WO2023171535A1 - 熱可塑性エラストマー - Google Patents

熱可塑性エラストマー Download PDF

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Publication number
WO2023171535A1
WO2023171535A1 PCT/JP2023/007889 JP2023007889W WO2023171535A1 WO 2023171535 A1 WO2023171535 A1 WO 2023171535A1 JP 2023007889 W JP2023007889 W JP 2023007889W WO 2023171535 A1 WO2023171535 A1 WO 2023171535A1
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WIPO (PCT)
Prior art keywords
block copolymer
aromatic vinyl
film
polymer block
conjugated diene
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Ceased
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PCT/JP2023/007889
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English (en)
French (fr)
Japanese (ja)
Inventor
雄太 石井
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Zeon Corp
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Zeon Corp
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Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2024506122A priority Critical patent/JPWO2023171535A1/ja
Priority to US18/845,094 priority patent/US20250179288A1/en
Priority to EP23766711.8A priority patent/EP4491668A4/en
Priority to CN202380025011.2A priority patent/CN118804950A/zh
Publication of WO2023171535A1 publication Critical patent/WO2023171535A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08F297/046—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 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • 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
    • C08F297/044—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 using a coupling agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
    • A61F13/49—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape specially adapted to be worn around the waist, e.g. diapers, nappies
    • A61F13/49007—Form-fitting, self-adjusting disposable diapers
    • A61F13/49009—Form-fitting, self-adjusting disposable diapers with elastic means
    • A61F13/4902—Form-fitting, self-adjusting disposable diapers with elastic means characterised by the elastic material
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Definitions

  • the present invention relates to a thermoplastic elastomer, and more particularly to a thermoplastic elastomer that has high stress, high expansion/contraction rate, and can provide a wide film-like elastic body.
  • Aromatic vinyl-conjugated diene-aromatic vinyl block copolymers are particularly elastic and flexible among thermoplastic elastomers, so they are used as materials for stretch films used in sanitary products such as disposable diapers and sanitary products. is one of its typical uses.
  • Patent Document 1 discloses a composition containing a specific block copolymer as a composition for providing an elastic body for use as a sanitary product such as a disposable diaper. According to Patent Document 1, an elastic body with little thickness variation and low permanent elongation is obtained.
  • the elastic resin material constituting the elastic member is heated and melted and discharged in the form of a film or a line, and then, A process for obtaining a stretchable member (stretchable composite sheet) by laminating and bonding a base sheet to an elastic resin material that has been stretched in the MD direction has been studied, and the composition disclosed in Patent Document 1 mentioned above has been studied.
  • a product is applied to such a process, there is a large decrease in the film width after discharge, and furthermore, a large decrease in the film width when it is stretched in the MD direction. There was also the problem that parts could not be obtained efficiently.
  • the present invention was made in view of the above circumstances, and an object of the present invention is to provide a thermoplastic elastomer that has high stress, low permanent elongation, and can provide a wide film-like elastic body. do.
  • thermoplastic elastomer whose storage modulus and loss tangent (tan ⁇ ) were controlled within a specific range, and which were made into a film by melt extrusion.
  • the inventors have discovered that the above object can be achieved by making the film have specific characteristics, and have completed the present invention.
  • thermoplastic elastomer The storage modulus at 23°C is more than 0.3 MPa, The loss tangent (tan ⁇ ) at 23°C is 0.20 or less,
  • the ratio of the stress at 100% elongation (M MD ) to the stress at 100% elongation (M MD /M TD ) is less than 2.5, When the film is pulled in the MD direction, it does not have a yield point at an elongation rate of 200% or less.
  • a thermoplastic elastomer is provided.
  • the thermoplastic elastomer of the present invention preferably contains an aromatic vinyl block copolymer.
  • the aromatic vinyl block copolymer is preferably an aromatic vinyl-conjugated diene block copolymer.
  • the elastomer of the present invention preferably contains the aromatic vinyl block copolymer in a proportion of more than 50% by weight, and contains the polyolefin elastomer in a proportion of more than 1% by weight and less than 50% by weight.
  • the polyolefin elastomer preferably contains ethylene units.
  • thermoplastic elastomer of the present invention is preferably used for a stretchable member that is used by being stretched in the MD direction.
  • the thermoplastic elastomer of the present invention is preferably formed into a film by melt extrusion, and is used as an elastic member by being continuously laminated and bonded to a base sheet.
  • an elastic body obtained using the above thermoplastic elastomer is provided.
  • a film obtained using the above thermoplastic elastomer is provided.
  • the elastic body or film of the present invention can be used by being stretched in the CD direction, it is preferably used by being stretched in the MD direction.
  • a porous film obtained using the above thermoplastic elastomer is provided.
  • an elastic member obtained using the above thermoplastic elastomer there is provided an elastic member obtained using the above thermoplastic elastomer.
  • thermoplastic elastomer that has high stress, low permanent elongation, and can provide a wide film-like elastic body.
  • FIG. 1 is a schematic diagram of a manufacturing apparatus for manufacturing a stretchable laminate according to an embodiment of the present invention.
  • thermoplastic elastomer of the present invention satisfies all of the following (1) to (4).
  • Storage modulus at 23°C is more than 0.3 MPa.
  • Loss tangent (tan ⁇ ) at 23°C is 0.20 or less.
  • the MD direction of the film is the melt flow direction when the film is made into a film by melt extrusion, extrusion into a film shape, and cooling and solidification using a melt extrusion device
  • the TD direction of the film is This is the perpendicular direction of the melt flow when the film is made into a film by extruding it into a film by melt-extruding it and solidifying it by cooling.
  • thermoplastic elastomers that have high stress, low permanent elongation, and can provide a wide film-like elastic body, and found that the above (1) to (4) The inventors have discovered that a thermoplastic elastomer that satisfies all of these requirements can provide a film-like elastic body that has high stress, low permanent elongation, and wide width, and has thus completed the present invention.
  • the thermoplastic elastomer of the present invention has a storage modulus at 23°C of more than 0.3 MPa, preferably more than 0.3 MPa and less than 8 MPa, more preferably 0.4 to 5 MPa, more preferably 0.45 to 3 MPa. , more preferably 0.5 to 2.5 MPa, even more preferably 0.55 to 2.1 MPa, particularly preferably 0.6 to 1.8 MPa. If the storage modulus at 23°C is too low, the stress will be low.
  • the storage modulus at 23° C. can be measured by the method described in Examples below.
  • the thermoplastic elastomer of the present invention has a loss tangent (tan ⁇ ) at 23°C of 0.20 or less, preferably less than 0.16, more preferably less than 0.14, and most preferably less than 0.12. It is.
  • the lower limit of the loss tangent (tan ⁇ ) at 23° C. is not particularly limited, but is usually 0.01 or more. If the loss tangent (tan ⁇ ) at 23° C. is too high, permanent elongation will become large.
  • the loss tangent (tan ⁇ ) at 23° C. can be measured by the method described in the Examples below.
  • the stress at 100% elongation in the MD direction of the film (M MD ) and the stress at 100% elongation in the TD direction (M TD ) (M MD /M TD ) is less than 2.5, preferably 1.0 to 2.0, more preferably 1.05. -1.9, most preferably 1.1-1.5. If the ratio (M MD / M TD ) is too large, when the film is melted by heating and discharged into a film, the width of the film after discharge will decrease significantly (the width of the obtained film will be smaller than the width at the time of discharge).
  • thermoplastic elastomer of the present invention when the thermoplastic elastomer of the present invention is made into a film by melt-extruding it into a film using a melt-extrusion device and cooling and solidifying it, when the film is pulled in the MD direction, the elongation rate is 200. % or less, it has no yield point. If it has a yield point at an elongation rate of 200% or less, the permanent elongation will become large. Note that the presence or absence of a yield point at an elongation rate of 200% or less can be measured by the method described in Examples described later.
  • thermoplastic elastomer of the present invention is not particularly limited as long as it satisfies all of the above (1) to (4), but it preferably contains an aromatic vinyl block copolymer, and is preferably one containing an aromatic vinyl block copolymer. It is more preferable that the thermoplastic elastomer contains a block copolymer as a main component (for example, a thermoplastic elastomer containing an aromatic vinyl block copolymer in an amount exceeding 50% by weight of the entire thermoplastic elastomer). It is more preferable that the block copolymer be contained in a proportion of more than 75% by weight.
  • aromatic vinyl block copolymers aromatic vinyl-conjugated diene block copolymers are preferred.
  • block copolymer D represented by general formula (D): (Ar d -D d ) n -X at least one and Preferred examples include aromatic vinyl block copolymer compositions containing the following.
  • the block copolymer A represented by the general formula (A): Ar1 a -D a -Ar2 a is preferably the following block copolymer. That is, in the formula, Ar1 a is an aromatic vinyl polymer block with a weight average molecular weight of 7,000 to 17,000, D a is a conjugated diene polymer block with a weight average molecular weight of 50,000 to 200,000, and Ar2 a is an aromatic vinyl polymer block with a weight average molecular weight of 50,000 to 200,000. Represents an aromatic vinyl polymer block of more than 20,000 and less than 300,000.
  • the weight average molecular weight of block copolymer A i.e., the weight average molecular weight of the entire block copolymer A
  • the molecular weight distribution (Mw/Mn) of block copolymer A i.e., block The molecular weight distribution (Mw/Mn) of the entire copolymer A is 1.0 to 1.2
  • the content of aromatic vinyl monomer units in the block copolymer A is
  • the block copolymer B represented by the general formula (B): Ar1 b -D b -Ar2 b is preferably the following block copolymer. That is, in the formula, Ar1 b is an aromatic vinyl polymer block with a weight average molecular weight of 7,000 to 17,000, D b is a conjugated diene polymer block with a weight average molecular weight of 50,000 to 200,000, and Ar2 b is an aromatic vinyl polymer block with a weight average molecular weight of 50,000 to 200,000. Represents 7,000 to 17,000 aromatic vinyl polymer blocks.
  • the weight average molecular weight of block copolymer B (that is, the weight average molecular weight of the entire block copolymer B) is 75,000 to 300,000
  • the molecular weight distribution (Mw/Mn) of block copolymer B (that is, the weight average molecular weight of block copolymer B as a whole) is 75,000 to 300,000.
  • the molecular weight distribution (Mw/Mn) of the entire copolymer B is 1.0 to 1.2, and the content of aromatic vinyl monomer units in the block copolymer B is
  • the block copolymer C represented by the general formula (C): Ar1 c -D c -Ar2 c is preferably the following block copolymer. That is, in the formula, Ar1 c is an aromatic vinyl polymer block with a weight average molecular weight of 7,000 to 17,000, D c is a conjugated diene polymer block with a weight average molecular weight of 80,000 to 250,000, and Ar2 c is an aromatic vinyl polymer block with a weight average molecular weight of 80,000 to 250,000. Represents 7,000 to 17,000 aromatic vinyl polymer blocks.
