymer composition can be made suitable for a heat-shrinkable film.
  • the flexural modulus can be controlled, for example, by adjusting the structure of the block copolymer; for example, a block copolymer having a structure represented by any one of formulas (i) to (iv) By adopting , the bending modulus of elasticity can be increased. Also, increasing the amount of vinyl aromatic monomer units contained in 100% by mass of the total mass of vinyl aromatic monomer units and conjugated diene monomer units of the block copolymer composition.
  • the flexural modulus can also be increased by
  • Flexural modulus is measured according to ISO178.
  • the block copolymer composition according to an embodiment of the present invention is dynamically processed in a fixed three-point bending mode under the conditions of a heating rate of 4° C./min, a frequency of 1 Hz, and a strain of 0.02% in accordance with ISO 6721-1.
  • the loss tangent value (tan ⁇ ) when performing viscoelasticity measurement has at least one peak in the range of 80°C or higher and 110°C or lower, preferably at least one peak in the range of 82°C or higher and 108°C or lower.
  • the loss tangent value has at least one peak at 80, 85, 90, 95, 100, 105, or 110°C, and has a range between any two of the numerical values exemplified here. may have one or more peaks within it.
  • the heat-shrinkable film obtained from the resin composition containing the block copolymer composition is suitable as a heat-shrinkable film. It is thought that it may have a shrinkage characteristic.
  • the temperature at which the peak of the loss tangent value (tan ⁇ ) appears is determined, for example, when a random copolymer block composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit is present in the block copolymer. can be controlled by adjusting the content ratio of vinyl aromatic monomer units and conjugated diene monomer units in the random copolymer block.
  • the loss tangent value (tan ⁇ ) is determined in accordance with ISO6721-1 using, for example, a dynamic viscoelasticity measurement device RSA-III (manufactured by TA Instruments) at a heating rate of 4°C/min, a frequency of 1 Hz, and a strain of 0.02%. It is measured by dynamic viscoelasticity measurement in a fixed three-point bending mode.
  • RSA-III manufactured by TA Instruments
  • the specific gravity at 23°C of the block copolymer composition according to one embodiment of the present invention is preferably 0.950 or more and less than 1.000, more preferably 0.950 or more and 0.999 or less, More preferably, it is 0.960 or more and 0.997 or less.
  • the specific gravity of the block copolymer composition is 0.950, 0.960, 0.970, 0.980, 0.990, 0.991, 0.992, 0.993, 0.994 , 0.995, 0.996, 0.997, 0.998, or 0.999, and may be within a range between any two of the numerical values exemplified here.
  • the heat-shrinkable film obtained from the resin composition containing the block copolymer composition can have excellent specific gravity separability with water.
  • the specific gravity of the block copolymer composition is, for example, the vinyl aromatic monomer unit and the conjugated diene monomer unit when the total mass of the vinyl aromatic monomer unit and the conjugated diene monomer unit in the block copolymer composition is 100% by mass. It can be controlled by adjusting the content of monomer units in the system.
  • the specific gravity of the block copolymer composition at 23°C can be measured by the procedure described in JIS Z8807:2012.
  • the block copolymer composition according to one embodiment of the present invention includes one or more block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, and various additives as necessary. obtained by mixing. Any known method can be used for mixing these block copolymers and additives. For example, dry blending may be carried out using a Henschel mixer, ribbon blender, super mixer, V-blender, etc., and furthermore, it may be melted and pelletized using an extruder. In one embodiment, melt mixing is preferred. Alternatively, a method of removing the solvent after mixing the polymer solutions can also be used.
  • a resin composition according to an embodiment of the present invention contains one or more block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit according to an embodiment of the present invention. Contains a block copolymer composition.
  • the resin composition according to an embodiment of the present invention contains the block copolymer composition in 100% by mass of the resin composition at 80% by mass or more and 100% by mass or less, preferably 85% by mass or more and 100% by mass or less. However, the content is more preferably 90% by mass or more and 100% by mass or less. Specifically, the content of the block copolymer composition in 100% by mass of the resin composition is 80, 82, 85, 90, 95, 98, or 100% by mass, and any of the values exemplified here or within a range between the two. In one embodiment, the resin composition may consist essentially only of the block copolymer composition.
