WO2010126098A1 - Copolymère bloc de polyuréthane - Google Patents

Copolymère bloc de polyuréthane Download PDF

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Publication number
WO2010126098A1
WO2010126098A1 PCT/JP2010/057610 JP2010057610W WO2010126098A1 WO 2010126098 A1 WO2010126098 A1 WO 2010126098A1 JP 2010057610 W JP2010057610 W JP 2010057610W WO 2010126098 A1 WO2010126098 A1 WO 2010126098A1
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Prior art keywords
block copolymer
polyurethane
polymer
mass
polyol
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PCT/JP2010/057610
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English (en)
Japanese (ja)
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秀和 齋藤
和正 服部
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株式会社クラレ
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Priority to JP2011511445A priority Critical patent/JPWO2010126098A1/ja
Publication of WO2010126098A1 publication Critical patent/WO2010126098A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the present invention relates to a polyurethane block copolymer having a specific addition polymerization block and a specific polyurethane block, a polyurethane block copolymer composition and a thermoplastic polymer composition containing the same, and using these
  • the present invention relates to a molded body and a composite molded body to be obtained.
  • Silicone is excellent in releasability, heat resistance, cold resistance, weather resistance, water repellency, and electrical insulation, and exhibits stable physical properties in a wide temperature range. It is used. However, silicones have a limited range of use due to their poor mechanical properties (such as tensile break strength and wear resistance) and poor adhesion to other materials.
  • Patent Documents 1 and 2 disclose a coating agent for coating a silicone rubber substrate, and the coating material is a polyurethane having an aliphatic unsaturated group in a molecule produced using an organotin compound catalyst or the like.
  • Patent Document 3 discloses an overcoat material for silicone rubber, which comprises a linear polymer having a hydroxyl group or an amino group at both ends and a bifunctional isocyanate compound, wherein the molar ratio of the former is the latter.
  • the main component is a urethane resin having a weight average molecular weight of 10,000 to 500,000 obtained by reacting so as to be larger than 1.0.
  • these coating agents (coating materials) still have insufficient adhesion to silicone, and even if these coating agents (coating materials) are coated on a silicone rubber substrate, both polyurethane and silicone are excellent. Thus, a composite molded body having the above characteristics cannot be obtained.
  • Patent Document 4 discloses a method for producing a composite molded body in which a silicone rubber layer and a thermoplastic resin layer are laminated and integrated. After the primary injection molding in the mold cavity, the addition curing type silicone rubber composition is subjected to secondary injection molding on the thermoplastic resin layer formed in the cavity, and the silicone rubber composition is made to be above the softening point of the thermoplastic resin. Cure at a temperature below the melting point.
  • this method may not provide a sufficient effect depending on the type of thermoplastic resin. For example, even if this method is applied to the production of a composite molded body of polyurethane and silicone rubber, a composite molded body in which the polyurethane layer and the silicone rubber layer are well bonded cannot be obtained.
  • polyurethane block copolymers having a specific addition polymerization block and a specific polyurethane block are themselves various materials ( Especially excellent in adhesiveness with silicone); and by blending the polyurethane block copolymer into various thermoplastic polymers as a masterbatch, the thermoplastic polymer has excellent adhesiveness with various materials (especially silicone). It was found that a composition was obtained.
  • the present inventors have further studied based on the above findings and completed the present invention. The features of the present invention are as follows.
  • a polyurethane block copolymer having an addition polymerization block ( ⁇ ) and a polyurethane block ( ⁇ ) is selected from a block copolymer having a polymer block (A) containing an aromatic vinyl compound unit and a polymer block (B) containing a conjugated diene unit; and a hydrogenated product thereof.
  • the polyurethane block ( ⁇ ) has the following general formula (I):
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the content of the structural unit (I) is 0.2 to 40% by mass in the total mass of the polyurethane block copolymer, as described in any one of the above [1] to [4] Polyurethane block copolymer.
  • the functional group-containing addition polymerization block copolymer has a functional group capable of reacting with at least one component selected from the group consisting of a polymer polyol (a p ), an organic polyisocyanate (b), and a chain extender (c).
  • the functional group-containing addition polymerization block copolymer has a functional group capable of reacting with at least one component selected from the group consisting of a polymer polyol (a p ), an organic polyisocyanate (b), and a chain extender (c).
  • [8] At least one selected from the group consisting of the polyurethane block copolymer according to any one of [1] to [5] above, and an organic zinc compound, an organic bismuth compound, an organic titanium compound, and an organic zirconium compound.
  • a polyurethane block copolymer composition comprising a seed metal compound, wherein the content of the metal compound is 0.1 to 2,000 ppm by mass based on the mass of the polyurethane block copolymer.
  • thermoplastic polymer composition comprising the polyurethane block copolymer according to any one of [1] to [5] above and a thermoplastic polymer other than the polyurethane block copolymer.
  • the content of the structural unit (I) of the polyurethane block ( ⁇ ) is 0.1 to 20% by mass in the total mass of the thermoplastic polymer composition, according to the above [9].
  • Thermoplastic polymer composition is 0.1 to 20% by mass in the total mass of the thermoplastic polymer composition, according to the above [9].
  • At least one metal compound selected from the group consisting of an organic zinc compound, an organic bismuth compound, an organic titanium compound, and an organic zirconium compound is added in an amount of 0.1 to 2, based on the mass of the polyurethane block copolymer.
  • the thermoplastic polymer is polyamide; polyester; polyvinylidene chloride; polyvinyl chloride; polycarbonate; acrylic resin; polyoxymethylene resin; saponified ethylene-vinyl acetate copolymer; aromatic vinyl compound and cyanide A copolymer with at least one selected from a vinyl fluoride compound, a conjugated diene and an olefin; a polyurethane; a styrenic polymer; and at least one selected from the group consisting of polyolefins.
  • the thermoplastic polymer composition according to any one of the above.
  • thermoplastic polymer composition according to any one of [9] to [12] above, wherein the polyurethane block copolymer and the thermoplastic polymer are A production method comprising a step of melt-kneading.
  • thermoplastic polymer composition according to any one of [9] to [12] above.
  • the present invention it is excellent in adhesiveness with various materials (especially silicone), and can be sufficiently adhered to the various materials without prior surface activation treatment (primer treatment or the like).
  • a polyurethane block copolymer is obtained.
  • the polyurethane block copolymer has excellent adhesion to various materials (particularly silicone), and the various materials can be used without prior surface activation treatment (primer treatment, etc.).
  • a thermoplastic polymer composition that can be sufficiently bonded is obtained.
  • the present invention provides a method for producing the polyurethane block copolymer in addition to the polyurethane block copolymer and the thermoplastic polymer composition; a polyurethane block copolymer composition containing the polyurethane block copolymer; A method for producing the thermoplastic polymer composition; a master batch capable of efficiently producing the thermoplastic polymer composition; the polyurethane block copolymer, the polyurethane block copolymer composition, or A molded body composed of the thermoplastic polymer composition; a composite molded body in which a member containing the polyurethane block copolymer and a member made of various materials typified by silicone are sufficiently bonded; and the composite molding A method for producing a body.
  • the polyurethane block copolymer of the present invention has an addition polymerization block ( ⁇ ) and a polyurethane block ( ⁇ ).
  • the addition polymerization block ( ⁇ ) is a block copolymer having a polymer block (A) containing an aromatic vinyl compound unit and a polymer block (B) containing a conjugated diene unit; and the block copolymer It is derived from an addition polymerization block copolymer selected from hydrogenated products.
  • the bonding form of the addition polymerization block ( ⁇ ) and the polyurethane block ( ⁇ ) is not particularly limited, and is a straight chain, a branched chain, a radial, or a combination thereof. Any form may be sufficient. Among these, a linear bond form is preferable.
  • the structure of the polyurethane block copolymer is represented by the formula: ⁇ - ⁇ , ⁇ - ⁇ , where the above addition polymerization block ( ⁇ ) is simply represented by “ ⁇ ” and the polyurethane block ( ⁇ ) is simply represented by “ ⁇ ”.
  • diblock type polyurethane block copolymer, and the polyurethane block copolymer composition and thermoplastic polymer composition containing the same are more excellent in adhesiveness to silicone.
  • the addition polymerization blocks ( ⁇ ) may be blocks having the same contents or different contents. Also good.
  • the polyurethane block copolymer has two or more polyurethane blocks ( ⁇ )
  • the polyurethane blocks ( ⁇ ) may be blocks having the same contents or different contents.
  • the block ( ⁇ )] may be the same or different in the type of structural units constituting them, the bonding type, the number average molecular weight, and the like.
  • the mass ratio of the addition polymerization block ( ⁇ ) / polyurethane block ( ⁇ ) is preferably within the range of 10/90 to 95/5, more preferably within the range of 10/90 to 90/10, and even more preferably 20 / It is in the range of 80 to 80/20, particularly preferably in the range of 30/70 to 70/30.
  • a polyurethane block copolymer having an addition polymerization block ( ⁇ ) / polyurethane block ( ⁇ ) at a preferred mass ratio is more excellent in adhesion to silicone.
  • Examples of the aromatic vinyl compound unit constituting the polymer block (A) containing the aromatic vinyl compound unit contained in the addition polymerization block ( ⁇ ) include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, and o-methyl.
  • Styrene m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2- Examples include structural units derived from ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, vinylanthracene, indene, acetonaphthylene, monofluorostyrene, difluorostyrene, monochlorostyrene, methoxystyrene, and the like.
  • the polymer block (A) may be composed of one type of aromatic vinyl compound unit, or may be composed of two or more types of aromatic vinyl compound units.
  • the polymer block (A) is preferably composed mainly of structural units derived from styrene and / or ⁇ -methylstyrene.