  • the weight average molecular weight of the block copolymer C (i.e., the weight average molecular weight of the entire block copolymer C) is 100,000 to 300,000, and the molecular weight distribution (Mw/Mn) of the block copolymer C (i.e., the block copolymer C's weight average molecular weight) is 100,000 to 300,000.
  • the molecular weight distribution (Mw/Mn) of the entire copolymer C is 1.0 to 1.2, and the content of aromatic vinyl monomer units in the block copolymer C is
  • the block copolymer D represented by the general formula (D): (Ar d -D d ) n -X is preferably the following block copolymer. That is, in the formula, Ar d is an aromatic vinyl polymer block having a weight average molecular weight of 7,000 to 17,000, D d is a conjugated diene polymer block having a weight average molecular weight of 60,000 to 190,000, and n is an integer of 2 or more. X represents the residue of a coupling agent).
  • the weight average molecular weight of the block copolymer D (that is, the weight average molecular weight of the entire block copolymer D) is 100,000 to 400,000, and the molecular weight distribution (Mw/Mn) of the block copolymer D is 1.0. ⁇ 1.2, and the content of aromatic vinyl monomer units in block copolymer D is 11 to 22% by weight based on the total monomer units constituting block copolymer D,
  • block copolymer D when block copolymer D is a mixture of multiple polymers with different values of n, the molecular weight distribution (Mw/Mn) of the polymers that can be determined to have the same value of n falls within the above range. It should be the one in .
  • the molecular weight distribution (Mw/Mn) of each of the branched product and the 4-branched product may be within the above range (that is, each branched product has a molecular weight distribution (Mw/Mn) of 1.0 to 1.0. 1.2).
  • the block copolymer A, block copolymer B, block copolymer C, and block copolymer D have different weight average molecular weights of the aromatic vinyl polymer block and the conjugated diene polymer block, and the block copolymer
  • the molecular weight distribution (Mw/Mn) of the entire block copolymer is in the range of 1.0 to 1.2
  • the conjugated diene The cis/trans ratio of the conjugated diene monomer units constituting the polymer block is in the range of 1.5 to 4.
  • block copolymer A, block copolymer B, block copolymer C, and block copolymer D whose molecular weight distribution (Mw/Mn) and cis/trans ratio are within a predetermined range are prepared.
  • an aromatic vinyl block copolymer composition containing at least one of the above all of the above (1) to (4) are suitably satisfied, and thereby the composition has high stress and a low expansion/contraction rate. It is possible to provide a film-like elastic body that is high and wide.
  • Block copolymer A is a copolymer represented by the following general formula (A).
  • the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) are composed of aromatic vinyl monomer units obtained by polymerizing aromatic vinyl monomers as a main repeating unit. It is a polymer block.
  • the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) may be any aromatic vinyl compound.
  • aromatic vinyl compound examples include, but are not limited to, styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropyl Styrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl Examples include -4,6-dichlorostyrene, 2,4-dibromostyrene, and vinyl
  • aromatic vinyl monomers can be used alone or in combination of two or more.
  • the two aromatic vinyl polymer blocks may be composed of the same aromatic vinyl monomer unit or may be composed of different aromatic vinyl monomer units.
  • the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) do not contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit. It's okay to stay.
  • monomers constituting monomer units other than the aromatic vinyl monomer units that may be contained in the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) include 1 , 3-butadiene, conjugated diene monomers such as isoprene (2-methyl-1,3-butadiene), ⁇ , ⁇ -unsaturated nitrile monomers, unsaturated carboxylic acid or acid anhydride monomers, unsaturated Examples include carboxylic acid ester monomers and non-conjugated diene monomers.
  • the content of monomer units other than aromatic vinyl monomer units in the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) is preferably 20% by weight or less, It is more preferably 10% by weight or less, and particularly preferably substantially 0% by weight. That is, the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) are substantially composed only of one or more types of aromatic vinyl monomer units. is preferable, and it is particularly preferable that it consists only of styrene units.
  • the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ) have different weight average molecular weights.
  • the weight average molecular weight of the aromatic vinyl polymer block (Ar1 a ) is 7,000 to 17,000, preferably 9,000 to 15,000, and more preferably 10,000 to 14,000.
  • the weight average molecular weight of the aromatic vinyl polymer block (Ar2 a ) is more than 20,000 and less than 300,000, preferably 25,000 to 240,000, more preferably 30,000 to 190,000, and even more preferably 35,000 to 180,000. The most preferred range is 35,000 to 99,000.
  • the conjugated diene polymer block (D a ) is a polymer block constituted as a main repeating unit of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer.
  • the conjugated diene monomer used to constitute the conjugated diene monomer unit of the conjugated diene polymer block (D a ) is not particularly limited as long as it is a conjugated diene compound, but for example, 1,3-butadiene, isoprene, etc. , 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene, farnesene and the like. Among these, it is preferable to use 1,3-butadiene and/or isoprene, and it is particularly preferable to use isoprene.
  • These conjugated diene monomers can be used alone or in combination of two or more. Furthermore, a hydrogenation reaction may be performed on some of the unsaturated bonds of the conjugated diene polymer block (D a ).
  • the conjugated diene polymer block (D a ) may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit.
  • Monomers constituting monomer units other than conjugated diene monomer units that may be contained in the conjugated diene polymer block (D a ) include aromatic vinyl monomers such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitrile monomer, unsaturated carboxylic acid or acid anhydride monomer, unsaturated carboxylic acid ester monomer, and non-conjugated diene monomer.
  • the content of monomer units other than conjugated diene monomer units in the conjugated diene polymer block (D a ) is preferably 20% by weight or less, more preferably 10% by weight or less, and substantially It is particularly preferred that the content is 0% by weight. That is, the conjugated diene polymer block (D a ) preferably consists essentially only of one or more types of conjugated diene monomer units, and preferably consists only of isoprene units. Particularly preferred.
  • the vinyl bond content of the conjugated diene monomer units constituting the conjugated diene polymer block (D a ) is not particularly limited, but is preferably 1 to 20 mol%, and preferably 2 to 15 mol%. The amount is more preferably 3 to 10 mol%.
  • the weight average molecular weight of the conjugated diene polymer block (D a ) is 50,000 to 200,000, preferably 70,000 to 150,000, and more preferably 80,000 to 120,000.
  • the weight average molecular weight of block copolymer A (that is, the weight average molecular weight of block copolymer A as a whole) is 80,000 to 400,000, preferably 110,000 to 330,000, and more preferably 130,000 to 270,000.
  • the molecular weight distribution (Mw/Mn) of block copolymer A (that is, the molecular weight distribution (Mw/Mn) of the entire block copolymer A) is 1.0 to 1.2, preferably 1.005 to 1.0. 1, more preferably 1.01 to 1.05.
  • the weight average molecular weight of each polymer block shall be sought as.
  • the weight average molecular weight of each polymer block and the weight average molecular weight of the entire block polymer are the amount of each monomer used to form each polymer block used when obtaining a block copolymer by a polymerization reaction. It can be adjusted by adjusting the amount of the polymerization initiator and the amount of the polymerization terminator.
  • the content of aromatic vinyl monomer units in block copolymer A is 39 to 85% by weight, preferably 40 to 76% by weight, based on the total monomer units constituting block copolymer A. , more preferably 41 to 70% by weight.
  • Block copolymer A is obtained by a manufacturing method in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are sequentially polymerized to form a polymer block. It is preferable. Therefore, block copolymer A preferably does not contain any coupling agent residues. Details of such a manufacturing method will be described later. However, the method is not particularly limited as long as it can obtain a product having the structure represented by Ar1 a -D a -Ar2 a , and methods that are manufactured using a coupling agent and contain residues of the coupling agent It may be.
  • Block copolymer B is a copolymer represented by the following general formula (B).
  • the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) are composed of aromatic vinyl monomer units obtained by polymerizing aromatic vinyl monomers as a main repeating unit. It is a polymer block.
  • the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) may be any aromatic vinyl compound. Although not particularly limited, examples thereof include those similar to the above-mentioned aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar2 a ).
  • the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit.
  • monomers constituting monomer units other than aromatic vinyl monomer units include the same as aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar2 a ). The content thereof may be the same.
  • the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) must also substantially consist only of one or more types of aromatic vinyl monomer units. is preferable, and it is particularly preferable that it consists only of styrene units.
  • the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) both have a weight average molecular weight within the range of 7,000 to 17,000.
  • the weight average molecular weights of the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) are both 7,000 to 17,000, preferably 9,000 to 15,000, and more preferably 10,000 to 14,000. It is.
  • the weight average molecular weights of the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) may be the same or different from each other as long as they are within the above ranges.
  • the ratio of "weight average molecular weight of aromatic vinyl polymer block (Ar1 b )/weight average molecular weight of aromatic vinyl polymer block (Ar2 b )" is preferably 0.7 to 1.3, More preferably 0.8 to 1.2, more preferably 0.9 to 1.1, even more preferably 0.95 to 1.05, most preferably substantially equal. .
  • the weight average molecular weights of the aromatic vinyl polymer block (Ar1 b ) and the aromatic vinyl polymer block (Ar2 b ) are the same as those of the aromatic vinyl polymer block (Ar2 b ) having a relatively small weight average molecular weight of block copolymer A.
  • weight average molecular weight of aromatic vinyl polymer block (Ar1 b )/weight average molecular weight of aromatic vinyl polymer block (Ar1 a )” or “weight average molecular weight of aromatic vinyl polymer block (Ar1 a )” is preferably 0.7 to 1.3, more preferably 0.8 to 1.2. It is more preferably 0.9 to 1.1, still more preferably 0.95 to 1.05, and most preferably substantially equal.
  • the conjugated diene polymer block (D b ) is a polymer block constituted as a main repeating unit of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer.
  • the conjugated diene monomer used to constitute the conjugated diene monomer unit of the conjugated diene polymer block (D b ) is not particularly limited as long as it is a conjugated diene compound, but for example, the conjugated diene polymer block described above Those similar to (D a ) can be mentioned.
  • the conjugated diene polymer block (D b ) may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit, and the conjugated diene polymer block (D b ) may contain other monomer units than the conjugated diene monomer unit.
  • the monomer constituting the monomer unit include those similar to the conjugated diene polymer block (D a ), and the content and vinyl bond content thereof may also be the same.
  • the conjugated diene polymer block (D b ) is also preferably composed essentially only of one or more types of conjugated diene monomer units, and is preferably composed only of isoprene units. Particularly preferred.
  • the vinyl bond content of the conjugated diene polymer block (D b ) is preferably substantially equal to the vinyl bond content of the conjugated diene polymer block (D a ) of block copolymer A.