  • the heat-shrinkable film obtained from the resin composition containing the block copolymer composition has good specific gravity separation properties with water, and heat shrinkage is improved.
  • the rigidity can be made suitable for a flexible film.
  • the resin composition according to one embodiment of the present invention may contain other materials other than a block copolymer containing a vinyl aromatic monomer unit and a conjugated diene monomer unit, within a range that does not impair the effects of the present invention. May include polymers. Such other polymers are, in other words, polymers that do not contain block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units. Specific examples include styrene polymers such as general-purpose polystyrene, high-impact polystyrene, and styrene-(meth)acrylate copolymer resins.
  • the resin composition according to one embodiment of the present invention can be obtained by mixing the block copolymer composition according to one embodiment of the present invention, and optionally additives and other polymers described above.
  • the resin composition may be obtained by mixing one or more block copolymers, and optionally additives and other polymers, without passing through the block copolymer composition.
  • a method for mixing these block copolymer compositions, additives, and other polymers, or a known method for mixing the block copolymer composition, additives, and other polymers can be adopted.
  • dry blending may be carried out using a Henschel mixer, ribbon blender, super mixer, V-blender, etc., and furthermore, it may be melted and pelletized using an extruder. In one embodiment, melt mixing is preferred.
  • a method of removing the solvent after mixing the polymer solutions can also be used.
  • a heat-shrinkable film according to an embodiment of the present invention contains a block copolymer composition containing one or more block copolymers containing a vinyl aromatic monomer unit and a conjugated diene monomer unit.
  • This is a heat-shrinkable film including a layer made of a resin composition.
  • the heat-shrinkable film is stretched in at least one of the MD direction and the TD direction of the heat-shrinkable film.
  • the MD direction of the heat-shrinkable film in the present invention means the feeding direction (Machine Direction) of the film in the line that produces the heat-shrinkable film
  • the TD direction of the heat-shrinkable film means the direction in the MD direction of the heat-shrinkable film.
  • the direction in which the heat-shrinkable film is stretched to a greater extent may be referred to as the main stretching direction.
  • the heat-shrinkable film may be a single-layer film in which only a layer containing the resin composition is used, or may be a heat-shrinkable multilayer film in which another resin layer is laminated on at least one surface thereof.
  • another resin layer may be laminated on the stretched heat-shrinkable film, or another resin layer may be laminated on an unstretched film obtained by forming the resin composition into a film.
  • a multilayer film obtained by laminating the resin composition and another resin by multilayer extrusion molding may be drawn.
  • the resin used for the other resin layer styrene resin is preferable.
  • the heat-shrinkable film is preferably non-foamed.
  • all layers must be formed using the commonly used method for foaming, i.e., when the resin and chemical foaming agent are melted and kneaded, the chemical foaming agent is thermally decomposed and generated.
  • the molding may be performed without using a chemical foaming method in which the resin is foamed with gas, a physical foaming method in which gas is injected into the melted resin in an extruder, and the resin is foamed.
  • Non-foaming can be considered as non-foaming if, for example, when a cross section of a heat-shrinkable film is observed using a laser microscope, the area ratio of air bubbles to the cross-sectional area is 1% or less. Since the heat-shrinkable film is non-foamed, the heat-shrinkable film has good transparency and surface smoothness.
  • a heat-shrinkable film according to an embodiment of the present invention is a film including a layer made of a resin composition according to an embodiment of the present invention.
  • the heat-shrinkable film is obtained by stretching a sheet including a layer made of a resin composition according to an embodiment of the present invention.
  • the method of manufacturing the sheet is not particularly limited, but for example, a method of forming the sheet by extrusion using a resin composition can be used. Further, during extrusion, the sheet may be extruded together with a resin composition to form a sheet composed of a plurality of layers including a layer composed of the resin composition.
  • sheet and “film” are not used to distinguish between different thicknesses, but when the thickness changes (thinners) due to an operation such as stretching, the term “sheet” refers to the film before it becomes thinner. ” is sometimes called.