  • the polymer block (A) may contain a small amount of a structural unit derived from another copolymerizable monomer, if necessary, along with the aromatic vinyl compound unit.
  • the content of structural units derived from other copolymerizable monomers is preferably 30% by mass or less, more preferably 10% by mass or less, based on the mass of the polymer block (A).
  • Examples of other copolymerizable monomers include 1-butene, 1-pentene, 1-hexene, butadiene, 2-methyl-1,3-butadiene (isoprene), methyl vinyl ether, and the like.
  • Examples of the conjugated diene unit constituting the polymer block (B) containing the conjugated diene unit contained in the addition polymerization block ( ⁇ ) include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene). ), Structural units derived from 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.
  • the polymer block (B) may be composed of one type of conjugated diene unit or may be composed of two or more types of conjugated diene units. When the polymer block (B) contains two or more kinds of conjugated diene units, the bonding form thereof may be random, tapered, or partially blocky, and even if they are mixed Good.
  • the content of the conjugated diene unit in the polymer block (B) is preferably in the range of 70 to 100% by mass, and in the range of 90 to 100% by mass based on the mass of the polymer block (B). It is more preferable.
  • the addition polymerization block ( ⁇ ) may be a hydrogenated product of a block copolymer having a polymer block (A) and a polymer block (B).
  • the hydrogenated product may be one in which only a part of the unsaturated double bond of the polymer block (B) is hydrogenated, or one in which all of the hydrogenated product is hydrogenated.
  • the hydrogenation rate in the block in which the polymer block (B) is hydrogenated is 50 mol% or more based on the total number of unsaturated double bonds of the polymer block (B) before hydrogenation. Is preferably 60 mol% or more, and more preferably 80 mol% or more. If the hydrogen conversion rate of the polymer block (B) is 50 mol% or more, a polyurethane block copolymer excellent in heat resistance, weather resistance and light resistance can be obtained.
  • the addition polymerization block ( ⁇ ) is hydrogenated as a polymer block (B) which may be hydrogenated. It is preferable to have an isoprene polymer block that may be hydrogenated, a butadiene polymer block that may be hydrogenated, or a copolymer block of isoprene and butadiene that may be hydrogenated.
  • the addition polymerization system block ( ⁇ ) is an optionally hydrogenated isoprene polymer block or hydrogenated as an optionally hydrogenated polymer block (B).
  • the proportion is 30 mol% or more based on the number of moles of all isoprene units and butadiene units contained in the polymer block (B) (preferably 4 It is a mol% or more).
  • the addition polymerization system block ( ⁇ ) has an optionally hydrogenated butadiene polymer block as the optionally hydrogenated polymer block (B), And (4) the proportion of 1,2-bonded butadiene units contained in the polymer block (B) is 60 mol% or more based on the number of moles of all butadiene units contained in the polymer block (B). (Preferably 80 mol% or more).
  • the conjugated diene unit (for example, isoprene unit, butadiene unit, etc.) in the block in which the polymer block (B) is hydrogenated includes a hydrogenated conjugated diene unit (for example, hydrogenated isoprene unit). , Hydrogenated butadiene units, etc.).
  • the bonding form of the polymer block (A) in the addition polymerization system block ( ⁇ ) and the polymer block (B) or a block in which it is hydrogenated is not particularly limited, and is linear, branched or radial. , Or a combined form in which they are combined, but is preferably a linear combined form.
  • the addition polymerization block ( ⁇ ) includes the above polymer block (A) (hereinafter sometimes simply referred to as “A”) and the polymer block (B) or a block in which it is hydrogenated (hereinafter referred to as “A”).
  • the structure is simply represented by “B”, and the structure thereof is represented by the formula: (AB) m -A, (AB) n , B- (AB) p (wherein , M, n, and p each represents an integer of 1 or more).
  • the addition polymerization block ( ⁇ ) has two or more A and one or more B directly. It is preferably in the form of a chain-bonded block copolymer, and more preferably in the form of a triblock copolymer represented by the formula: ABA.
  • the polymer blocks (A) may be blocks having the same contents or different contents.
  • the addition polymerization system block ( ⁇ ) has two or more polymer blocks (B) or a block in which it is hydrogenated
  • the polymer block (B) or the block in which it is hydrogenated has the same content.
  • the block may be a block with different contents.
  • two A in the triblock structure represented by ABA or two B in the triblock structure represented by BAB are aromatic vinyl compounds or conjugates constituting them.
  • the type of diene, the bonding type thereof, the number average molecular weight of the block, etc. may be the same or different.
  • the content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block ( ⁇ ) is preferably in the range of 5 to 90% by mass with respect to the total mass of the addition polymerization block ( ⁇ ).
  • a polyurethane block copolymer having an addition polymerization block ( ⁇ ) in which the content of a structural unit derived from an aromatic vinyl compound is within the above range is further excellent in adhesiveness to silicone.
  • the content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block ( ⁇ ) is more preferably in the range of 10 to 90% by mass with respect to the total mass of the addition polymerization block ( ⁇ ). .
  • the content of structural units derived from an aromatic vinyl compound in the addition polymerization block ( ⁇ ) Is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass.
  • a structural unit derived from an aromatic vinyl compound in the addition polymerization block ( ⁇ ) The content of is preferably in the range of 40 to 90% by mass, more preferably in the range of 50 to 90% by mass. If the content rate of the said structural unit exists in the preferable range, the thermoplastic polymer composition which was further excellent in adhesiveness with silicone will be obtained.
  • the number average molecular weights of the polymer block (A) and the polymer block (B) are not particularly limited.
  • the number average molecular weight of the polymer block (B) is preferably in the range of 10,000 to 150,000.
  • the polyurethane block copolymer in which the number average molecular weight of each block is within the above range is further excellent in adhesiveness with silicone.
  • the total number average molecular weight of the addition polymerization block ( ⁇ ) is preferably in the range of 10,000 to 300,000, more preferably 20,000 to 100,000, from the viewpoint of adhesion to silicone. Within range.
  • polyurethane block ( ⁇ ) of the polyurethane block copolymer of the present invention Is the following general formula (I);
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Both R 1 and R 2 may be hydrogen atoms, one may be a hydrogen atom and the other may be an alkyl group, or both may be an alkyl group.
  • R 1 are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group.
  • R 1 is preferably a hydrogen atom, a methyl group, or an ethyl group.
  • R 2 examples include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, Examples thereof include a cyclohexyl group, and R 2 is preferably a hydrogen atom, a methyl group, or an ethyl group.
  • the structural unit (I) includes the above-mentioned (Ia), (Ib), ( Ic) and (Id) are preferable, and (Ia), (Ib) and (Ic) are more preferable.
  • the polyurethane-based block copolymer of the present invention preferably has the structural unit (I) of the polyurethane block ( ⁇ ) in a proportion of 0.2 to 40% by mass based on the total mass.
  • the content of the structural unit (I) contained in the polyurethane block ( ⁇ ) is less than 0.2% by mass, the adhesion of the resulting polyurethane block copolymer to silicone tends to decrease.
  • the content is more than 40% by mass, the moldability of the obtained polyurethane block copolymer tends to be lowered, and the molding and composite molding obtained from the polyurethane block copolymer have a tendency to deteriorate. Characteristics, heat resistance, weather resistance and the like tend to decrease.
  • the content of the structural unit (I) of the polyurethane block ( ⁇ ) in the polyurethane block copolymer is more preferably 1 to 35% by mass based on the total mass of the polyurethane block copolymer.
  • the content is more preferably 5 to 35% by mass, and particularly preferably 2 to 30% by mass.
  • Polyurethane block (beta) is at least, polymer polyols containing polymer polyol having a structural unit (I) in a molecule (a p -1) and (a p), formed by the reaction of an organic polyisocyanate (b) be able to.
  • the polymer polyol (a p ) is a polymer polyol other than the polymer polyol (a p -1) [that is, a polymer polyol having no structural unit (I), hereinafter referred to as “other polymer polyol (a p -2)”. It may be abbreviated].
  • the polyurethane block ( ⁇ ) is preferably formed by the reaction of the polymer polyol (a p ), the organic polyisocyanate (b) and the chain extender (c). These reactions are preferably carried out in the presence of a urethanization reaction catalyst comprising at least one metal compound selected from the group consisting of an organic zinc compound, an organic bismuth compound, an organic titanium compound and an organic zirconium compound.
  • the hydroxyl group which said polymer polyol ( ap ) has is located in the molecular terminal.
  • the hydroxyl group located at the molecular end is involved in the main chain extension during polyurethane formation.
  • the number of hydroxyl groups in the polymer polyol (a p ) is preferably 0.7 or more on average per molecule, more preferably 0.7 to 3, and preferably 1.8 to 2.5. More preferably it is.
  • the number average molecular weight of the polymer polyol (a p ) is preferably 500 to 10,000, more preferably 500 to 8,000, still more preferably 600 to 5,000, and particularly preferably 800 to 5,000.
  • a polymer polyol (a p ) having a preferred number average molecular weight, non-adhesiveness, melt moldability, mechanical properties (such as wear resistance and tensile breaking strength), flexibility, flexibility, low residual strain Polyurethane block copolymer, molded body, composite molded body and the like having excellent properties and oil resistance can be obtained.
  • the number average molecular weights of the polymer polyol (a p -1) and the other polymer polyol (a p -2) used in the above case are preferably 500 to 10,000, more preferably 500 to 8,000, It is preferably 600 to 5,000, particularly preferably 800 to 5,000.
  • a polymer polyol ( ap- 1) having a number average molecular weight and another polymer polyol ( ap- 2) a polyurethane block copolymer excellent in non-adhesiveness, mechanical strength, heat resistance, etc., molding Body, composite molded body and the like can be obtained.