  • the weight average molecular weight of the conjugated diene polymer block (D b ) is 50,000 to 200,000, preferably 70,000 to 150,000, and more preferably 80,000 to 120,000.
  • the weight average molecular weight of the conjugated diene polymer block (D b ) is the weight average molecular weight of the conjugated diene polymer block (D a ) of the block copolymer A.
  • the ratio of "molecular weight/weight average molecular weight of conjugated diene polymer block (D a )" is not particularly limited, but is preferably 0.5 to 2.0, more preferably 0.7 to 1.3, More preferably, they are substantially equal.
  • the weight average molecular weight of block copolymer B (that is, the weight average molecular weight of block copolymer B as a whole) is preferably 75,000 to 300,000, more preferably 80,000 to 180,000, and even more preferably 90,000 to 150,000. .
  • the molecular weight distribution (Mw/Mn) of block copolymer B (that is, the molecular weight distribution (Mw/Mn) of the entire block copolymer B) is 1.0 to 1.2, preferably 1.005 to 1.0. 1, more preferably 1.01 to 1.05.
  • the content of aromatic vinyl monomer units in block copolymer B is 21 to 30% by weight, preferably 22 to 29% by weight, based on the total monomer units constituting block copolymer B. , more preferably 23 to 28% by weight.
  • Block copolymer B is obtained by a manufacturing method in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are sequentially polymerized to form a polymer block. It is preferable. Therefore, block copolymer B preferably does not contain any coupling agent residues. Details of such a manufacturing method will be described later. However, this is not particularly limited as long as it is possible to obtain a product having the structure represented by Ar1 b -D b -Ar2 b , and methods that are manufactured using a coupling agent and contain residues of the coupling agent It may be.
  • Block copolymer C is a copolymer represented by the following general formula (C).
  • the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) are composed of aromatic vinyl monomer units obtained by polymerizing aromatic vinyl monomers as a main repeating unit. It is a polymer block.
  • the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) may be any aromatic vinyl compound. Although not particularly limited, examples thereof include those similar to the above-mentioned aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar2 a ).
  • the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit.
  • monomers constituting monomer units other than aromatic vinyl monomer units include the same as aromatic vinyl polymer block (Ar1 a ) and aromatic vinyl polymer block (Ar2 a ). The content thereof may be the same.
  • the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) must also substantially consist only of one or more types of aromatic vinyl monomer units. is preferable, and it is particularly preferable that it consists only of styrene units.
  • the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) both have a weight average molecular weight within the range of 7,000 to 17,000.
  • the weight average molecular weights of the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) are both 7,000 to 17,000, preferably 8,000 to 15,000, and more preferably 9,000 to 14,000. It is.
  • the weight average molecular weights of the aromatic vinyl polymer block (Ar1 c ) and the aromatic vinyl polymer block (Ar2 c ) may be the same or different from each other as long as they are within the above ranges.
  • the ratio of "weight average molecular weight of aromatic vinyl polymer block (Ar1 c )/weight average molecular weight of aromatic vinyl polymer block (Ar2 c )" is preferably 0.7 to 1.3, More preferably 0.8 to 1.2, more preferably 0.9 to 1.1, even more preferably 0.95 to 1.05, most preferably substantially equal. .
  • the conjugated diene polymer block (D c ) is a polymer block constituted as a main repeating unit of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer.
  • the conjugated diene monomer used to constitute the conjugated diene monomer unit of the conjugated diene polymer block (D c ) is not particularly limited as long as it is a conjugated diene compound, but for example, the conjugated diene polymer block described above Those similar to (D a ) can be mentioned.
  • the conjugated diene polymer block (D c ) may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit, and the conjugated diene polymer block (D c ) may contain other monomer units than the conjugated diene monomer unit.
  • the monomer constituting the monomer unit include those similar to the conjugated diene polymer block (D a ), and the content and vinyl bond content thereof may also be the same.
  • the conjugated diene polymer block (D c ) is also preferably composed essentially only of one or more types of conjugated diene monomer units, and is preferably composed only of isoprene units. Particularly preferred.
  • the vinyl bond content of the conjugated diene monomer units constituting the conjugated diene polymer block (D c ) is not particularly limited, but is preferably 1 to 20 mol%, and preferably 2 to 15 mol%. The amount is more preferably 3 to 10 mol%.
  • the weight average molecular weight of the conjugated diene polymer block (D c ) is 80,000 to 250,000, preferably 120,000 to 200,000, and more preferably 150,000 to 185,000.
  • the weight average molecular weight of the block copolymer C (that is, the weight average molecular weight of the entire block copolymer C) is preferably 100,000 to 300,000, more preferably 130,000 to 240,000, and still more preferably 160,000 to 200,000. .
  • the molecular weight distribution (Mw/Mn) of the block copolymer C (that is, the molecular weight distribution (Mw/Mn) of the entire block copolymer C) is 1.0 to 1.2, preferably 1.005 to 1.0. 1, more preferably 1.01 to 1.05.
  • the content of aromatic vinyl monomer units in block copolymer C is 12 to 22% by weight, preferably 13 to 21% by weight, based on the total monomer units constituting block copolymer C. , more preferably 15 to 20% by weight.
  • Block copolymer C is obtained by a manufacturing method in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are sequentially polymerized to form a polymer block. It is preferable. Therefore, block copolymer C preferably does not contain any coupling agent residues. Details of such a manufacturing method will be described later.
  • Block copolymer D is a copolymer represented by the following general formula (D).
  • Block copolymer D has a structure in which n diblock bodies (Ar d -D d ) are bonded to each other via a coupling agent residue (X).
  • n in the general formula (D) represents the number of branches in the block copolymer D.
  • the block copolymer D may be a mixture of two or more block copolymers in which different numbers of diblock bodies are bonded.
  • n is an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 4. Note that the value of n is the average value of the plurality of block copolymers D.
  • the coupling agent residue (X) is not particularly limited as long as it is a residue of an n-valent coupling agent, but is preferably a residue of a silicon atom-containing coupling agent, and is preferably a residue of a halogenated silane or an alkoxysilane. More preferably, it is a residue.
  • Examples of the coupling agent constituting the residue of the coupling agent include those described below.
  • the block copolymer D may be a mixture of a block copolymer D1 where n is 2, a block copolymer D2 where n is 3, and a block copolymer D3 where n is 4, among others.
  • the weight ratio (D1/D2/D3) of the block copolymers D1 to D3 is preferably 40 to 80/30 to 10/30 to 10.
  • the aromatic vinyl polymer block (Ar d ) is a polymer block constituted as a main repeating unit of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer.
  • the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block (Ar d ) is not particularly limited as long as it is an aromatic vinyl compound; Examples include those similar to the group vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ).
  • the aromatic vinyl polymer block (Ar d ) may contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit, and may contain other monomer units other than aromatic vinyl monomer units.
  • Examples of the monomer constituting the monomer unit include those similar to the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ), and the content thereof is also as follows: The same may be used.
  • each aromatic vinyl polymer block in block copolymer D may be composed of the same aromatic vinyl monomer unit or may be composed of different aromatic vinyl monomer units. .
  • the aromatic vinyl polymer block (Ar d ) is also preferably composed essentially only of one or more aromatic vinyl monomer units, and is composed only of styrene units. It is particularly preferable.
  • the weight average molecular weight of the aromatic vinyl polymer block (Ar d ) is 7,000 to 17,000, preferably 8,000 to 15,000, and more preferably 8,500 to 14,000.
  • the weight average molecular weights of the plurality of aromatic vinyl polymer blocks (Ar d ) of the block copolymer D may be the same or different as long as they are within the above range, Preferably, they are substantially equal.
  • the conjugated diene polymer block (D d ) is a polymer block constituted as a main repeating unit of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer.
  • the conjugated diene monomer used to constitute the conjugated diene monomer unit of the conjugated diene polymer block (D d ) is not particularly limited as long as it is a conjugated diene compound, but for example, the conjugated diene polymer block described above Those similar to (D a ) can be mentioned. Further, each conjugated diene polymer block in block copolymer D may be composed of the same conjugated diene monomer unit, or may be composed of different conjugated diene monomer units.
  • the conjugated diene polymer block (D d ) may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit, and the conjugated diene polymer block (D d ) may contain other monomer units than the conjugated diene monomer unit.
  • the monomer constituting the monomer unit include those similar to the conjugated diene polymer block (D a ), and the content and vinyl bond content thereof may also be the same.
  • the conjugated diene polymer block (D d ) is also preferably composed essentially only of one or more conjugated diene monomer units, and is preferably composed only of isoprene units. Particularly preferred.
  • the vinyl bond content of the conjugated diene monomer units constituting the conjugated diene polymer block (D d ) is not particularly limited, but is preferably 1 to 20 mol%, and preferably 2 to 15 mol%. The amount is more preferably 3 to 10 mol%.
  • the weight average molecular weight of the conjugated diene polymer block (D d ) is 60,000 to 190,000, preferably 70,000 to 160,000, and more preferably 80,000 to 140,000.
  • the weight average molecular weights of the plurality of conjugated diene polymer blocks (D d ) of the block copolymer D may be the same or different as long as they are within the above range, but substantially It is preferable that they are the same.
  • the weight average molecular weight of block copolymer D (that is, the weight average molecular weight of block copolymer D as a whole) is 100,000 to 400,000, preferably 140,000 to 350,000, and more preferably 180,000 to 320,000.
  • the molecular weight distribution (Mw/Mn) of block copolymer D is 1.0 to 1.2, preferably 1.005 to 1.1, and more preferably 1.01 to 1.05.
  • Mw/Mn molecular weight distribution of the polymers that can be determined to have the same value of n falls within the above range. It should be the one in .
  • each of the branched product and the 4-branched product may be within the above range (that is, each branched product has a molecular weight distribution (Mw/Mn) of 1.0 to 1.0. 1.2).
  • the content of aromatic vinyl monomer units in block copolymer D is 11 to 22% by weight, preferably 11.5 to 20% by weight, based on the total monomer units constituting block copolymer D. % by weight, more preferably 12-18% by weight.
  • Block copolymer D is produced by a production method in which an aromatic vinyl monomer and a conjugated diene monomer are polymerized to form a diblock chain, and the diblock chain is reacted with a coupling agent to perform coupling. It is preferable that it is obtained. Block copolymer D therefore contains residues of a coupling agent. Details of such a manufacturing method will be described later.
  • Block copolymer E The aromatic vinyl block copolymer composition used in the present invention may further contain block copolymer E.
  • Block copolymer E is a copolymer represented by the following general formula (E).
  • the aromatic vinyl polymer block ( Are ) is a polymer block constituted as a main repeating unit of an aromatic vinyl monomer unit obtained by polymerizing an aromatic vinyl monomer.