  • the stretching may be uniaxially, biaxially, or multiaxially.
  • uniaxial stretching include stretching an extruded sheet in a direction perpendicular to the extrusion direction (TD direction) using a tenter, stretching an extruded tubular film in the circumferential direction (TD direction), and stretching an extruded sheet in a direction perpendicular to the extrusion direction (TD direction).
  • MD direction stretching an extrusion direction
  • biaxial stretching examples include a method in which an extruded sheet is stretched in the extrusion direction (MD direction) with a roll, and then stretched in a direction perpendicular to the extrusion direction (TD direction) with a tenter, etc., and an extruded tubular film
  • MD direction extrusion direction
  • TD direction direction perpendicular to the extrusion direction
  • the stretching temperature is preferably, for example, 60 to 120°C.
  • a temperature of 60° C. or higher makes it difficult for the film to break during stretching, and a temperature of 120° C. or lower provides a film with good shrinkage characteristics, which is preferable.
  • Particularly preferred is a range of Tg+5°C to Tg+20°C with respect to the glass transition temperature (Tg) of the composition constituting the film.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • the glass transition temperature (Tg) can be determined, for example, from the temperature at the peak of the loss modulus.
  • the stretching ratio in the main stretching direction which is stretched more greatly, is not particularly limited, but is preferably 1.5 to 8.0 times.
  • a stretching ratio of 1.5 times or more in the main stretching direction allows a film with good shrinkage characteristics to be obtained, and a stretching ratio of 8.0 times or less makes it possible to easily produce a stretched film, which is preferable. .
  • the heat-shrinkable film according to one embodiment of the present invention has excellent specific gravity separation properties with water. Excellent specific gravity separation with water can be achieved, for example, by setting the specific gravity of the heat-shrinkable film to less than 1.000.
  • the heat-shrinkable film according to an embodiment of the present invention preferably has a specific gravity at 23° C. of, for example, 0.950 or more and less than 1.000. If the specific gravity of the heat-shrinkable film is less than 1.000, it is preferable because it floats on water and can be separated by water from those having a specific gravity of 1.000 or more.
  • the specific gravity of the heat-shrinkable film can be controlled by making the heat-shrinkable film contain a layer made of the resin composition according to one embodiment of the present invention, or by adjusting the specific gravity of other layers. Specific gravity is measured at 23° C., for example, according to JIS Z8807:2012.
  • a heat-shrinkable film according to an embodiment of the present invention may have shrinkage characteristics suitable for a heat-shrinkable film.
  • the shrinkage characteristic here means, for example, the balance between thermal shrinkage rate and natural shrinkage rate. Thermal shrinkage rate and natural shrinkage rate are generally in a trade-off relationship, but it is desirable to strike a balance between them depending on the application.
  • the heat-shrinkable film according to one embodiment of the present invention may have a heat-shrinkage rate suitable for a heat-shrinkable film.
  • the heat shrinkage rate in at least one direction is preferably 60% or more at 100° C. for 10 seconds, and preferably 40% or more at 80° C. for 10 seconds. With such a heat shrinkage rate, the temperature does not need to be high at the time of shrinkage, so that the effect on the article to be coated can be suppressed.
  • the heat shrinkage rate of the heat-shrinkable film according to an embodiment of the present invention is determined in the TD direction of the heat-shrinkable film when the main stretching direction (the direction in which it is stretched more greatly) of the heat-shrinkable film is the TD direction. means a measured value.
  • the main stretching direction of the heat-shrinkable film is the MD direction, it means the value measured in the MD direction of the heat-shrinkable film.
  • the heat shrinkage rate is calculated, for example, by immersing a heat-shrinkable film in hot water for a certain period of time and calculating the difference in length before and after shrinkage.
  • the heat-shrinkable film according to one embodiment of the present invention may have a natural shrinkage rate suitable for a heat-shrinkable film. Specifically, for example, it is preferably 4% or less at 40° C. for 7 days. If the natural shrinkage rate is 4% or less, shrinkage of the heat-shrinkable film during storage can be reduced, resulting in excellent storage properties.