  • the number average molecular weight of the polymer polyol referred to in the present specification is a number average molecular weight calculated based on a hydroxyl value measured in accordance with JIS K-1557.
  • the number of hydroxyl groups per molecule in the polymer polyol (a p -1) and the other polymer polyol (a p -2) is preferably 2.0 to 2.1, more preferably 2.0 to It is in the range of 2.07, particularly preferably 2.005 to 2.05.
  • a polymer polyol (a p -1) having a preferred number of hydroxyl groups and another polymer polyol (a p -2) are used, a polyurethane block excellent in moldability, non-adhesiveness, mechanical properties (for example, abrasion resistance), etc.
  • a copolymer can be obtained.
  • the molecular weight of the polymer polyol (a p -2), the molecular weight and amount of the organic polyisocyanate (b), the molecular weight and amount of the chain extender (c), and the like can be adjusted.
  • the content of the structural unit (I) in the finally obtained polyurethane block copolymer is preferably in the range of 0.2 to 40% by mass, more preferably 1 to 35% by mass.
  • the polymer polyol (a p -1) in the polymer polyol (a p ) so that it is in the range of 1.5 to 35% by mass, more preferably in the range of 2 to 30% by mass.
  • the content rate may be adjusted.
  • the polymer polyol (a p -1) having the structural unit (I) in the molecule the polymer polyol having a desired amount of the structural unit (I) in the molecule and having a plurality of hydroxyl groups reactive with isocyanate groups Any may be used.
  • polystyrene polyol examples include polybutadiene polyol in which butadiene is mainly polymerized by 1,2-bonds; polyisoprene polyol in which isoprene is polymerized mainly by 1,2-bonds and / or 3,4-bonds; A butadiene / isoprene copolymer polyol in which isoprene is polymerized mainly by 1,2-bonds and / or 3,4-bonds; butadiene and / or isoprene is predominantly by 1,2-bonds and / or 3,4-bonds Polymerized butadiene and / or isoprene and other monomers [eg styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (P
  • the polymer polyol (a p -1) is preferably at least one selected from the group consisting of polybutadiene polyol, polyisoprene polyol and butadiene / isoprene copolymer polyol.
  • the total proportion of 1,2-bond units and 3,4-bond units in all structural units derived from butadiene and / or isoprene is generally 80 to 100 mol%. Preferably, it is 85 to 100 mol%, more preferably 90 to 100 mol%.
  • the proportion of the structural unit derived from butadiene and / or isoprene in the copolymer polyol is preferably 80% by mass or more, more preferably 85%. It is 90% by mass or more, particularly preferably 90 to 99% by mass. With such a ratio, a desired amount of the structural unit (I) can be easily contained in the copolymer polyol, and adhesiveness with silicone is effectively expressed.
  • polymer polyol (a p) As part of the polymer polyol (a p), as the other polymer polyols that may be used with the polymer polyol having a structural unit (I) (a p -1) (a p -2), conventionally used for the production of polyurethane Any polymer polyol can be used.
  • Such other polymer polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyester polycarbonate polyols, polyolefin polyols, castor oil-based polyols, vinyl polymer-based polyols, etc. (however, the structural unit (I )).
  • These other polymer polyols (a p -2) may be used alone or in combination of two or more.
  • polyester polyol, polyether polyol, and polyolefin polyol are preferable, and polyester polyol and / or polyether polyol are more preferable.
  • polyester polyol examples include (1) a polyol component and a polycarboxylic acid component [polycarboxylic acid or an ester-forming derivative thereof (for example, an ester thereof) according to a conventional method.
  • Polyester anhydride obtained by direct esterification reaction or transesterification reaction; and (2) polyester polyol obtained by ring-opening polymerization of a lactone using a polyol as an initiator; be able to.
  • the aforementioned polyol component (a diol diol having two hydroxyl groups per molecule and a polyol having three or more hydroxyl groups per molecule) used in the production of a polyester polyol obtained by reacting a polyol component and a polycarboxylic acid component is: Any of those generally used in the production of polyester may be used.
  • diol examples include aliphatic diols having 2 to 15 carbon atoms (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octane Diol, 1,9-nonanediol, 2-methyl-1,9-n
  • the polycarboxylic acid component that can be used in the production of a polyester polyol obtained by reacting a polyol component and a polycarboxylic acid component may be any as long as it is generally used in the production of polyester.
  • aliphatic dicarboxylic acids having 4 to 12 carbon atoms for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid, 3- Methyl glutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, etc.); alicyclic dicarboxylic acids (eg cyclohexanedicarboxylic acid, dimer acid, water) Dimer acid, etc.]; aromatic dicarboxy
  • polycarboxylic acid components may be used individually by 1 type, and may use 2 or more types together.
  • aliphatic dicarboxylic acids having 6 to 12 carbon atoms, particularly one or more of adipic acid, azelaic acid and sebacic acid are preferably used.
  • lactones used in the production of polyester polyols obtained by ring-opening polymerization of lactones include ⁇ -caprolactone and ⁇ -methyl- ⁇ -valerolactone.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol obtained by ring-opening polymerization of a cyclic ether in the presence of the polyol.
  • polytetramethylene glycol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol obtained by ring-opening polymerization of a cyclic ether in the presence of the polyol.
  • Methodyl tetramethylene glycol and the like can be mentioned. These may be used alone or in combination of two or more. Of these, polytetramethylene glycol and poly (methyltetramethylene glycol) are preferred.
  • Examples of the polycarbonate polyol that can be used as the other polymer polyol (a p -2) include those obtained by reacting a polyol with a carbonate compound (eg, dialkyl carbonate, alkylene carbonate, diaryl carbonate, etc.).
  • a carbonate compound eg, dialkyl carbonate, alkylene carbonate, diaryl carbonate, etc.
  • the polyol component illustrated previously as a component used for manufacture of a polyester polyol can be used.
  • Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate
  • examples of the alkylene carbonate include ethylene carbonate
  • examples of the diaryl carbonate include diphenyl carbonate.
  • polyester polycarbonate polyol that can be used as the other polymer polyol (a p -2) include, for example, (1) those obtained by reacting a polyol, a polycarboxylic acid and a carbonate compound at the same time; And a compound obtained by reacting it with a carbonate compound; and (3) a compound obtained by previously synthesizing a polycarbonate polyol and then reacting with a polycarboxylic acid.
  • polystyrene copolymer polyol examples include conjugated dienes such as polyisoprene polyol, polybutadiene polyol, butadiene / isoprene copolymer polyol, butadiene / acrylonitrile copolymer polyol, and butadiene / styrene copolymer polyol.
  • conjugated dienes such as polyisoprene polyol, polybutadiene polyol, butadiene / isoprene copolymer polyol, butadiene / acrylonitrile copolymer polyol, and butadiene / styrene copolymer polyol.
  • Examples thereof include hydrogenated products of polymer polyols.
  • the conjugated diene polymer polyol is obtained by subjecting only a conjugated diene (for example, butadiene, isoprene, etc.) or a conjugated diene and another monomer to living polymerization in the presence of a polymerization initiator, and then a hydroxyl group-containing epoxy compound at the polymerization active terminal. It can be obtained by reaction.
  • the said hydrogenation thing may be used individually by 1 type, and may use 2 or more types together.
  • the type of the organic polyisocyanate (b) is not particularly limited, and any organic polyisocyanate conventionally used in the production of polyurethane can be used.
  • the organic polyisocyanate (b) include aromatic diisocyanates (for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dichloro-4, 4'-diphenylmethane diisocyanate, etc.); and aliphatic or cycloaliphatic diisocyanates (eg, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc.). These organic polyisocyanates may be used alone or in combination of two or more. Of the
  • chain extender (c) a low molecular weight compound having a molecular weight of 450 or less and having two or more active hydrogen atoms, which is usually used as a chain extender in the production of polyurethane, can be used.
  • chain extender (c) that can be used in the present invention include diols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis ( ⁇ -hydroxyethoxy).
  • the molecular weight is in the range of 100 to 450, and two or more active hydrogen atoms and the structural unit (I) are included. You may use the compound which has as chain extender (c).
  • the polyurethane block copolymer of the present invention is (I) a functional group-containing addition polymerization block copolymer; (Ii) a polymer polyol containing a polymer polyol having a structural unit (I) that in the molecule represented by the above general formula (I) (a p -1) (a p); (Iii) an organic polyisocyanate (b); and optionally (iv) a chain extender (c) Can be obtained by a production method including a step of reacting (hereinafter, sometimes abbreviated as “production method 1”).
  • the functional group-containing addition polymerization block copolymer is a functional group capable of reacting with at least one component selected from the group consisting of a polymer polyol (a p ), an organic polyisocyanate (b), and a chain extender (c).
  • the production method 1 includes a reaction product of the polymer polyol (a p ), the organic polyisocyanate (b) and a chain extender (c) as an optional component, the functional group-containing addition polymerization block copolymer, A mode in which is reacted is included.
  • the polyurethane block copolymer of the present invention is (I) a polymer containing a polymer polyol having a structural unit (I) that in the molecule represented by the above general formula (I) (a p -1) polyol (a p); (Ii) an organic polyisocyanate (b); and optionally (iii) a chain extender (c) Polyurethane formed by reacting with (Iv) It can also be obtained by a production method including a step of reacting a functional group-containing addition polymerization block copolymer (hereinafter sometimes abbreviated as “production method 2”). The description of the functional group-containing addition polymerization block copolymer of Production Method 2 is the same as that of Production Method 1 above.