  • the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block ( Are ) is not particularly limited as long as it is an aromatic vinyl compound, but for example, the above-mentioned aromatic Examples include those similar to the group vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ).
  • the aromatic vinyl polymer block ( Are ) may contain other monomer units as long as the aromatic vinyl monomer unit is the main repeating unit, and may contain other monomer units other than the aromatic vinyl monomer unit.
  • Examples of the monomer constituting the monomer unit include those similar to the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar2 a ), and the content thereof is also as follows: The same may be used.
  • the aromatic vinyl polymer block (Ar e ) is also preferably one consisting essentially only of one or more types of aromatic vinyl monomer units, and is one consisting only of styrene units. It is particularly preferable.
  • the weight average molecular weight of the aromatic vinyl polymer block (Ar e ) is 7,000 to 17,000, preferably 8,000 to 15,000, and more preferably 8,500 to 14,000.
  • the weight average molecular weight of the aromatic vinyl polymer block (Ar e ) is the weight average molecular weight of the aromatic vinyl polymer block (Ar d ) of the block copolymer D.
  • the ratio of "weight average molecular weight of aromatic vinyl polymer block (Ar d ) to weight average molecular weight of aromatic vinyl polymer block (Ar d )" is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, and more It is preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and most preferably substantially equal.
  • the conjugated diene polymer block (D e ) is a polymer block constituted as a main repeating unit of a conjugated diene monomer unit obtained by polymerizing a conjugated diene monomer.
  • the conjugated diene monomer used to constitute the conjugated diene monomer unit of the conjugated diene polymer block (D e ) is not particularly limited as long as it is a conjugated diene compound, but for example, the conjugated diene polymer block described above Those similar to (D a ) can be mentioned.
  • the conjugated diene polymer block (D e ) may contain other monomer units as long as the conjugated diene monomer unit is the main repeating unit, and may contain other monomer units other than the conjugated diene monomer unit. Examples of the monomer constituting the monomer unit include those similar to the conjugated diene polymer block (D a ), and the content and vinyl bond content thereof may also be the same. Further, the conjugated diene polymer block (D e ) is also preferably composed essentially only of one or more types of conjugated diene monomer units, and is preferably composed only of isoprene units. Particularly preferred.
  • the vinyl bond content of the conjugated diene polymer block (D e ) is preferably substantially equal to the vinyl bond content of the conjugated diene polymer block (D d ) of block copolymer E.
  • the weight average molecular weight of the conjugated diene polymer block (D e ) is 60,000 to 190,000, preferably 70,000 to 160,000, and more preferably 80,000 to 140,000.
  • the weight average molecular weight of the conjugated diene polymer block (D e ) is the weight average molecular weight of the conjugated diene polymer block (D e ) of the block copolymer D.
  • the ratio of "molecular weight/weight average molecular weight of conjugated diene polymer block (D d )" is not particularly limited, but is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, More preferably, it is 0.9 to 1.1, still more preferably 0.95 to 1.05, and most preferably substantially equal.
  • the weight average molecular weight of the block copolymer E (that is, the weight average molecular weight of the entire block copolymer E) is 50,000 to 200,000, preferably 70,000 to 170,000, and more preferably 80,000 to 150,000.
  • the molecular weight distribution (Mw/Mn) of the block copolymer E (that is, the molecular weight distribution (Mw/Mn) of the entire block copolymer E) is 1.0 to 1.2, preferably 1.005 to 1.0. 1, more preferably 1.01 to 1.05.
  • the content of aromatic vinyl monomer units in block copolymer E is 11 to 22% by weight, preferably 11.5 to 20% by weight, based on the total monomer units constituting block copolymer E. % by weight, more preferably 12-18% by weight.
  • the aromatic vinyl block copolymer composition used in the present invention contains at least one selected from the above-mentioned block copolymer A, block copolymer B, block copolymer C, and block copolymer D. , and optionally further contains block copolymer E.
  • the weight ratio (A/B/C+D) of each block copolymer A to D in the aromatic vinyl block copolymer composition used in the present invention is preferably 5 to 50/10 to 55/75 to 25.
  • the ratio is more preferably 10 to 30/25 to 50/60 to 30, and even more preferably 15 to 25/33 to 49/45 to 26.
  • At least one type selected from the above-mentioned block copolymer A, block copolymer B, block copolymer C, and block copolymer D in the aromatic vinyl block copolymer composition used in the present invention is at least one type selected from the above-mentioned block copolymer A, block copolymer B, block copolymer C, and block copolymer D in the aromatic vinyl block copolymer composition used in the present invention.
  • the content of block copolymer E includes aromatic vinyl containing block copolymers A to D. It is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, and even more preferably 3 to 9% by weight in the block copolymer composition.
  • Block copolymers A to E constituting the aromatic vinyl block copolymer composition used in the present invention can be produced according to conventional methods, and the most common method is anion living. Using a polymerization method, an aromatic vinyl monomer and a conjugated diene monomer are each sequentially polymerized to form a polymer block, and if necessary, a coupling agent is reacted to perform coupling. can be mentioned. Alternatively, a method may be used in which an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer are sequentially polymerized in this order to form a polymer block.
  • each polymer separately according to conventional polymerization methods, blending other polymer components as necessary, and then mixing them according to conventional methods such as kneading or solution mixing. , can be manufactured. Furthermore, as will be described later, it is also possible to simultaneously manufacture block copolymer A and block copolymer B, or to manufacture block copolymer D and block copolymer E simultaneously.
  • Block copolymer A and block copolymer B are produced by sequentially polymerizing an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer to form a polymer block. Preferably, it is manufactured.
  • block copolymer A and block copolymer B are preferably produced by the following production method. That is, A first polymerization step of obtaining a solution containing an aromatic vinyl polymer block chain by polymerizing a monomer containing an aromatic vinyl monomer in a solvent in the presence of a polymerization initiator; A second polymerization step in which a monomer containing a conjugated diene monomer is added to a solution containing an aromatic vinyl polymer block chain and polymerized to obtain a solution containing a diblock chain; A third polymerization step in which a monomer containing an aromatic vinyl monomer is added to a solution containing a diblock chain and polymerized to obtain a solution containing a triblock chain; A polymerization terminator is added to the solution containing the triblock chain in an amount that is less than 1 molar equivalent with respect to the active terminal possessed by the triblock chain to deactivate a part of the active terminal, thereby producing block copolymer B.
  • a solution containing block copolymer A and block copolymer B is obtained by adding a monomer containing an aromatic vinyl monomer to a solution containing a triblock chain and block copolymer B and polymerizing it.
  • a fourth polymerization step to obtain A manufacturing method comprising:
  • the method for producing block copolymer A and block copolymer B is not limited to these methods, and any method that can obtain block copolymer A and block copolymer B may be used.
  • an aromatic vinyl monomer and a conjugated diene monomer may be polymerized to obtain a diblock product, and the resulting diblock product is subjected to a coupling reaction using a coupling agent. It may also be manufactured by In this case, block copolymer A and block copolymer B usually contain a residue of a coupling agent.
  • a monomer containing an aromatic vinyl monomer as a main component is polymerized using a polymerization initiator in a solvent (first polymerization step).
  • a polymerization initiator such as water is used as the aromatic vinyl monomer. It is preferable to use one in which the amount of deactivating component that deactivates is suppressed to 1 ⁇ 10 ⁇ 3 mol/kg or less.
  • each block copolymer the aromatic vinyl monomer used in the production of each block copolymer will be described below from the viewpoint of suitably controlling the molecular weight distribution (Mw/Mn) of each block copolymer obtained within the above-mentioned range. It is preferable to use one in which the amount of deactivated component is controlled within the above range.
  • organic alkali metal compounds organic alkaline earth metal compounds, which are generally known to have anionic polymerization activity toward aromatic vinyl monomers and conjugated diene monomers, Organic lanthanide series rare earth metal compounds and the like can be used.
  • an organic lithium compound having one or more lithium atoms in the molecule is particularly preferably used, and specific examples thereof include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, Organic monolithium compounds such as sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbene lithium, dialkylaminolithium, diphenylaminolithium, ditrimethylsilylaminolithium, methylene dilithium, tetramethylene dilithium, hexamethylene Examples include organic dilithium compounds such as dilithium, isoprenyldilithium, and 1,4-dilithio-ethylcyclohexane, and organic trilithium compounds such as 1,3,5-trilithiobenzene. Among these, organic monolithium compounds are particularly preferably used.
  • organic alkaline earth metal compound used as a polymerization initiator examples include n-butylmagnesium bromide, n-hexylmagnesium bromide, ethoxycalcium, calcium stearate, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethylmercaptobarium, Examples include t-butoxybarium, phenoxybarium, diethylaminobarium, barium stearate, and ethylbarium.
  • polymerization initiators include composite catalysts consisting of lanthanoid rare earth metal compounds containing neodymium, samarinium, gadolinium, etc./alkyl aluminum/alkyl aluminum halide/alkyl aluminum hydride, titanium, vanadium, samarinium, gadolinium, etc. Examples include those that form a homogeneous system in an organic solvent and have living polymerizability, such as metallocene-type catalysts containing the following. In addition, these polymerization initiators may be used individually, and may be used as a mixture of 2 or more types.
  • the amount of the polymerization initiator to be used may be determined depending on the desired molecular weight, and is not particularly limited, but is preferably 0.01 to 20 mmol, more preferably 0.05 to 20 mmol, per 100 g of total monomers used. The amount is 15 mmol, more preferably 0.1 to 10 mmol.
  • the solvent used for polymerization is not particularly limited as long as it is inert to the polymerization initiator, and for example, a chain hydrocarbon solvent, a cyclic hydrocarbon solvent, or a mixed solvent thereof is used.
  • Chain hydrocarbon solvents include n-butane, isobutane, 1-butene, isobutylene, trans-2-butene, cis-2-butene, 1-pentene, trans-2-pentene, cis-2-pentene, n-pentane.
  • Examples include linear alkanes and alkenes having 4 to 6 carbon atoms, such as , isopentane, neo-pentane, and n-hexane.
  • cyclic hydrocarbon solvent examples include aromatic compounds such as benzene, toluene, and xylene; and alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane. These solvents may be used alone or in combination of two or more.
  • the amount of solvent used in the polymerization is not particularly limited, but the concentration of the block copolymer in the finally obtained block copolymer solution is preferably in the range of 5 to 60% by weight, more preferably 15 to 55% by weight. %, particularly preferably in the range of 25 to 50% by weight.
  • a Lewis base compound may be added to the reactor used for polymerization.
  • Lewis base compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; amines; alkali metal alkoxides such as potassium t-amyl oxide and potassium t-butyl oxide; phosphines such as triphenylphosphine; and the like.