  • the natural shrinkage rate is calculated, for example, by leaving the heat-shrinkable film in an atmosphere at 40° C. for 7 days and calculating the difference in length before and after shrinkage.
  • the heat-shrinkable film according to one embodiment of the present invention may have a rigidity suitable for a heat-shrinkable film. Therefore, the heat-shrinkable film has a suitable stiffness, and the work and processing when attaching the heat-shrinkable film to a container can be performed without any problem.
  • the stiffness can be expressed by the Young's modulus of the heat-shrinkable film in the MD direction. Specifically, for example, if the Young's modulus in the MD direction at 23° C. is 500 MPa or more, it can be said that the film has a rigidity suitable for a heat-shrinkable film. Young's modulus can be measured at a tensile rate of 200 mm/min at 23° C. in an environment with a humidity of 50 ⁇ 5%.
  • the thickness of the heat-shrinkable film according to one embodiment of the present invention is preferably 20 to 100 ⁇ m, more preferably 50 to 95 ⁇ m.
  • the heat-shrinkable film according to an embodiment of the present invention can be attached to a container by taking advantage of its heat-shrinkability, as a non-printed film, as a label with a product name printed thereon, or as a cap seal or other packaging material.
  • a container by taking advantage of its heat-shrinkability, as a non-printed film, as a label with a product name printed thereon, or as a cap seal or other packaging material. can do.
  • a polymer solution containing a block copolymer having polystyrene blocks was obtained.
  • This polymerization solution was preliminarily concentrated and further devolatilized and extruded using a twin-screw extruder equipped with a vacuum vent to obtain the desired pelletized block copolymer (P-4).
  • the internal temperature of the reaction system is raised to 80°C, and while maintaining the internal temperature, 40 kg of styrene and 60 kg of 1,3-butadiene are added at 40.0 kg/h and 60 kg/h, respectively. They were added simultaneously at a constant addition rate of .0 kg/h.
  • the internal temperature of the reaction system was lowered to 60°C, 50 kg of styrene was added, and styrene was anionically polymerized. The internal temperature rose to 87°C.
  • Block structure of block copolymer The block structures of the obtained block copolymers (P-1) to (P-8) are shown in Tables 1 and 2.
  • the block structure of the block copolymer can be determined by the procedure for adding each monomer. Furthermore, the content of each block structure contained in the block copolymer and the content of monomer units contained in each block structure can be calculated from the amount of monomers used as raw materials.
  • Block copolymer composition > [Raw materials used] ⁇ Block copolymer: (P-1) to (P-8) obtained by the above polymerization ⁇ Anti-blocking agent: E640N (high impact polystyrene, manufactured by Toyo Styrene Co., Ltd.)
  • Example 1> After dry-blending 1.3% by mass of E640N to 100% by mass of block copolymer (P-1), a block copolymer composition (RA-1) was obtained by melting and pelletizing in an extruder. Ta.
  • (A2) The content of butadiene (rubber content) was calculated based on the amount of double bonds obtained by the method of (A1). Regarding the styrene content, the value obtained by subtracting the butadiene content from the entire sample was calculated as the styrene content.
  • Resin composition The above block copolymer compositions (RA-1) to (RA-4) and (RB-1) to (RB-3) were used as resin compositions as they were.
  • Heat shrinkage rate (%) (L1-L2)/L1 ⁇ 100
  • Natural shrinkage rate (%) (L1-L2)/L1 x 100
  • L1 Length before contraction
  • L2 Length after contraction
  • Young's modulus was measured at 23° C. in the TD direction and MD direction of the heat-shrinkable film at a tensile rate of 200 mm/min in an environment with humidity of 50 ⁇ 5%.
  • the heat-shrinkable film molded using the block copolymer composition and resin composition according to the examples of the present invention had a specific gravity of less than 1.000 at 23°C. Therefore, it has excellent specific gravity separation with water.
  • the heat-shrinkable film molded using the block copolymer composition and resin composition according to the examples of the present invention has a Young's modulus in the MD direction of 500 MPa or more, and has a rigidity suitable for a heat-shrinkable film. It was confirmed that Therefore, the heat-shrinkable film has a suitable stiffness, and the work and processing when attaching the heat-shrinkable film to a container can be performed without any problem.