  • Examples of the reactive functional group possessed by the functional group-containing addition polymerization block copolymer include functional groups that can react with the polymer polyol (a p ) and / or the chain extender (c) (for example, carboxyl groups, acid anhydrides). Groups, thiocarboxyl groups, isocyanate groups, etc.), and functional groups that can react with the organic polyisocyanate (b) (for example, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, acid anhydride groups, thiocarboxyl groups, isocyanate groups, etc.) Is mentioned.
  • the functional group-containing addition polymerization block copolymer may contain two or more of these functional groups.
  • the reactive functional group is preferably a functional group capable of reacting with the organic polyisocyanate (b), more preferably a hydroxyl group. If a functional group-containing addition polymerization block copolymer containing a hydroxyl group is used, a uniform polyurethane-forming reaction can be performed in the production of the polyurethane block copolymer.
  • the reactive functional group is preferably located at the end of the functional group-containing addition polymerization block copolymer.
  • the reactive functional group is involved in the main chain extension by the polyurethane formation reaction when the polyurethane block copolymer is produced.
  • the polyurethane block copolymer thus obtained is further excellent in adhesiveness with silicone.
  • the number of reactive functional groups is preferably an average of 0.6 or more, more preferably 0.7 or more per molecule per molecule of the functional group-containing addition polymerization block copolymer.
  • the production method of the functional group-containing addition polymerization block copolymer is not limited in any way, and examples thereof include ionic polymerization methods (anionic polymerization methods and cationic polymerization methods), single site polymerization methods, radical polymerization methods, and the like. be able to.
  • anionic polymerization method for example, an aromatic vinyl compound and a conjugated diene are sequentially polymerized in an inert organic solvent (eg, n-hexane, cyclohexane, etc.) using a polymerization initiator (eg, an alkyl lithium compound).
  • a compound having an oxirane skeleton for example, ethylene oxide, propylene oxide, styrene oxide, etc.
  • a lactone compound for example, ⁇ -caprolactone, ⁇ -propiolactone, dimethylpropiolactone ( Pivalolactone), methylvalerolactone, etc.
  • an active hydrogen-containing compound for example, alcohols, carboxylic acids, water, etc.
  • the obtained block copolymer is subjected to hydrogenation reaction in an inert organic solvent (eg, n-hexane, cyclohexane, etc.) in the presence of a hydrogenation reaction catalyst (eg, a Ziegler catalyst comprising an alkylaluminum compound and cobalt, nickel, etc.).
  • a hydrogenation reaction catalyst eg, a Ziegler catalyst comprising an alkylaluminum compound and cobalt, nickel, etc.
  • the hydrogenated product can also be obtained by hydrogenation under the conditions of a reaction temperature of 20 to 150 ° C. and a hydrogen pressure of 1 to 150 kg / cm 2 .
  • the block copolymer before or after hydrogenation may be modified with maleic anhydride or the like.
  • the number average molecular weight of the functional group-containing addition polymerization block copolymer is preferably in the range of 15,000 to 300,000, and more preferably in the range of 20,000 to 100,000.
  • the number average molecular weight of the functional group-containing addition polymerization block copolymer is a value measured in terms of standard polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • MFR melt flow rate of the functional group-containing addition polymerization block copolymer measured at 230 ° C. under a load of 2.16 kg is preferably in the range of 0.01 to 100 g / 10 min.
  • melt flow rate (MFR) of the functional group-containing addition polymerization block copolymer measured at 230 ° C. under a load of 2.16 kg is more preferably in the range of 0.05 to 80 g / 10 minutes.
  • the melt flow rate of the functional group-containing addition polymerization block copolymer is a value measured according to ASTM D-1238.
  • the reaction of the above production methods 1 and 2 (in production method 2, at least one of the two reactions, preferably two reactions, the same shall apply hereinafter) is melt kneaded in the absence of a solvent. Preferably it is done. In particular, the reaction is more preferably carried out by continuously melt-kneading using a multi-screw extruder.
  • the melt kneading temperature is generally in the range of 180 to 280 ° C., preferably in the range of 200 to 260 ° C.
  • the urethanization reaction catalyst may be abbreviated as at least one metal compound selected from the group consisting of an organic zinc compound, an organic bismuth compound, an organic titanium compound, and an organic zirconium compound (hereinafter referred to as “metal compound (M)”). .) Is preferably used. By doing so, a polyurethane block copolymer composition containing at least one metal compound (M) together with the polyurethane block copolymer is obtained.
  • an organic titanium compound and / or an organic zirconium compound are preferably used, and an organic titanium compound is more preferably used.
  • the polyurethane system containing the catalyst obtained thereby is used.
  • the block copolymer composition and the thermoplastic polymer composition of the present invention described later tend to have poor adhesion to silicone.
  • the reason may be that the organotin compound and / or the tertiary amine causes a decrease in the curing function of a silicone curing catalyst (for example, a platinum catalyst), but the exact reason is not clear. From this point, it is preferable that the polyurethane block copolymer composition and the thermoplastic polymer composition of the present invention described later do not contain an organic tin compound and a tertiary amine.
  • organic zinc compound examples include zinc acetylacetonate, zinc propionate, zinc octoate, zinc 2-ethylhexanoate, zinc neodecanoate, zinc laurate, zinc stearate, zinc linoleate, zinc naphthenate, Examples thereof include zinc benzoate and zinc salicylate.
  • organic bismuth compound examples include bis (acetylacetone) bismuth, bismuth 2-ethylhexanoate, bismuth neodecanoate, and bismuth salicylate.
  • organic titanium compounds include tetraalkoxy titanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, and tetrastearyl titanate; titanium acylate compounds such as polyhydroxy titanium stearate; Examples include titanium chelate compounds such as titanium acetylacetonate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium octylene glycol.
  • titanium chelate compounds such as titanium acetylacetonate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium octylene glycol.
  • organic zirconium compound examples include zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium 2-ethylhexanoate, zirconium neodecanoate, zirconium acetylacetonate and the like. it can.
  • the metal compound (M) is preferably used in an amount in the range of 0.1 to 2,000 mass ppm (0.2 mass%) with respect to the mass of the polyurethane block copolymer to be obtained.
  • amount of the metal compound (M) used is less than 0.1 mass ppm, the melt-formability of the resulting polyurethane block copolymer and the adhesion to silicone tend to be reduced.
  • usage-amount of the said metal compound (M) exceeds 2,000 mass ppm, there exists a tendency for the melt moldability (especially melt residence stability) of a polyurethane-type block copolymer to fall.
  • the amount of the metal compound (M) used is more preferably in the range of 0.5 to 200 ppm by mass, and still more preferably in the range of 1 to 200 ppm by mass, with respect to the mass of the resulting polyurethane block copolymer. Particularly preferably, it is in the range of 1 to 100 ppm by mass.
  • the present invention contains the polyurethane block copolymer of the present invention and at least one metal compound (M), and the content of the metal compound (M) is based on the mass of the polyurethane block copolymer.
  • a polyurethane block copolymer composition having a content of 0.1 to 2,000 ppm by mass (preferably 0.5 to 200 ppm by mass, more preferably 1 to 200 ppm by mass, and even more preferably 1 to 100 ppm by mass). Include.
  • the polyurethane block copolymer composition may be abbreviated as at least one compound selected from the group consisting of a phosphorus compound and a phenol compound (hereinafter referred to as “compound (Q)”) together with the metal compound described above. ) Is preferably contained.
  • the compound (Q) functions as a deactivator of the above-described metal compound that can be used as a urethanization reaction catalyst, and the processing stability and durability (water resistance, heat resistance) of the polyurethane block copolymer composition. , Weather resistance, etc.) can be made better.
  • the compound (Q) is mainly used for the purpose of deactivation of the metal compound, it is preferably added after completion of the urethane forming reaction.
  • phosphorus compounds which is one of the compounds (Q)
  • phosphorus compounds represented by the following general formulas (IIa) to (IIc) are preferable.
  • R 3 to R 5 each independently represents a hydrogen atom or a monovalent hydrocarbon group, a and b each represents 0 or 1; in the formula (IIb), R 6 and R 7 represent Each independently a monovalent hydrocarbon group, d, e, f and g each represents 0 or 1; in formula (IIc), R 8 to R 11 are each independently a monovalent hydrocarbon group, R 12 is a divalent hydrocarbon group, h, i, j and k each represents 0 or 1; ]
  • the monovalent hydrocarbon group of R 3 to R 11 is preferably a hydrocarbon group having 1 to 30 carbon atoms.
  • the hydrocarbon group include aliphatic hydrocarbon groups (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group).
  • the aromatic hydrocarbon group may have a substituent such as a halogen atom, an alkoxy group, a phenoxy group or a hydroxyl group on the aromatic ring.
  • the divalent hydrocarbon group for R 12 is preferably a divalent hydrocarbon group having 1 to 50 carbon atoms.
  • the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group (for example, a methylene group, an ethylene group, a propylene group, and a butylene group); a divalent alicyclic hydrocarbon group (for example, a cyclohexylene group); A divalent aromatic hydrocarbon group (for example, a phenylene group, a biphenylene group, a 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl) group, a 4,4′-isopropylidene diphenyl group, etc.) Can be mentioned.
  • the divalent aromatic hydrocarbon group may have a substituent such as a halogen atom, an alkoxy group, a phenoxy group or a hydroxyl group on the aromatic ring.
  • Examples of the phosphorus compound represented by the formula (IIa) include phosphorous acid; phosphoric acid; phosphite ester [for example, methyl phosphite, ethyl phosphite, isopropyl phosphite, butyl phosphite, 2-ethylhexyl phosphite.
  • Examples of the phosphorus compound represented by the formula (IIb) include phosphites [for example, didodecyl pentaerythritol diphosphite, bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite.