  • These Lewis base compounds may be used alone or in combination of two or more, and are appropriately selected within a range that does not impair the object of the present invention.
  • the timing of adding the Lewis base compound during the polymerization reaction is not particularly limited, and may be appropriately determined depending on the structure of each target block copolymer. For example, it may be added in advance before starting polymerization, it may be added after some polymer blocks have been polymerized, or it may be added in advance before starting polymerization and then some of the polymer blocks may be added before starting polymerization. Further additions may be made after the polymer block has been polymerized.
  • the amount of the Lewis base compound to be used is determined from the viewpoint of controlling the molecular weight distribution (Mw/Mn) of the resulting block copolymer and the cis/tonlass ratio of the conjugated diene block within the above-mentioned ranges.
  • the polymerization reaction temperature is preferably 30 to 90°C, more preferably 35 to 85°C, and still more preferably 40 to 80°C.
  • the time required for polymerization varies depending on the conditions, but is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and still more preferably 2 to 5 hours.
  • the polymerization pressure may be within a pressure range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range, but the polymerization pressure is preferably 1 kPa or more, and preferably 10 kPa or more. More preferably, the pressure is 50 kPa or more.
  • the stirring Reynolds number of the liquid phase constituting the polymerization reaction system is 100. It is preferable to carry out the above conditions, more preferably to carry out the stirring Reynolds number of 500 to 1,000,000, and even more preferably to carry out the stirring Reynolds number of 1,000 to 100,000. Alternatively, it is preferable that the liquid phase constituting the polymerization reaction system is stirred using a stirring blade, and the stirring is performed under conditions of a required stirring power of 0.5 kW/m 3 or more.
  • the required power is 1 to 20 kW/m 3
  • the molecular weight distribution (Mw/Mn) of the resulting block copolymer is suitably within the above range. can be controlled.
  • the stirring Reynolds number or It is preferable to carry out the polymerization by controlling the power required for stirring by the stirring blade within the above range.
  • a solution containing an aromatic vinyl polymer block chain is obtained by polymerizing a monomer containing an aromatic vinyl monomer as a main component using a polymerization initiator in a solvent under the above conditions. be able to.
  • the aromatic vinyl polymer block chain obtained by polymerization usually has an active terminal.
  • this first polymerization step The amount of the monomer used may be determined depending on the weight average molecular weights of the aromatic vinyl polymer block (Ar1 a ) and the aromatic vinyl polymer block (Ar1 b ).
  • a monomer containing a conjugated diene monomer as a main component is added to the solution containing the aromatic vinyl polymer block chain obtained in the first polymerization step, and polymerization is performed (second polymerization step).
  • second polymerization step a solution containing diblock chains can be obtained.
  • the diblock chain obtained by polymerization usually has an active end.
  • the diblock chain obtained in the second polymerization step will form the aromatic vinyl polymer block (Ar1 a ) or the aromatic vinyl polymer block (Ar1 b ) obtained in the first polymerization step.
  • the polymer chain used in this second polymerization step is The amount of the monomer may be determined depending on the weight average molecular weight of the conjugated diene polymer block (D a ) and the conjugated diene polymer block (D b ). Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • a polymerization initiator such as water is used as the conjugated diene monomer. It is preferable to use one in which the amount of deactivated component to be deactivated is suppressed to 1 ⁇ 10 ⁇ 3 mol/kg or less.
  • the conjugated diene monomer used in the production of each block copolymer from the viewpoint of suitably controlling the molecular weight distribution (Mw/Mn) of each block copolymer obtained within the above-mentioned range, It is preferable to use one in which the amount of deactivated component is controlled within the above range.
  • the triblock chain obtained by polymerization usually has an active end.
  • the triblock chain obtained in the third polymerization step is the aromatic vinyl polymer block (Ar1 a ) or the aromatic vinyl polymer block (Ar1 b ) and the conjugated diene polymer block obtained in the second polymerization step.
  • a part of the aromatic vinyl polymer block (Ar2 a ) or an aromatic vinyl polymer block (Ar2 b ) is added to the polymer chain that will form the ( D a ) or conjugated diene polymer block (D b ) . ), the amount of monomer used in this third polymerization step depends on the weight average molecular weight of the aromatic vinyl polymer block (Ar2 b ). You just have to decide. Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • a polymerization terminator is added to the solution containing the triblock chain obtained in the third polymerization step in an amount that is less than 1 molar equivalent relative to the active end of the triblock chain (termination step).
  • a part of the active end of the triblock chain is deactivated, and a block copolymer with the active end deactivated is obtained.
  • This block copolymer becomes block copolymer B represented by the general formula (B): Ar1 b -D b -Ar2 b .
  • the polymerization terminator is not particularly limited as long as it can react with the active end to deactivate the active end and does not react with another active end after reacting with one active end, but the resulting composition From the viewpoint of suppressing moisture absorption, it is preferable to use a polymerization terminator that is a compound that does not contain a halogen atom, and in particular, a polymerization terminator that produces a metal alkoxide, metal aryl oxide, or metal hydroxide when reacting with the active end.
  • Particularly preferred are polymerization terminators that allow Compounds particularly preferably used as polymerization terminators include water, monohydric alcohols such as methanol and ethanol, and monohydric phenols such as phenol and cresol.
  • the amount of polymerization terminator used is determined according to the weight ratio of block copolymer A and block copolymer B contained in the aromatic vinyl block copolymer composition, and is There is no particular limitation as long as the amount is less than 1 molar equivalent for the active terminal, but the range is usually 0.18 to 0.91 molar equivalent of the polymerization terminator to the active terminal, and 0.35 to 0.80 molar equivalent. It is preferable that the amount is in a molar equivalent range.
  • the polymerization terminator when a polymerization terminator is added to a solution containing triblock chains having active ends in an amount that is less than 1 molar equivalent with respect to the active ends, the polymerization terminator is added to the solution containing triblock chains having active ends. A part of the active terminals is deactivated, and the polymer in which the active terminals are deactivated becomes block copolymer B. The remaining part of the triblock chain having an active end that did not react with the polymerization terminator remains unreacted in the solution.
  • a monomer containing an aromatic vinyl monomer as a main component is added to the solution containing the triblock chain and block copolymer B obtained in the termination step, and polymerization is performed (fourth polymerization step).
  • a solution containing block copolymer A and block copolymer B represented by the general formula (A): Ar1 a -D a -Ar2 a can be obtained.
  • the block copolymer A obtained in the fourth polymerization step forms a part of the aromatic vinyl polymer block (Ar2 a ) at the active end of the triblock chain obtained in the third polymerization step.
  • the amount of monomer used in this fourth polymerization step may be determined depending on the weight average molecular weight of the aromatic vinyl polymer block (Ar2 a ). Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • the polymer component may be recovered from the solution containing block copolymer A and block copolymer B (recovery step).
  • the method of recovery may be any conventional method and is not particularly limited.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid, and if necessary, add additives such as an antioxidant.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid
  • additives such as an antioxidant.
  • the polymer component When the polymer component is recovered as a slurry by applying steam stripping or the like, it is dehydrated using any dehydrator such as an extruder type squeezer to form a crumb having a moisture content below a predetermined value, and then The crumb may be dried using any dryer such as a band dryer, an expansion extrusion dryer, or a twin-screw extruder dryer.
  • the block copolymer obtained as described above may be used after being processed into a pellet shape or the like according to a conventional method.
  • Block copolymer A and block copolymer B can be produced in the manner described above.
  • the block copolymer C is preferably produced by a method of sequentially polymerizing an aromatic vinyl monomer, a conjugated diene monomer, and then an aromatic vinyl monomer to form a polymer block.
  • block copolymer C is preferably produced by the following production method. That is, A first polymerization step of obtaining a solution containing an aromatic vinyl polymer block chain by polymerizing a monomer containing an aromatic vinyl monomer in a solvent in the presence of a polymerization initiator; A second polymerization step in which a monomer containing a conjugated diene monomer is added to a solution containing an aromatic vinyl polymer block chain and polymerized to obtain a solution containing a diblock chain; A third polymerization step of obtaining a solution containing block copolymer C by adding a monomer containing an aromatic vinyl monomer to a solution containing diblock chains and polymerizing it; A manufacturing method comprising:
  • a monomer containing an aromatic vinyl monomer as a main component is polymerized using a polymerization initiator in a solvent (first polymerization step).
  • the solvent and the amount used in the first polymerization step, the polymerization initiator and the amount used in the first polymerization step are the same as those in the first polymerization step in the preferred method for producing block copolymer A and block copolymer B described above. good.
  • a Lewis base compound may be added, and the amount used may be the same.
  • the same polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system as in the first polymerization step in the preferred method for producing block copolymer A and block copolymer B described above can be employed.
  • a solution containing an aromatic vinyl polymer block chain is obtained by polymerizing a monomer containing an aromatic vinyl monomer as a main component using a polymerization initiator in a solvent under the above conditions. be able to.
  • the aromatic vinyl polymer block chain obtained by polymerization usually has an active terminal.
  • the amount of monomer used in this first polymerization step is It may be determined according to the weight average molecular weight of the vinyl polymer block ( Arc ).
  • a monomer containing a conjugated diene monomer as a main component is added to the solution containing the aromatic vinyl polymer block chain obtained in the first polymerization step, and polymerization is performed (second polymerization step).
  • second polymerization step a solution containing diblock chains can be obtained.
  • the diblock chain obtained by polymerization usually has an active end.
  • the diblock chain obtained in the second polymerization step is added to the polymer chain that will form the aromatic vinyl polymer block (Ar1 c ) obtained in the first polymerization step, and the conjugated diene polymer block ( Since the polymer chains that will form D c ) are further bonded, the amount of monomer used in this second polymerization step depends on the weight average molecular weight of the conjugated diene polymer block (D c ). You can decide accordingly. Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • a monomer containing an aromatic vinyl monomer as a main component is added to the solution containing the diblock chain obtained in the second polymerization step, and polymerization is performed (third polymerization step).
  • a solution containing the block copolymer C represented by the general formula (C): Ar1 c -D c -Ar2 c can be obtained.
  • the block copolymer C obtained in the third polymerization step is a polymer that will form the aromatic vinyl polymer block (Ar1 c ) and the conjugated diene polymer block (D c ) obtained in the second polymerization step.
  • the amount of monomer used in this third polymerization step is It may be determined according to the weight average molecular weight of the polymer block (Ar2 c ). Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • the polymer component may be recovered from the solution containing block copolymer C (recovery step).
  • the method of recovery may be any conventional method and is not particularly limited.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid, and if necessary, add additives such as an antioxidant.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid
  • additives such as an antioxidant.
  • the polymer component When the polymer component is recovered as a slurry by applying steam stripping or the like, it is dehydrated using any dehydrator such as an extruder type squeezer to form a crumb having a moisture content below a predetermined value, and then The crumb may be dried using any dryer such as a band dryer, an expansion extrusion dryer, or a twin-screw extruder dryer.