  • the heat-shrinkable film formed using the block copolymer composition and resin composition according to the examples of the present invention had shrinkage characteristics suitable for a heat-shrinkable film. . Since the temperature does not need to be high during shrinkage, the effect on the article to be coated can be suppressed. Furthermore, since shrinkage of the heat-shrinkable film during storage can be reduced, storage properties are excellent.
  • the heat-shrinkable film molded using the block copolymer composition and resin composition according to the examples of the present invention has excellent properties as described above even when molded without foaming. It was confirmed that it was possible to obtain a heat-shrinkable film having specific gravity separability with water.
  • block copolymer compositions and resin compositions with a flexural modulus of less than 1000 MPa when block copolymer compositions and resin compositions with a flexural modulus of less than 1000 MPa are used, some of them become soft and difficult to form into a film (poor rigidity).
  • the content of vinyl aromatic monomer units is 69% by mass when the total mass of vinyl aromatic monomer units and conjugated diene monomer units in the block copolymer is 100% by mass.
  • % of the block copolymer composition and the resin composition had a specific gravity of 1.000 or more at 23°C.
  • the peak of the loss tangent value does not have a peak in the range of 80 ° C. or higher and 110 ° C. or lower.
  • the block copolymer composition according to the present invention is characterized in that when a heat-shrinkable film is obtained from a resin composition containing the block copolymer composition, even if the heat-shrinkable film is non-foamed, A heat-shrinkable film that can be separated by specific gravity can be obtained.
  • the resin composition containing the block copolymer composition according to the present invention can provide a heat-shrinkable film with excellent specific gravity separation properties with water, and has industrial applicability.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une composition de copolymère séquencé qui permet d'obtenir un film thermorétractable qui peut être séparé par densité en utilisant de l'eau même si le film thermorétractable n'est pas expansé lors de l'obtention d'un film thermorétractable à partir d'une composition de résine contenant la composition de copolymère séquencé.　L'invention concerne une composition de copolymère séquencé contenant un ou plusieurs copolymères séquencés qui comprennent un motif monomère aromatique vinylique et un motif monomère diène conjugué. Lorsque la masse totale des motifs monomères aromatiques vinyliques et des motifs monomères diènes conjugués est prise comme étant de 100 % en masse, la composition de copolymère séquencé contient de 52 % en masse à 69 % en masse des motifs monomères aromatiques vinyliques. La composition de copolymère séquencé a un module de flexion mesuré selon la norme ISO 178 de 1000 MPa ou plus, et la composition de copolymère séquencé a au moins un pic dans la plage de tangente de perte (tan δ) de 80 °C à 110 °C lorsqu'une mesure de viscoélasticité dynamique est effectuée selon un mode de flexion à trois points fixe à une vitesse de chauffage de 4 °C/min, une fréquence de 1 Hz, et une courbure de 0,02 % selon la norme ISO 6721-1.
PCT/JP2023/030927 2022-09-02 2023-08-28 Composition de copolymère séquencé, composition de résine contenant une composition de copolymère séquencé, film thermorétractable WO2024048506A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002038642A1 (fr) * 2000-11-10 2002-05-16 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere bloc, sa composition et films en etant faits
JP2004027029A (ja) * 2002-06-26 2004-01-29 Denki Kagaku Kogyo Kk 熱収縮性フィルム
WO2008117591A1 (fr) * 2007-03-28 2008-10-02 Denki Kagaku Kogyo Kabushiki Kaisha Matière de moulage pour un retrait dans le sens machine et un film à retrait dans le sens machine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002038642A1 (fr) * 2000-11-10 2002-05-16 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere bloc, sa composition et films en etant faits
JP2004027029A (ja) * 2002-06-26 2004-01-29 Denki Kagaku Kogyo Kk 熱収縮性フィルム
WO2008117591A1 (fr) * 2007-03-28 2008-10-02 Denki Kagaku Kogyo Kabushiki Kaisha Matière de moulage pour un retrait dans le sens machine et un film à retrait dans le sens machine

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