  • Examples of the phosphorus compound represented by the above formula (IIc) include phosphites [for example, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, 4,4 '-Isopropylidenediphenoltetrakis (tridecyl) diphosphite etc.]; phosphonites [eg tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphonite etc.] and the like.
  • phosphites for example, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, 4,4 '-Isopropylidenediphenoltetrakis (tridecyl) diphosphite etc.
  • phosphonites eg tetrakis (2,4-d
  • the above phosphorus compounds may be used alone or in combination of two or more.
  • phosphate esters and diesters of phosphonic acid derivatives are preferred, and lauryl phosphate, oleyl phosphate, stearyl phosphate, dilauryl phosphate, dioleyl phosphate, distearyl phosphate, tris (2-ethylhexyl) phosphate, bis (octadecyl)
  • Particularly preferred are pentaerythritol diphosphate, diethyl phenylphosphonate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.
  • Examples of the phenolic compound that is one of the compounds (Q) include hindered phenolic compounds [for example, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-butyl-6- (3′-t-butyl-2′-hydroxy-5′-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-dipentylphenyl) ethyl] -4,6- Dipentylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3 -T-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,1,3-tris (2-methyl-4-hydroxy- -T-butylphenyl) butane, 1,3,5- (t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,
  • the amount used is preferably 1 to 20,000 mass ppm (2 mass%) based on the mass of the polyurethane block copolymer.
  • the usage-amount of the said compound (Q) is less than 1 mass ppm, the melt moldability (especially melt residence stability) of a polyurethane-type block copolymer composition may fall.
  • the amount of the compound (Q) used exceeds 20,000 mass ppm (2 mass%), there are the following problems (1) to (3): (1) Obtained polyurethane block copolymer composition There exists a tendency for the surface state of the molded object comprised from a thing to be impaired.
  • the amount of the compound (Q) used is more preferably in the range of 5 to 2,000 ppm by mass (0.2% by mass), more preferably 5 to 1, based on the mass of the polyurethane block copolymer. It is within the range of 000 mass ppm (0.1 mass%), particularly preferably within the range of 5 to 500 mass ppm, and most preferably within the range of 10 to 250 mass ppm.
  • the blending ratio of the compound (Q) to the metal compound (M) will be described.
  • the ratio of the phosphorus atom in the phosphorus compound is preferably relative to 1 mol of the metal atom in the metal compound (M) present in the polyurethane block copolymer composition. Is from 0.1 to 500 mol, more preferably from 0.2 to 200 mol, and even more preferably from 0.5 to 100 mol.
  • the proportion of the hydroxyl group of the phenol compound is preferably relative to 1 mol of the metal atom in the metal compound (M) present in the polyurethane block copolymer composition. Is 1 to 5,000 mol, more preferably 2 to 2,000 mol, still more preferably 5 to 1,000 mol.
  • an organic polyisocyanate is used per 1 mol of active hydrogen atoms contained in the polymer polyol (a p ) and the chain extender (c).
  • the ratio of the isocyanate group that (b) has is preferably in the range of 0.9 to 1.3 mol.
  • the polyurethane block copolymer obtained by performing the polyurethane forming reaction at the above ratio is further excellent in adhesiveness with silicone.
  • the content of nitrogen atoms derived from isocyanate groups is the polyurethane block ( ⁇ ) obtained in production method 1 or production method 2 Is preferably in the range of 1 to 6.5% by mass based on the mass of the polyurethane obtained in (1).
  • the polyurethane block copolymer obtained by performing the polyurethane forming reaction at the above ratio is further excellent in adhesiveness with silicone.
  • the content of nitrogen atoms derived from the isocyanate group is more preferably in the range of 1 to 6% by mass based on the mass of the polyurethane block ( ⁇ ) obtained by Production Method 1 or the polyurethane obtained by Production Method 2. It is preferably in the range of 1.3 to 5.5% by mass, particularly preferably in the range of 1.6 to 5% by mass.
  • Production method 2 includes an embodiment in which a reaction mixture of a polymer polyol (a p ), an organic polyisocyanate (b), and optionally a chain extender (c) is reacted with a functional group-containing addition polymerization block copolymer. .
  • the reaction mixture also includes a urethane prepolymer.
  • the reaction mixture may contain an unreacted raw material (for example, polymer polyol or the like) or may be post-treated according to a conventional method.
  • a commercial product of a urethane prepolymer formed from a polymer polyol ( ap ), an organic polyisocyanate (b) and optionally a chain extender (c) can also be used as part of the reaction mixture.
  • a functional group-containing addition polymerization block copolymer When a polyurethane block copolymer is produced by production methods 1 and 2, a functional group-containing addition polymerization block copolymer, a polymer polyol (a p ), an organic polyisocyanate (b), and a chain extender as an optional component
  • the ratio to (c) is [mass of functional group-containing addition polymerization block copolymer]: [mass of polymer polyol (a p ) + mass of organic polyisocyanate (b) + mass of chain extender (c) ] Is preferably within the range of 10:90 to 90:10, more preferably within the range of 20:80 to 80:20, and further preferably within the range of 30:70 to 70:30. preferable.
  • the polyurethane block copolymer obtained by the production methods 1 and 2 includes an unreacted functional group-containing addition polymerization block copolymer, an unreacted polymer polyol (a p ), It may be obtained as a polymer composition containing unreacted organic polyisocyanate (b) or unreacted chain extender (c). These contents vary depending on the reaction conditions such as the ratio of raw materials used in the reaction and the reaction temperature.
  • the said polymer composition may contain the polyurethane formed from a polymer polyol ( ap ), organic polyisocyanate (b), and the chain extender (c) as an arbitrary component.
  • the block copolymer composition described above has a polymer block (A) and a polymer block (B), and has no functional group, or a hydrogenated product (addition polymerization block ( ⁇ And a polymer having the same structure as
  • the polymer composition obtained by the above method is pelletized as necessary, and further pulverized to an appropriate size, and then treated with a polyurethane good solvent (such as dimethylformamide),
  • a polyurethane good solvent such as dimethylformamide
  • the polyurethane that did not react with the functional group-containing addition polymerization block copolymer (if present in the polymer composition) is removed, and then a good solvent for the functional group-containing addition polymerization block copolymer
  • a good solvent for the functional group-containing addition polymerization block copolymer For example, when it is present in the polymer composition, it is treated with an unreacted functional group-containing addition polymerization block copolymer and a polymer having the same structure as the addition polymerization block ( ⁇ ). ) Is extracted and removed, and the remaining solid is dried to obtain a polyurethane block copolymer.
  • thermoplastic polymer composition of the present invention contains the above-mentioned polyurethane block copolymer of the present invention and a thermoplastic polymer other than the polyurethane block copolymer.
  • the thermoplastic polymer is not particularly limited, but polyamide, polyester, polyvinylidene chloride, polyvinyl chloride, polycarbonate, acrylic resin, polyoxymethylene resin, saponified ethylene-vinyl acetate copolymer, aromatic vinyl
  • the compound is a copolymer of at least one selected from a vinyl cyanide compound, a conjugated diene and an olefin; a polyurethane; a styrenic polymer; and at least one selected from the group consisting of polyolefins. preferable.
  • polyamide those having an amide bond (—CO—NH—) in the polymer main chain and capable of being melted by heating can be used.
  • polyamide obtained by ring-opening polymerization of a lactam having 3 or more members polylactam
  • polyamide obtained by polycondensation of ⁇ -amino acid polycondensation of dicarboxylic acid and diamine Polyamide obtained; and the like, and one or more of these polyamides
  • specific examples of the lactam include ⁇ -caprolactam, enantolactam, capryllactam, lauryllactam, ⁇ -pyrrolidone and the like.
  • Specific examples of the ⁇ -amino acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like.
  • examples of the dicarboxylic acid used as a raw material for polyamide include aliphatic dicarboxylic acids (for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid).
  • aliphatic dicarboxylic acids for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid.
  • Adipic acid sebacic acid, suberic acid, etc.
  • alicyclic dicarboxylic acids eg, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.
  • aromatic dicarboxylic acids eg, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4 '-Oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4, '- dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, etc.); and the like.
  • diamine examples include aliphatic diamines (for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decane).
  • aliphatic diamines for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decane.
  • alicyclic diamines eg, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, etc
  • polyester those having an ester bond in the polymer main chain and capable of being melted by heating can be used.
  • polyester obtained by reaction of dicarboxylic acid component and diol component; (2) polyester obtained by ring-opening polymerization of lactone (polylactone); (3) hydroxycarboxylic acid or its ester-forming derivative And polyester obtained by condensation.
  • a polyester substantially formed from a dicarboxylic acid component and a diol component is preferable.
  • dicarboxylic acid component used as a raw material for the polyester examples include aromatic dicarboxylic acids (for example, terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4 '-Oxydibenzoic acid, sodium 5-sulfoisophthalate, tetrabromophthalic acid, etc.); saturated aliphatic dicarboxylic acids (eg glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, etc.); alicyclic And dicarboxylic acids (for example, cyclohexane dicarboxylic acid); unsaturated aliphatic dicarboxylic acids (for example, maleic acid, fumaric acid, itaconic acid, etc.); and ester-forming derivatives thereof.
  • diol component used as a raw material for the polyester examples include aliphatic diols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane).
  • aliphatic diols for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane.
  • alicyclic diols eg cyclohexanedimethanol, cyclohexanediol etc.
  • polyalkylene glycols having a molecular weight of 6,000 or less eg diethylene glycol, polyethylene glycol, polypropylene glycol
  • the polyester may contain one or more structural units derived from, for example, a trifunctional or higher functional compound (glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc.). You may have a small amount.