  • the block copolymer obtained as described above may be used after being processed into a pellet shape or the like according to a conventional method.
  • Block copolymer C can be produced in the manner described above.
  • Block copolymer D is produced by a method in which an aromatic vinyl monomer and a conjugated diene monomer are polymerized to form a diblock chain, and the diblock chain is reacted with a coupling agent to perform coupling. It is preferable to do so.
  • block copolymer D is preferably produced by the following production method. That is, A first polymerization step of obtaining a solution containing an aromatic vinyl polymer block chain by polymerizing a monomer containing an aromatic vinyl monomer in a solvent in the presence of a polymerization initiator; A second polymerization step in which a monomer containing a conjugated diene monomer is added to a solution containing an aromatic vinyl polymer block chain and polymerized to obtain a solution containing a diblock chain; A reaction step of adding a coupling agent to a solution containing diblock chains to obtain block copolymer D; A manufacturing method comprising:
  • a monomer containing an aromatic vinyl monomer as a main component is polymerized using a polymerization initiator in a solvent (first polymerization step).
  • the solvent and the amount used in the first polymerization step, the polymerization initiator and the amount used in the first polymerization step are the same as those in the first polymerization step in the preferred method for producing block copolymer A and block copolymer B described above. good.
  • a Lewis base compound may be added, and the amount used may be the same.
  • the same polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system as in the first polymerization step in the preferred method for producing block copolymer A and block copolymer B described above can be employed.
  • a solution containing an aromatic vinyl polymer block chain is obtained by polymerizing a monomer containing an aromatic vinyl monomer as a main component using a polymerization initiator in a solvent under the above conditions. be able to.
  • the aromatic vinyl polymer block chain obtained by polymerization usually has an active terminal.
  • the amount of monomer used in this first polymerization step is It may be determined according to the weight average molecular weight of the vinyl polymer block (Ar d ).
  • a monomer containing a conjugated diene monomer as a main component is added to the solution containing the aromatic vinyl polymer block chain obtained in the first polymerization step, and polymerization is performed (second polymerization step).
  • second polymerization step a solution containing diblock chains can be obtained.
  • the diblock chain obtained by polymerization usually has an active end.
  • the diblock chain obtained in the second polymerization step is added to the polymer chain that will form the aromatic vinyl polymer block (Ar d ) obtained in the first polymerization step, and the conjugated diene polymer block ( Since the polymer chains that will form D d ) are further bonded, the amount of monomer used in this second polymerization step depends on the weight average molecular weight of the conjugated diene polymer block (D d ). You can decide accordingly. Further, the polymerization reaction temperature, polymerization time, polymerization pressure, and stirring conditions of the polymerization reaction system may be controlled within the same range as in the first polymerization step.
  • a coupling agent is added to the solution containing diblock chains (reaction step).
  • the active ends of the diblock chains react with the coupling agent, and two or more diblock chains are bonded together via the residues of the coupling agent, forming block copolymer D.
  • the coupling agent is not particularly limited as long as it has two or more functional groups in one molecule that can react with the active end of the diblock chain.
  • a coupling agent having 2 to 8 functional groups per molecule is preferred, and a coupling agent having 2 to 4 functional groups per molecule that can react with the active end of the diblock chain is more preferred.
  • the coupling agent preferably contains a silicon atom, and halogenated silanes and alkoxysilanes are more preferable.
  • Examples of coupling agents (bifunctional coupling agents) having two functional groups in one molecule that can react with the active end of the diblock chain include dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane.
  • Functional halogenated silanes include difunctional alkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; difunctional halogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, and dibromomethane; dichlorotin, monomethyldichlorotin, dimethyldichlorotin Difunctional tin halides such as , monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, and dibutyldichlorotin; dibromobenzene, benzoic acid, CO, 2-chloropropene, and the
  • Examples of the coupling agent (trifunctional coupling agent) having three functional groups in one molecule that can react with the active end of the diblock chain include trifunctional halogenated alkanes such as trichloroethane and trichloropropane; Trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; trifunctional alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; and the like. These trifunctional coupling agents may be used alone or in combination of two or more.
  • Examples of coupling agents having four functional groups in one molecule include carbon tetrachloride, carbon tetrabromide, and tetrachloroethane.
  • Tetrafunctional halogenated alkanes Tetrafunctional halogenated silanes such as tetrachlorosilane and tetrabromosilane; Tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; Tetrafunctional halogens such as tetrachlorotin and tetrabromostin Examples include tin oxide; etc.
  • These tetrafunctional coupling agents may be used alone or in combination of two or more.
  • the number of n in block copolymer D can be adjusted by adjusting the type of coupling agent, amount used, timing of addition, amount of Lewis base compound used, etc. I can do it.
  • the number of branches of the block copolymer D can also be adjusted by adjusting the coupling rate using a reaction terminator such as methanol.
  • the number of branches of the block copolymer D can also be adjusted by using a combination of two or more coupling agents having different numbers of functional groups capable of reacting with the active end of the diblock chain. Furthermore, by these means, the diblock chain obtained in the second polymerization step may be left unreacted and finally recovered as block copolymer E.
  • the amount of the coupling agent used is adjusted to an appropriate amount depending on the number of branches of the target block copolymer D.
  • the amount of the coupling agent used is preferably 0.05 to 1.0 molar equivalent, more preferably 0.50 to 1.0 molar equivalent, and further Preferably it is 0.85 to 1.0 molar equivalent.
  • the reaction temperature is preferably 10 to 100°C, more preferably 20 to 90°C, and even more preferably 30 to 80°C.
  • the time required for the reaction varies depending on the conditions, but is usually within 48 hours, preferably 0.05 to 2 hours, and more preferably 0.1 to 1.0 hours.
  • the polymer component may be recovered from the solution containing block copolymer D and optionally block copolymer E (recovery step).
  • the method of recovery may be any conventional method and is not particularly limited.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid, and if necessary, add additives such as an antioxidant.
  • a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid
  • additives such as an antioxidant.
  • the polymer component When the polymer component is recovered as a slurry by applying steam stripping or the like, it is dehydrated using any dehydrator such as an extruder type squeezer to form a crumb having a moisture content below a predetermined value, and then The crumb may be dried using a dryer such as a band dryer, an expansion extrusion dryer, or a twin-screw extruder dryer.
  • the block copolymer obtained as described above may be used after being processed into a pellet shape or the like according to a conventional method. In the manner described above, block copolymer D and optionally block copolymer E can be produced.
  • the aromatic vinyl block copolymer composition used in the present invention further contains fatty acid amide, polyethylene wax, antioxidant, tackifier resin, softener, antibacterial agent, light stabilizer, and ultraviolet absorber, if necessary. , dyes, lubricants, etc.
  • the fatty acid amide may be an aliphatic monoamide or an aliphatic bisamide.
  • Aliphatic monoamides are not particularly limited as long as they are compounds formed by bonding a hydrocarbon group and one amide group (-NHCO), but monoamides of higher saturated fatty acids having 12 or more carbon atoms (i.e., monoamides of higher saturated fatty acids having 12 or more carbon atoms)
  • a compound formed by bonding a chain alkyl group with one amide group (--NHCO) is preferably used.
  • fatty acid monoamides include saturated fatty acid monoamides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide; unsaturated fatty acids such as oleic acid amide and erucic acid amide. Examples include monoamide; and the like.
  • the content of fatty acid amide is determined by at least one selected from block copolymer A, block copolymer B, block copolymer C, and block copolymer D, and optionally containing block copolymer E.
  • the amount is preferably 0.2 to 10 parts by weight, more preferably 0.3 to 8 parts by weight, and still more preferably 0.5 to 6 parts by weight.
  • Polyethylene wax is a wax whose main constituent unit is an ethylene monomer unit.
  • the polyethylene wax used in the present invention is not particularly limited, but one having a viscosity of 20 to 6,000 mPa ⁇ s at 140° C. is preferably used.
  • Polyethylene wax is generally produced by polymerizing ethylene or decomposing polyethylene, but either polyethylene wax may be used in the present invention.
  • commercially available polyethylene waxes are available, and specific examples include “A-C polyethylene” (manufactured by Honeywell), “Mitsui Hiwax” (manufactured by Mitsui Chemicals), and “Sunwax” (manufactured by Sanyo Chemical Co., Ltd.). (manufactured by Kogyo Co., Ltd.) and "Epolene” (manufactured by Eastman Chemical Co.).
  • the antioxidant is not particularly limited, and examples thereof include pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-p-cresol, di-t-butyl-4-methylphenol, 4-[[4,6-bis(octylthio)-1,3 ,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,4-bis[(dodecylthio)methyl]-6-methylphenol, 4,6-bis(octylmethyl)-o - Hindered phenolic compounds such as cresol; Thiodicarboxylate esters such as dilaurylthiopropionate; Tris(nonylphenyl)phosphite,
  • the content of the antioxidant is at least one selected from block copolymer A, block copolymer B, block copolymer C, and block copolymer D, and optionally containing block copolymer E.
  • the amount is preferably 10 parts by weight or less, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight in total.
  • the aromatic vinyl block copolymer composition used in the present invention may further contain a wax containing a linear hydrocarbon and a branched hydrocarbon.
  • the wax used in the present invention may be a natural wax or a synthetic wax, but is preferably a natural wax, and more preferably a petroleum wax.
  • a blended wax consisting mainly of petroleum wax mixed with a portion of other natural waxes or synthetic waxes may also be used. Further, in order to improve the functions and processability of these waxes, waxes may be used in which a small amount of resin or the like is further blended with the waxes.
  • the linear hydrocarbon is preferably a linear aliphatic saturated hydrocarbon.
  • Straight chain hydrocarbons are sometimes called normal paraffins.
  • the branched hydrocarbon is preferably a branched aliphatic saturated hydrocarbon. Branched hydrocarbons are sometimes called isoparaffins.
  • straight chain hydrocarbons and branched chain hydrocarbons straight chain hydrocarbons and branched chain hydrocarbons contained in petroleum wax are preferred.
  • the wax used in the present invention may contain cyclic hydrocarbons in addition to straight-chain hydrocarbons and branched-chain hydrocarbons, but the sum of the straight-chain hydrocarbons and branched-chain hydrocarbons in the wax
  • the amount is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and most preferably 90% by weight or more.
  • the weight ratio (n-form/iso-form) of linear hydrocarbons (n-form) and branched chain hydrocarbons (iso-form) in the wax is 30/70 to 99/1,
  • the ratio is preferably 50/50 to 97/3, more preferably 70/30 to 95/5, and most preferably 75/25 to 90/10.
  • the melting point of the wax is less than 80°C, preferably 76°C or less, more preferably 73°C or less, preferably 30°C or more, more preferably 40°C or more, and even more preferably 45°C. That's all.