  • a trifunctional or higher functional compound glycolin, trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc.
  • polyvinylidene chloride examples include a polymer having a structural unit derived from vinylidene chloride, preferably in a proportion of 50% by mass or more, more preferably in a proportion of 70 to 98% by mass.
  • a copolymer of polyvinylidene chloride and one or more other unsaturated monomers for example, vinyl chloride, acrylonitrile, acrylic acid ester, acrylic acid, etc.
  • the degree of polymerization of polyvinylidene chloride is not particularly limited, but in general, the degree of polymerization is preferably in the range of 100 to 10,000, more preferably in the range of 400 to 5,000.
  • polyvinyl chloride examples include homopolymers and copolymers of vinyl chloride. These may be used alone or in combination of two or more.
  • vinyl chloride copolymer those having a structural unit derived from vinyl chloride in a proportion of 70% by mass or more are preferable.
  • Polyvinyl chloride copolymers include vinyl chloride and one or more other copolymerizable monomers (eg, ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, acrylonitrile, maleimide, etc.) And a copolymer are preferred.
  • the degree of polymerization of polyvinyl chloride is not particularly limited, but the degree of polymerization is preferably in the range of 100 to 10,000, more preferably in the range of 400 to 5,000.
  • polycarbonate examples include polycarbonate obtained by reacting a dihydroxy compound with phosgene, a carbonic acid diester, or a haloformate.
  • raw material dihydroxy compound examples include aromatic dihydroxy compounds (for example, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl) -p. -Diisopropylbenzene, hydroquinone, resorcinol, etc.), among which bisphenol A is preferred.
  • acrylic resin examples include acrylic resins mainly composed of structural units derived from (meth) acrylic acid esters.
  • the ratio of the structural unit derived from the (meth) acrylic acid ester in the acrylic resin is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • examples of the (meth) acrylic acid ester constituting the structural unit of the acrylic resin include alkyl esters of (meth) acrylic acid (for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate) Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • the acrylic resin can have one or more structural units derived from these (meth) acrylic acid esters.
  • acrylic resin may have 1 type, or 2 or more types of structural units induced
  • the acrylic resin may have a structural unit derived from a vinyl cyanide monomer (for example, (meth) acrylonitrile or the like), preferably in a proportion of 50% by mass or less.
  • the acrylic resin has a structure derived from an aromatic vinyl compound (for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.). You may have a unit in the ratio of preferably 10 mass% or less.
  • aromatic vinyl compound for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.
  • the polyoxymethylene resin is a polymer compound having an oxymethylene group as a main structural unit.
  • the polyoxymethylene resin include: (1) a polymer composed of one or more oxymethylene monomers (for example, formaldehyde, trioxane, tetraoxane, etc.); (2) the oxymethylene monomer; Copolymers comprising other cyclic ethers (ethylene oxide, propylene oxide, oxacyclobutane, 1,3-dioxolane, etc.); (3) the oxymethylene monomers and cyclic esters (for example, ⁇ -propiolactone, ⁇ A copolymer with -butyrolactone, etc.).
  • a terminal-modified polyoxymethylene resin can also be used.
  • a terminal-modified polyoxymethylene resin whose terminal is acetylated with acetic anhydride or the like has better heat resistance than an unmodified one.
  • Examples of the saponified ethylene-vinyl acetate copolymer include those having an ethylene unit in the range of 20 to 60 mol% (more preferably 25 to 60 mol%) and a saponification degree of 95 mol% or more. Preferably used.
  • the melt index of the saponified ethylene-vinyl acetate copolymer is preferably in the range of 0.1 to 25 g / 10 minutes, and more preferably in the range of 0.3 to 20 g / 10 minutes.
  • a saponified ethylene-vinyl acetate copolymer having a preferred melt index has good moldability. The melt index was measured under the conditions of 190 ° C. and 2160 g load according to ASTM D-1238-65T.
  • Examples of the aromatic vinyl compound used in the copolymer include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p- Examples thereof include t-butyl styrene, ethyl styrene, vinyl naphthalene and the like, and one or more of these can be used. Of these, styrene is particularly preferred.
  • Examples of the vinyl cyanide compound used in the copolymer include acrylonitrile and methacrylonitrile.
  • Examples of the conjugated diene used in the copolymer include 1,3-butadiene, 2-methyl-1,3-butadiene [isoprene], 2,3-dimethyl-1,3-butadiene, 2- And neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated petanedienes, substituted linear conjugated hexadienes, and the like. Species or two or more can be used. Of these, 1,3-butadiene and / or 2-methyl-1,3-butadiene are particularly preferred.
  • Examples of the olefin used in the copolymer include ethylene and propylene.
  • copolymer examples include styrene-acrylonitrile copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and acrylonitrile-ethylene-propylene-styrene copolymer (AES resin).
  • AS resin styrene-acrylonitrile copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • AES resin acrylonitrile-ethylene-propylene-styrene copolymer
  • polyurethane examples include polyurethanes other than the polyurethane block copolymer of the present invention. Examples thereof include those obtained by reacting the above other polymer polyol (a p -2), organic polyisocyanate (b) and optionally a chain extender (c).
  • the styrenic polymer examples include polymers containing a structural unit derived from a styrenic monomer, preferably 10% by mass or more, more preferably 50% by mass or more.
  • the styrene monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, 3,4-dimethylstyrene, and the like.
  • the styrenic polymer can have one or more structural units derived from the styrenic monomer.
  • the styrenic polymer together with the structural unit derived from the styrenic monomer, is preferably a structural unit derived from another vinyl monomer at a ratio of preferably 90% by mass or less, more preferably 50% by mass or less. You may have.
  • vinyl monomers include, for example, vinyl cyanide monomers (for example, acrylonitrile, methacrylonitrile, etc.); (meth) acrylic acid alkyl having 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, n -Butyl, i-butyl, hexyl, 2-ethylhexyl, dodecyl, okdadecyl, etc.) esters; esters of (meth) acrylic acid and diols (eg ethylene glycol, propylene glycol, butanediol, etc.); carbons having 1 to 6 carbon atoms Vinyl esters of acids (eg, acetic acid, propionic acid, etc.); unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, maleic acid, etc.); unsaturated dicarboxylic acid anhydrides (eg, maleic anhydride, etc.); (meth) acrylamides ( For example,
  • Copolymers of styrene monomers and other vinyl monomers include at least one of styrene monomers, acrylonitrile, methyl methacrylate, butyl acrylate, N-phenylmaleimide, maleic anhydride
  • a copolymer with at least one selected from the group consisting of butadiene and butadiene is preferable from the viewpoint of mechanical properties and the like.
  • the above styrene polymer is A styrenic polymer containing a rubbery polymer as a constituent component may be used.
  • the glass transition temperature of the rubbery polymer is Preferably 0 ° C. or lower, More preferably, it is ⁇ 20 ° C. or lower.
  • Such rubbery polymers include: Polybutadiene; Styrene-butadiene copolymer; Styrene-butadiene copolymer containing (meth) acrylic acid lower alkyl ester in a proportion of 30% by mass or less; Polyisoprene; Polychloroprene; And so on.
  • Examples of other rubbery polymer that can be included in the styrene polymer include acrylic rubber.
  • the acrylic rubber is preferably a polyalkyl acrylate rubber mainly composed of a structural unit derived from an alkyl having 1 to 8 carbon atoms (more preferably, ethyl, butyl, 2-ethylhexyl) ester of acrylic acid (more preferably Are polyethyl acrylate rubber, polybutyl acrylate rubber, and 2-ethylhexyl polyacrylate rubber).
  • the polyalkyl acrylate rubber may have structural units derived from other monomers (for example, vinyl acetate, methyl methacrylate, styrene, acrylonitrile, vinyl ether, etc.) in an amount of 30% by mass or less in some cases. Good.
  • the polyalkyl acrylate rubber has a structural unit derived from a crosslinkable unsaturated monomer (for example, alkylene diol (meth) acrylate, divinylbenzene, triallyl cyanurate, etc.) in an amount of 5% by mass or less in some cases. You may do it.
  • styrene polymer examples include, for example, ethylene-propylene-nonconjugated diene copolymers (eg, ethylene-propylene-ethylidene norbornene copolymers); styrene polymer blocks— Examples thereof include a hydrogenated product of a block copolymer composed of a butadiene polymer block; a hydrogenated product of a block copolymer composed of a styrene polymer block-isoprene polymer block; and the like.
  • ethylene-propylene-nonconjugated diene copolymers eg, ethylene-propylene-ethylidene norbornene copolymers
  • styrene polymer blocks examples thereof include a hydrogenated product of a block copolymer composed of a butadiene polymer block; a hydrogenated product of a block copolymer composed of a styrene polymer block-isopre
  • the rubbery polymer that can be contained in the above-mentioned styrene polymer the styrene monomer and / or other various unsaturated monomers are grafted to the various rubber polymers mentioned above.
  • polymerization can be mentioned.
  • Styrenic polymer containing rubbery polymer contains one or more of polybutadiene, styrene-butadiene copolymer, polybutyl acrylate rubber, and ethylene-propylene-nonconjugated diene copolymer Styrenic polymers are preferred.
  • polystyrene resin examples include homopolymers of olefins (for example, ethylene, propylene, butylene, etc.); copolymers of two or more kinds of the olefins; one or two or more kinds of the olefins, and one or more kinds of other olefins. And a copolymer with a vinyl monomer.
  • polyolefin examples include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer (preferably vinyl acetate content of 5 to 30% by mass), ethylene-acrylic acid copolymer.
  • Examples thereof include a polymer (preferably having an acrylic acid content of 5 to 30% by mass), an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, and an ethylene-butylene copolymer.