  • the melting point of wax can be measured using a differential scanning calorimeter or the like. If the melting point of the wax is too high, it will be difficult to obtain an elastic body with excellent ozone crack resistance. If the melting point of the wax is too low, it tends to block during transportation and storage, and it also tends to melt during processing, resulting in poor handling.
  • the wax content in the aromatic vinyl block copolymer composition used in the present invention is selected from block copolymer A, block copolymer B, block copolymer C, and block copolymer D.
  • the amount is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3.5 parts by weight, based on a total of 100 parts by weight of at least one of the above and optionally contained block copolymer E. , more preferably 0.5 to 2 parts by weight.
  • the aromatic vinyl block copolymer composition used in the present invention at least one selected from block copolymer A, block copolymer B, block copolymer C, and block copolymer D is used.
  • the method of mixing the optionally contained block copolymer E and other components is not particularly limited. Examples include a method in which each component is dissolved in a solvent and mixed uniformly, and then the solvent is removed by heating or the like, and a method in which each component is melt-mixed using a screw extruder, a kneader, or the like. Among these, melt mixing is preferable from the viewpoint of performing mixing more efficiently. Note that the temperature during melt mixing is not particularly limited, but is usually in the range of 100 to 250°C.
  • Block copolymer A, block copolymer B, at least one selected from block copolymer C and block copolymer D, optionally contained block copolymer E, and other components are melt-mixed.
  • at least one selected from block copolymer A, block copolymer B, block copolymer C, and block copolymer D is optionally contained.
  • All or part of one or more components of block copolymer E and other components are kneaded in advance in a single screw extruder, twin screw extruder, Banbury mixer, kneader, etc. to prepare masterbatch pellets. You can leave it there.
  • the thermoplastic elastomer of the present invention is not particularly limited to such an aromatic vinyl block copolymer composition, A thermoplastic elastomer that satisfies all of the characteristics of ) to (4) may be used. By satisfying all of the above-mentioned characteristics (1) to (4), it is possible to provide a film-like elastic body with high stress, high expansion/contraction rate, and wide width.
  • thermoplastic elastomer of the present invention may be one that satisfies all of the properties (1) to (4) above, and its chemical composition, shape, size, etc. are not particularly limited. , pellet shape, or film shape.
  • the film shape may have a plurality of holes to provide breathability.
  • thermoplastic elastomer of the present invention may contain a polyolefin elastomer in addition to the aromatic vinyl block copolymer, and the proportion of the aromatic vinyl block copolymer exceeds 50% by weight. It is preferable that the polyolefin elastomer is contained in a proportion of more than 1% by weight and less than 50% by weight. By containing the polyolefin elastomer in such an amount, stress relaxation properties can be improved.
  • stretchable films used in sanitary products such as disposable diapers and sanitary products are desired to have high moisture permeability in order to prevent stuffiness.
  • An example of this method is to use a film with holes.
  • the stress relaxation properties can be improved, thereby effectively suppressing such defects even when the aperture ratio of the film is increased. can do.
  • the content of the polyolefin elastomer in the thermoplastic elastomer of the present invention is preferably more than 1% by weight and less than 50% by weight, more preferably 3% by weight or more and less than 25% by weight, even more preferably 5 to 17% by weight. , even more preferably 7 to 13% by weight.
  • the content of the aromatic vinyl block copolymer in the thermoplastic elastomer of the present invention is preferably more than 50% by weight, more preferably more than 75% by weight and less than 97% by weight, even more preferably 83 to 97% by weight. 95% by weight, even more preferably 87-93% by weight.
  • the aromatic vinyl block copolymer composition described above can be suitably used as the aromatic vinyl block copolymer.
  • the polyolefin elastomer is not particularly limited as long as it is a thermoplastic resin having an olefin as the main repeating unit, and includes homopolymers of ⁇ -olefins, copolymers of two or more types of ⁇ -olefins, and ⁇ -olefins. It may be a copolymer of and a monomer other than ⁇ -olefin, or it may be a modified version of these (co)polymers.
  • polyolefin elastomers include homopolymers or copolymers of ⁇ -olefins such as ethylene and propylene, such as linear low density polyethylene (LLDPE), low density polyethylene (LDPE), and medium density polyethylene (MDPE).
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • polyethylene such as high density polyethylene (HDPE), metallocene polyethylene, ⁇ -olefin homopolymers such as polypropylene, metallocene polypropylene, polymethylpentene, polybutene; copolymers of ethylene with other ⁇ -olefins, such as ethylene - Propylene random copolymer, ethylene-propylene block copolymer, ethylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-octene copolymer, and ethylene-cyclic olefin copolymer ; Copolymers of ⁇ -olefins and carboxylic acid unsaturated alcohols, mainly composed of ⁇ -olefins, and saponified products thereof, such as ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers; Copolymers of ⁇ -olefins and ⁇ , ⁇ -unsaturation
  • Modified olefin resins ionomer resins made of copolymers of ethylene and methacrylic acid with Na ions, Zn ions, etc.; mixtures thereof;
  • polyolefin elastomers those containing ethylene units are preferred, polyethylene or copolymers of ethylene and other ⁇ -olefins are more preferred, copolymers of ethylene and propylene are even more preferred, and ethylene and propylene copolymers are more preferred.
  • a block copolymer of and propylene is particularly preferred.
  • the weight average molecular weight of the polyolefin elastomer is not particularly limited, but is usually selected within the range of 10,000 to 5,000,000, preferably within the range of 50,000 to 800,000. Further, the specific gravity and melt index of the polyolefin elastomer are not particularly limited, but the specific gravity is usually selected within the range of 0.80 to 0.95 g/cm 3 , preferably 0.85 to 0.94 g/cm 3 . cm 3 and the melt index is typically selected in the range 0.1 to 1000 g/10 min as a value measured according to ASTM D-1238 (G conditions, 200 ° C., 5 kg), It is preferably selected in the range of 1 to 500 g/10 minutes, more preferably 2 to 15 g/10 minutes.
  • thermoplastic elastomer of the present invention can be used, for example, in films, threads (elastic strands), gloves, elastic bands, condoms, OA equipment, various rolls for office use, anti-vibration sheets for electrical and electronic equipment, anti-vibration rubber, shock absorbers, etc. Sheets, shock-absorbing films/sheets, vibration damping sheets for housing, molding materials used in vibration damper materials, adhesive tapes, adhesive sheets, adhesive labels, dust removal rollers, etc., sanitary products and bookbinding. It can be used for applications such as adhesives used in manufacturing, elastic fibers used in clothing, sporting goods, etc.
  • thermoplastic elastomer of the present invention can be suitably used for films, and in particular, can be suitably used for stretchable films for sanitary products such as disposable diapers and sanitary products (film-like stretchable members for sanitary materials).
  • the thickness of the film of the present invention is not particularly limited and may be adjusted depending on the application, but when it is used as a film for sanitary products such as disposable diapers and sanitary products, it is preferably 0.01 to 5 mm, more preferably is 0.01 to 1 mm, more preferably 0.02 to 0.2 mm, and most preferably 0.02 to 0.06 mm.
  • thermoplastic elastomer of the present invention contains an aromatic vinyl block copolymer in a proportion of more than 50% by weight, and contains a polyolefin elastomer in a proportion of more than 1% by weight and less than 50% by weight, It can be suitably used as a porous film (film-like porous body) for sanitary products such as disposable diapers and sanitary products.In this case, by increasing the aperture ratio of the film, it has excellent moisture permeability, Moreover, it can also have excellent stress relaxation properties.
  • the method of molding the thermoplastic elastomer of the present invention into a film is not particularly limited, and conventionally known film molding methods can be applied, but melt extrusion molding is preferred from the viewpoint of obtaining a smooth film with good productivity. Among these, melt extrusion using a T-die is particularly suitable.
  • thermoplastic elastomer of the present invention is applied to a layer of nonwoven fabric/stretchable film/nonwoven fabric by laminating a stretchable film for sanitary products such as disposable diapers and sanitary products from both sides with a nonwoven fabric as a base sheet.
  • the manufacturing method will be described by exemplifying the case of producing a stretchable laminate having the following structure.
  • FIG. 1 is a schematic diagram of a manufacturing apparatus for manufacturing a stretchable laminate according to an embodiment of the present invention.
  • the apparatus for manufacturing a stretchable laminate includes a melt extrusion mechanism 10, a cooling roll 11, a stretching mechanism 20, a lamination mechanism 30, and a control device (not shown).
  • the control device controls the melt extrusion mechanism 10, the cooling roll 11, the stretching mechanism 20, and the laminating mechanism 30 so that they operate in cooperation with each other.
  • the melt extrusion mechanism 10 discharges the heated and melted thermoplastic elastomer in the form of a film to form a film-like or linear melt 40.
  • the melt extrusion mechanism 10 is, for example, a melt extrusion molding mechanism using a T-die, or may be a twin-screw extruder equipped with a T-die.
  • a cooling roll 11 is arranged below the melt extrusion mechanism 10, and the melt 40 discharged from the melt extrusion mechanism 10 is stretched before reaching the cooling roll 11. That is, the cooling roll 11 rotates at a circumferential speed that is higher than the feeding speed of the thermoplastic elastomer when it is discharged from the discharge port of the melt extrusion mechanism 10, so that the thickness of the film-like melt 40 reaches a predetermined value. The melt 40 is stretched until it becomes .
  • the melt extrusion mechanism 10 is It is preferable to make the distance between the discharge port and the cooling roll 11 as close as possible, and preferably less than 50 mm.
  • a blowing mechanism (from the left to the right in the drawing) for blowing wind onto the melt 40 is provided. It is also preferable to provide a mechanism for blowing the wind flowing through the melt toward the melt 40 discharged from the discharge port of the melt extrusion mechanism 10.
  • the cooling roll 11 has a flow path (not shown) in which a refrigerant flows, and while the melt 40 is moving in the feeding direction while being in contact with the outer circumferential surface of the cooling roll 11, , the thermoplastic elastomer constituting the melt 40 is cooled and solidified to a temperature range where it is elastically deformed. Thereby, the melt 40 becomes a stretchable film 40a and is pulled out from the cooling roll 11.
  • the stretchable film 40a is sent to the stretching mechanism 20 via the guide roll 12.
  • the stretching mechanism 20 includes a drawing roll 13 , a drawing nip roll 14 facing the drawing roll 13 , a first stretching roll 15 , a stretching nip roll 16 facing the drawing roll 13 , and a second stretching roll 17 .
  • the stretchable film 40a is stretched in a section between the drawing roll 13 and the drawing nip roll 14, passing between the first stretching roll 15 and the stretching nip roll 16, and reaching the second stretching roll 17. be done. That is, the stretchable film 40a is stretched in two stages at a predetermined magnification by rotating the pull-out roll 13, the first stretching roll 15, and the second stretching roll 17 in this order at high circumferential speeds.
  • the stretchable film 40a is 1, and then, due to the difference in peripheral speed between the first stretching roll 15 and the second stretching roll 17 (due to the action of the second stretching roll 17 having a faster peripheral speed). ), the stretchable film 40a stretched at the first magnification is stretched at a second magnification.
  • the lamination mechanism 30 supplies the first nonwoven fabric 50 as the first base sheet to the second stretch roll 17 via the guide roll 18, and supplies the second nonwoven fabric 60 as the second base sheet. is supplied to the second stretching roll 17 via the guide roll 19.
  • the stretchable film 40a stretched along the second stretch roll 17 is sandwiched between the first nonwoven fabric 50 and the second nonwoven fabric 60, and the stretchable film 40a is sandwiched between the first nonwoven fabric 50 and the second nonwoven fabric 60.
  • a stretchable laminate 70 is formed between the second nonwoven fabric 60 and the second nonwoven fabric 60 .
  • the formed elastic laminate 70 may be subjected to ultrasonic bonding or thermal welding by heating, if necessary. In FIG. 1, a case where ultrasonic bonding is performed using an ultrasonic bonding machine 80 is illustrated.
  • the stretchable laminate 70 is a film-like porous body
  • pattern-shaped openings can be formed by applying ultrasonic waves by the ultrasonic bonding machine 80 when performing ultrasonic bonding.
  • the stretchable laminate 70 can be manufactured by using the manufacturing apparatus shown in FIG. By manufacturing as described above, the stretchable laminate 70 has stretchability at least in the MD direction.
  • thermoplastic elastomer of the present invention satisfies all of the following (1) to (4).
  • Storage modulus at 23°C is more than 0.3 MPa.
  • Loss tangent (tan ⁇ ) at 23°C is 0.20 or less.
  • thermoplastic elastomer of the present invention when manufactured using the manufacturing apparatus shown in FIG. It is also possible to suppress the reduction in film width due to stretching in the MD direction, and therefore, it is possible to provide a stretchable film or stretchable laminate with high stress, high stretch rate, and wide width. It is something.
  • the weight average molecular weight of each block copolymer was determined as a polystyrene equivalent molecular weight by high performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 ml/min.
  • the device is HLC8320 manufactured by Tosoh Corporation, the column is a combination of three Shodex KF-404HQ manufactured by Showa Denko Co., Ltd. (column temperature 40°C), the detector is a differential refractometer and an ultraviolet detector, and the molecular weight calibration is performed by Tosoh Corporation. The test was carried out on 12 points of standard polystyrene (5 million to 3 million) made by the manufacturer.
  • the reaction vessel was placed in a cooling tank and cooled to ⁇ 25° C., and then ozone generated by an ozone generator was introduced while oxygen was flowing into the reaction vessel at a flow rate of 170 ml/min. After 30 minutes from the start of the reaction, completion of the reaction was confirmed by introducing the gas flowing out from the reaction vessel into the aqueous potassium iodide solution. Next, 50 ml of diethyl ether and 470 mg of lithium aluminum hydride were placed in another reaction vessel purged with nitrogen, and while cooling the reaction vessel with ice water, the solution reacted with ozone was slowly dropped into the reaction vessel. Then, the reaction container was placed in a water bath, and the temperature was gradually raised to reflux at 40° C. for 30 minutes.
  • Weight average molecular weight of isoprene polymer block of each block copolymer The weight average molecular weight of the corresponding styrene polymer block was subtracted from the weight average molecular weight of the block copolymer determined as above, and the weight average molecular weight of the isoprene polymer block was determined based on the calculated value. .
  • the measurement conditions were a dynamic shear strain of 0.13% and a frequency of 1 Hz (angular velocity (6.28 rad/s ⁇ 1 )). Measurements were performed while increasing the temperature from -40°C to 150°C at a rate of 4°C/min, and the value at 23°C was read.
  • ⁇ Test piece shape width 25mm x length 90mm x thickness 0.050mm ⁇ Test temperature: 23°C ⁇ Distance between grips: 25mm ⁇ Test speed: 300mm/min
  • MD melt flow direction
  • TD melt flow perpendicular direction
  • Stress at 200% elongation in MD direction Regarding the film of the block copolymer composition, stress at 200% elongation in the melt flow direction (MD) during molding was measured using a Tensilon universal testing machine RTC-1210 manufactured by ORIENTEC in accordance with ISO527-3. It was measured and evaluated based on the following criteria.
  • ⁇ Stress at 200% elongation in MD direction is 0.8 MPa or more
  • ⁇ Stress at 200% elongation in MD direction is less than 0.8 MPa ⁇ Test piece shape: width 25 mm x length 90 mm x thickness 0.050 mm ⁇ Test temperature: 23°C ⁇ Distance between grips: 25mm ⁇ Test speed: 300mm/min
  • Permanent elongation (%) Strain at the point of zero stress (mm) / Distance between grips (mm) x 100 ⁇ Test piece shape: width 25mm x length 90mm x thickness 0.050mm ⁇ Test temperature: 23°C ⁇ Distance between grips: 25mm ⁇ Test speed: 300mm/min Based on the obtained results, evaluation was performed based on the following criteria. ⁇ : Permanent elongation in MD direction is 15% or less ⁇ : Permanent elongation in MD direction is over 15%
  • thermoplastic elastomer processing speed 5 kg/hour
  • Film take-off speed 4 m/min
  • Extruder L/D 30
  • lip 0.5mm Distance between T-die tip and cooling roll 2mm
  • Cooling roll temperature 23°C
  • the thermoplastic elastomer film was stretched and held by 200% in the melt flow direction (MD) during molding using a Tensilon universal testing machine RTC-1210 manufactured by ORIENTEC with reference to ISO527-3.
  • the width of the film in the stretched state immediately after was measured, and B ( film width at the time of stretching/film width before stretching) was evaluated.
  • ⁇ Test piece shape width 25mm x length 90mm x thickness 0.050mm ⁇ Test temperature: 23°C ⁇ Distance between grips: 25mm ⁇ Test speed: 300mm/min
  • the film width of the elastic member is determined by the product (C) of the film width retention rate in the step of cooling and solidifying the film and the step of joining the stretched film to the base sheet, and the larger this value is, the better , it can be judged that when used as a stretchable member such as a stretchable film, a wide product can be suitably obtained.
  • C: Ratio (%) of product film width to die width A x B x 100 ⁇ : Ratio of product film width to die width is 60% or more ⁇ : Ratio of product film width to die width is less than 60%
  • the polymerization conversion rate of styrene was 100%.
  • Polymer B1 was formed. Thereafter, 2.97 kg of styrene was continuously added over 1 hour while controlling the temperature to maintain the temperature at 50 to 60° C. and stirring at the same rotation speed. After the addition of styrene was completed, polymerization was further carried out for 1 hour while stirring was continued at the same rotation speed to form a triblock chain having an active end.
  • the stirring Reynolds number was maintained at 500.
  • the power required for stirring did not change significantly even if the solution viscosity changed, and was maintained at ⁇ 2.5 kW/m 3 (the same applies to Production Examples 2 to 7).
  • the amount of impurities such as water is controlled, and the amount of deactivating components such as water that deactivates the polymerization initiator is 1 ⁇ 10 -3 mol/kg or less. I used something that was restrained.
  • block copolymer A1 and block copolymer B1 in the above mixture was 57/43.
  • the viscosity of the solution increases, so even if stirring is continued at the same rotation speed, the stirring Reynolds number decreases in the latter stages of the process, but even in the final stage before the addition of the polymerization terminator, when the viscosity is highest.
  • the stirring Reynolds number was maintained at 500.
  • the power required for stirring did not change significantly even when the solution viscosity changed, and was maintained at ⁇ 2.5 kW/m 3 (the same applies to Production Example 9).
  • the amount of impurities such as water is controlled, and the amount of deactivating components such as water that deactivates the polymerization initiator is 1 ⁇ 10 -3 mol/kg or less. I used something that was restrained.
  • the power required for stirring did not change significantly even when the solution viscosity changed, and was maintained at ⁇ 2.5 kW/m 3 .
  • the amount of impurities such as water is controlled, and the amount of deactivating components such as water that deactivates the polymerization initiator is 1 ⁇ 10 -3 mol/kg or less. I used something that was restrained.
  • the weight ratio of block copolymer D1 and block copolymer E1 in the above mixture was 40/60.
  • Example 1 The mixture of block copolymer A1 and block copolymer B1 obtained in Production Example 1 and the block copolymer C1 obtained in Production Example 8 were mixed by weight of each block copolymer listed in Table 7.
  • a composition was prepared by mixing in the following ratio. The obtained composition was charged into a twin screw extruder equipped with a T-die. Then, in this twin-screw extruder, these are heated and melted at 200°C, kneaded, extruded for 20 minutes continuously onto a cooling roll to cool them, and then wound up with a winding roll to obtain an average thickness of It was molded into a film with a diameter of 0.05 mm.
  • Examples 2 to 6, Comparative Examples 1 to 6 A composition and a film were obtained in the same manner as in Example 1, except that the weight ratio of each block copolymer shown in Table 7 was changed, and evaluated in the same manner. The results are shown in Table 7.
  • Example 7 A mixture of block copolymer A4 and block copolymer B4 obtained in Production Example 4, block copolymer C2 obtained in Production Example 9, and polyolefin elastomer F1 (trade name "Vistamaxx3000", ExxonMobil Co., Ltd., ethylene-propylene block copolymer, ethylene content: 11% by weight, hardness (Shore A): 82, Vicat softening point: 66°C), and the weight ratio of each block copolymer listed in Table 8.
  • a composition and a film were obtained in the same manner as in Example 1, except that they were mixed so that the composition and film were mixed, and evaluated in the same manner. The results are shown in Table 8.
  • Example 7 the end-of-extension properties were measured by the following method.
  • ⁇ Size change is less than 30%
  • ⁇ Size change is 30% or more
  • Example 8 and 9 Comparative Example 1
  • the amounts of the mixture of block copolymer A4 and block copolymer B4 obtained in Production Example 4, block copolymer C2 obtained in Production Example 9, and polyolefin elastomer F1 were changed as shown in Table 8.
  • a composition and a film were obtained in the same manner as in Example 7, except that the composition and film were evaluated in the same manner. The results are shown in Table 8.

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WO2020045496A1 (ja) 2018-08-28 2020-03-05 日本ゼオン株式会社 組成物および弾性体

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JP2008007654A (ja) * 2006-06-30 2008-01-17 Nippon Zeon Co Ltd 伸縮性フィルム、伸縮性部材及び衛生用品
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