  • a polymer preferably having an acrylic acid content of 5 to 30% by mass
  • an ethylene-propylene copolymer preferably having an acrylic acid content of 5 to 30% by mass
  • an ethylene-propylene copolymer preferably having an acrylic acid content of 5 to 30% by mass
  • an ethylene-propylene copolymer ethylene-propylene-diene copolymer
  • an ethylene-butylene copolymer ethylene-butylene copolymer.
  • olefin homopolymers and copolymers are preferred.
  • the ratio of the polyurethane block copolymer to the other thermoplastic polymer is not particularly limited, but the content of the polyurethane block copolymer is the sum of the two. It is preferably in the range of 1 to 40% by mass, more preferably in the range of 3 to 35% by mass, and still more preferably in the range of 5 to 30% by mass with respect to the mass.
  • the thermoplastic polymer composition of the present invention may contain an optional component other than the polyurethane block copolymer and the thermoplastic polymer, if necessary, within a range not impairing the effects of the present invention.
  • optional components include various additives (for example, release agents, reinforcing agents, colorants, flame retardants, UV absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, antibacterial agents, and stabilizers. Etc.); various fibers (eg glass fiber, polyester fiber etc.); inorganic substances (eg talc, silica etc.); various coupling agents;
  • the proportion of the total mass of the polyurethane-based block copolymer and the thermoplastic polymer can be appropriately set according to the use of the thermoplastic polymer composition of the present invention, but the proportion is the thermoplasticity of the present invention.
  • the polymer composition it is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and still more preferably in the range of 95 to 100% by mass.
  • the thermoplastic polymer composition of the present invention can be produced by melt-kneading a polyurethane block copolymer and other thermoplastic polymers.
  • the melt kneading can be performed using a known apparatus such as an extruder, a mixing roll, or a kneader. Since kneading can be performed more efficiently, it is preferable to use an extruder.
  • the melt kneading temperature is preferably in the range of 150 to 300 ° C., more preferably in the range of 180 to 270 ° C., although it depends on the type of the thermoplastic polymer used.
  • thermoplastic polymers Prior to melt kneading, it is also possible to dry-blend a polyurethane block copolymer, other thermoplastic polymers, and optional components blended as necessary.
  • the polyurethane block copolymer may be melt-kneaded with the thermoplastic polymer in the form of a composition with other components.
  • the thermoplastic polymer may be melt-kneaded with the polyurethane block copolymer in the form of a composition with other components.
  • the polyurethane block copolymer [including the composition of the polyurethane block copolymer and other components] Can be regarded as a masterbatch for modifying the thermoplastic polymer.
  • the present invention also includes a masterbatch containing a polyurethane-based block copolymer.
  • the content of the polyurethane block copolymer in the masterbatch is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, still more preferably in the range of 95 to 100% by mass, in particular. Preferably it is 100 mass%.
  • the content of the structural unit (I) contained in the polyurethane block ( ⁇ ) is preferably 0.1 to 20 mass based on the total mass of the thermoplastic polymer composition. %, More preferably in the range of 0.2 to 10% by weight, still more preferably in the range of 0.4 to 4% by weight.
  • the thermoplastic polymer composition is more excellent in adhesiveness with silicone.
  • thermoplastic polymer composition of the present invention when the above-mentioned polyurethane block copolymer composition containing at least one metal compound (M) is used together with the polyurethane block copolymer, the metal A thermoplastic polymer composition containing the compound (M) is obtained.
  • the content of the metal compound (M) is 0.1 to 2,000 mass ppm (0.2 mass%) based on the mass of the polyurethane block copolymer. ) Is preferable.
  • the content of the metal compound (M) is less than 0.1 ppm by mass, the melt moldability and adhesiveness with silicone of the resulting thermoplastic polymer composition of the present invention tend to be lowered.
  • the content rate of the said metal compound (M) exceeds 2,000 mass ppm, there exists a tendency for the melt moldability (especially melt residence stability) of a polyurethane-type block copolymer to fall.
  • the content of the metal compound is more preferably in the range of 0.5 to 200 ppm by mass, and more preferably 1 to 1 in terms of the mass of the polyurethane block copolymer. It is in the range of 200 ppm by mass, particularly preferably in the range of 1 to 100 ppm by mass.
  • polyurethane block copolymer polyurethane block copolymer composition and thermoplastic polymer composition of the present invention
  • polyurethane block copolymer etc. are melt-molded. Excellent in properties. Therefore, various moldings (for example, for example, injection molding, extrusion molding, inflation molding, blow molding, calender molding, press molding, casting, etc.) from the polyurethane block copolymer of the present invention, etc. Sheet, film, plate, tubular body, rod-shaped body, hollow molded body, various containers, various block-shaped molded bodies, various molds, etc.) can be produced smoothly.
  • the polyurethane block copolymer of the present invention is non-adhesive, hardly adheres to a molding apparatus or a mold, etc., and is excellent in melt moldability. Therefore, various high-quality molded articles can be produced with high productivity. Can be manufactured.
  • thermoplastic polymers especially polyurethane
  • Conventionally employed molding methods, molding conditions, molding apparatuses, etc. can be used to produce a molded body using the.
  • the polyurethane-based block copolymers of the present invention are usually heated and melted at a temperature of 180 to 230 ° C., particularly 190 to 220 ° C., thereby forming the molding.
  • the body can be manufactured smoothly.
  • the polyurethane block copolymer or the like of the present invention is non-tacky and is excellent in adhesion to various materials typified by silicone. Further, the polyurethane block copolymer of the present invention has properties such as mechanical properties (especially abrasion resistance, tensile breaking strength, tensile breaking elongation, etc.), flexibility, oil resistance, water resistance, elastic recovery, etc. Excellent residual resistance, low residual strain, and moderate flexibility. Moreover, the polyurethane block copolymer of the present invention has a smooth surface and a good surface state. Therefore, the polyurethane block copolymer of the present invention can be used for various applications by taking advantage of the above-described properties.
  • Various applications include, for example, conveyor belts; various key sheets and keyboards used for push button switches (for example, those used for mobile phones, home appliances, automobile parts, communication devices, etc.); laminated products; films for various containers And hose; tube; automobile parts; machine parts; shoe soles; watch bands; packing materials; damping materials;
  • the polyurethane block copolymer of the present invention is excellent in adhesiveness with various materials (particularly silicone). Therefore, the polyurethane block copolymer and the like of the present invention can be used as a raw material of a composite molded body in which a member formed therefrom and other members are in contact with each other.
  • the present invention also includes an invention of a composite molded body.
  • the composite molded body has a member (X) containing the polyurethane block copolymer of the present invention and a member (Y) other than the member (X), and the member (X) and the member ( Y) is in contact.
  • the member (X) can be composed of any one of the polyurethane block copolymer, the polyurethane block copolymer composition, and the thermoplastic polymer composition of the present invention.
  • the composite molded body of the present invention is excellent in adhesion between the member (X) and the member (Y).
  • the member (X) of the composite molded body of the present invention can be obtained by the same method as the above-described method for manufacturing a molded body.
  • the member (X) and the member (Y) may be in contact with each other at least at a part of both members.
  • the composite molded body of the present invention has two or more members (X) and / or two or more members (Y), at least one member (X) and at least one member. (Y) may be in contact with at least a part of both members.
  • the configuration of the composite molded body of the present invention is not limited at all.
  • a composite molded body having one member (X) and one member (Y); between two members (Y) Composite molded body in which member (X) is interposed; Composite molded body in which member (Y) is interposed between two members (X); Composite molded body in which members (X) and members (Y) are alternately contacted And the like.
  • One or both of the members (X) and (Y) may be layered. Therefore, the composite molded body of the present invention includes a laminated structure.
  • a two-layer structure having one layered member (X) and one layered member (Y); a layered member (X) is intermediate between two layered members (Y)
  • a three-layer structure existing as a layer a three-layer structure in which a layered member (Y) exists as an intermediate layer between two layered members (X); a layered member (X) and a layered member (Y)
  • a multilayer structure in which four or more layers are alternately stacked.
  • thermoplastic polymers As a material constituting the member (Y), in addition to silicone described later, various thermoplastic polymers (however, other than the polyurethane block copolymer of the present invention) and compositions thereof (however, the polyurethane system of the present invention) Examples include block copolymer compositions and thermoplastic polymer compositions), thermosetting polymers, paper, fabrics, metals, wood, and ceramics.
  • the method for producing the composite molded body of the present invention is not particularly limited.
  • the above-described member (Y) is melt-coated with the polyurethane block copolymer of the present invention; two or more members (Y)
  • the polyurethane block copolymer of the present invention under melting is introduced, and these are bonded and integrated;
  • the member (Y) is placed (inserted) in the mold, and then the molten base A method of filling a polyurethane block copolymer of the present invention into a mold and bonding and integrating them; a thermoplastic member (Y) and a polyurethane block copolymer of the present invention which is thermoplastic A method of co-extrusion and the like to bond and integrate them; a method of pressing the member (X) and the member (Y); and a member (X) and the member (Y) using an adhesive Adhesion / integration method; Kill.
  • the polyurethane block copolymer of the present invention exhibits good melt adhesion to both high polarity polymers and low polarity polymers, and is particularly excellent in melt adhesion to highly polar polymers. . Therefore, for example, the polyurethane block copolymer of the present invention and the polymer (particularly polyamide; polyester; polyvinylidene chloride; polyvinyl chloride; polycarbonate; acrylic resin; polyoxymethylene resin; ethylene-vinyl acetate copolymer) Saponified products; copolymers of aromatic vinyl compounds and vinyl cyanide compounds, at least one selected from conjugated dienes and olefins; polyurethanes; styrenic polymers; Can be manufactured.
  • the polyurethane block copolymer of the present invention and the polymer particularly polyamide; polyester; polyvinylidene chloride; polyvinyl chloride; polycarbonate; acrylic resin; polyoxymethylene resin; ethylene-vinyl acetate copolymer
  • laminated structure (L1) and laminated structure (L2) can be mentioned as preferred embodiments of the composite molded body of the present invention.
  • Laminated structure (L1) a laminated structure having at least part of a structure in which these are laminated in the form of layer (X ′) / layer (Y′1), and the layer (X ′) Including the polyurethane block copolymer of the invention, the layer (Y′1) is composed of polyamide, polyester, polyvinylidene chloride, polyvinyl chloride, polycarbonate, acrylic resin, polyoxymethylene resin, ethylene-vinyl acetate copolymer.
  • the layer (Y′2) includes a combination, and the layer (Y
  • the layer (X ′) can be composed of any one of the polyurethane block copolymer, the polyurethane block copolymer composition, and the thermoplastic polymer composition of the present invention.
  • Examples of the polar polymer such as polyamide that can be included in the layer (Y′1) or the layer (Y′2) include the polymers exemplified above as the thermoplastic polymer included in the thermoplastic polymer composition of the present invention. Similar ones can be used.
  • the said layer (Y'1) may be comprised only from the said polar polymer, as long as the property is not impaired, it contains the 1 type, or 2 or more types of arbitrary component as needed. Also good.
  • the optional component include a heat stabilizer (eg, metal soap, phosphorus compound, sulfur compound, phenol compound, L-ascorbic acid, epoxy compound, etc.), light stabilizer, plasticizer (eg, aliphatic dicarboxylic acid).
  • the content of the polar polymer in the layer (Y′1) is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and 95 to 100%. More preferably, it is in the range of mass%.
  • the layer (Y′2) may be composed only of the nonpolar polymer, but contains one or more optional components as necessary as long as the properties are not impaired. You may do it.
  • the optional component include a heat stabilizer (eg, metal soap, phosphorus compound, sulfur compound, phenol compound, L-ascorbic acid, epoxy compound, etc.), light stabilizer, plasticizer (eg, aliphatic dicarboxylic acid). Ester, hydroxy polycarboxylic acid ester, fatty acid ester, polyester compound, phosphate ester, etc.), inorganic fine powder, lubricant (organic lubricant, etc.), dispersant, dye / pigment, antistatic agent, antioxidant, mold release agent And flame retardants and ultraviolet absorbers.
  • a heat stabilizer eg, metal soap, phosphorus compound, sulfur compound, phenol compound, L-ascorbic acid, epoxy compound, etc.
  • plasticizer eg, aliphatic dicarboxylic acid. Ester, hydroxy polycarboxylic acid
  • the content of the nonpolar polymer in the layer (Y′2) is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, More preferably, it is in the range of 100% by mass.
  • the unsaturated hydrocarbon group in the structural unit (I) contained in the polyurethane-based block copolymer or the like of the present invention is a silicone having a hydrogen atom bonded to a silicon atom (organohydrogenpolyethylene in the presence of a hydrosilylation catalyst. It also reacts with silicones having unsaturated groups such as vinyl groups in the molecule. Therefore, the polyurethane block copolymer and the like of the present invention and silicone can be firmly bonded without subjecting them to surface activation treatment (for example, primer treatment).
  • the polyurethane block copolymer of the present invention is a composite molded body [particularly, a member composed of the polyurethane block copolymer of the present invention, a member containing silicone (hereinafter referred to as “silicone member”). "Is sometimes abbreviated as”) is extremely effective in the production of a strongly bonded laminated structure]. Therefore, this invention also includes the said composite molded object whose said member (Y) is a silicone member.
  • the above-mentioned silicone-based member may be composed only of silicone or may be composed of a silicone composition containing silicone.
  • the silicone content in the silicone-based member is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and particularly preferably in the range of 95 to 100% by mass.
  • the adhesive strength of a silicone type member and member (X) can be improved as a silicone content rate exists in a preferable range.
  • the above-mentioned silicone composition includes, for example, various additives (for example, release agents, reinforcing agents, colorants, flame retardants, ultraviolet absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, antibacterial agents, and stable agents. Agents); various fibers (for example, glass fibers, polyester fibers, etc.); inorganic substances (for example, talc, silica, etc.); various coupling agents.
  • additives for example, release agents, reinforcing agents, colorants, flame retardants, ultraviolet absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, antibacterial agents, and stable agents.
  • various fibers for example, glass fibers, polyester fibers, etc.
  • inorganic substances for example, talc, silica, etc.
  • various coupling agents for example, glass fibers, polyester fibers, etc.
  • the silicone-based member is preferably formed by simply curing the curable silicone composition.
  • the curable silicone composition include (i) a room temperature curable silicone composition that cures at room temperature to form a silicone rubber or silicone resin, and (ii) heat that cures upon heating to form a silicone rubber or silicone resin.
  • a cross-linked silicone composition (such as a methyl vinyl silicone composition) can be used.
  • the room temperature curable silicone composition (i) is preferable, and a room temperature curable silicone rubber composition that is cured at room temperature to form a silicone rubber is more preferable.
  • the room temperature curable silicone composition is soft paste or semi-fluid before curing, and is excellent in handleability.
  • the (i) room-temperature curable silicone composition includes a one-part silicone composition that cures with moisture in the air and a two-part silicone composition that cures with a curing agent.
  • a one-component room-temperature curable silicone composition tends to be inferior in releasability and handleability because it has adhesiveness to a molding apparatus and different materials.
  • the two-component room temperature curable silicone composition exhibits excellent adhesion to dissimilar materials and is excellent in handleability. Accordingly, a two-pack type room temperature curable silicone composition is preferable, and a two-pack type room temperature curable silicone rubber composition is more preferable.
  • the two-pack type room temperature curable silicone composition is roughly classified into two types, a condensation reaction type and an addition reaction type, depending on the functional group introduced into the silicone.
  • a condensation reaction type a hydroxyl-terminated reactive diorganopolysiloxane and an alkoxy-terminated reactive diorganopolysiloxane are polymerized using a catalyst (for example, a tin compound).
  • a catalyst for example, a tin compound
  • an organopolysiloxane having an alkenyl group (for example, a vinyl group) and an organohydrogenpolysiloxane (hydrogenated polysiloxane) having a hydrogen atom bonded to a silicon atom are converted into a noble metal compound (for example, platinum).
  • Palladium, iridium, rhodium, osmium, ruthenium, etc. Palladium, iridium, rhodium, osmium, ruthenium, etc
  • the addition reaction type curable silicone composition is preferable.
  • the addition reaction type curable silicone composition is excellent in reactivity with the polyurethane block copolymer having the structural unit (I) in the molecule. By using this, the member (X) and the silicone member are used. And a composite molded body having improved adhesive strength can be produced smoothly.
  • the addition reaction type curable silicone composition includes a curable silicone composition containing an organohydrogenpolysiloxane and a hydrosilylation catalyst, particularly ( ⁇ ) an organohydrogenpolysiloxane and a hydrosilylation catalyst, and an alkenyl group.
  • a curable silicone composition containing no organopolysiloxane and having ( ⁇ ) an organohydrogenpolysiloxane, an alkenyl group-containing organopolysiloxane and a hydrosilylation catalyst can be used. It is.
  • the organohydrogenpolysiloxane may be any organohydrogenpolysiloxane having at least one hydrogen atom bonded to a silicon atom in one molecule, and is not particularly limited.
  • organohydrogenpolysiloxanes diorganohydrogenpolysiloxane in which one or more monovalent organic groups (organogroups) bonded to silicon atoms in the diorganopolysiloxane molecule are replaced with hydrogen atoms.
  • Siloxane is preferable, and dimethyl hydrogen polysiloxane in which one or more (particularly 2 to 10) methyl groups bonded to silicon atoms in the dimethylpolysiloxane molecule are replaced with hydrogen atoms is more preferable.
  • the diorganohydrogenpolysiloxane (particularly the dimethylhydrogenpolysiloxane) is excellent in flexibility, elastic properties, curability and the like and is easily available.
  • the organopolysiloxane having an alkenyl group may be any organopolysiloxane having one or more alkenyl groups (for example, vinyl group, allyl group) in one molecule, and is not particularly limited.
  • organopolysiloxanes having such alkenyl groups diorganopolysiloxanes having one or more alkenyl groups bonded to silicon atoms are preferred, and one of the methyl groups bonded to silicon atoms in the dimethylpolysiloxane molecule. More preferred is dimethylpolysiloxane in which one or more (particularly 2 to 10) are replaced by alkenyl groups.
  • the diorganopolysiloxane (particularly the dimethylpolysiloxane) is excellent in flexibility, elastic properties, curability and the like and is easily available.
  • the molecular weight of the organohydrogenpolysiloxane and the organopolysiloxane having an alkenyl group is not particularly limited, and those suitable for each application can be used depending on the application of the composite molded article of the present invention. .
  • the type of hydrosilylation catalyst used in the curable silicone composition is not particularly limited, and any conventionally used hydrosilylation catalyst can be used.
  • a noble metal for example, platinum, palladium, iridium, rhodium, osmium, ruthenium, etc.
  • an organic peroxide for example, an organic peroxide; an azo compound; Among them, a platinum complex having high reactivity and excellent handleability is preferable.
  • an alcohol solution of chloroplatinic acid; a compound in which an aliphatic unsaturated hydrocarbon group-containing compound is coordinated after neutralizing the chloroplatinic acid solution is more preferable.
  • the content of the hydrosilylation catalyst in the curable silicone composition is usually preferably about 1 ppm by mass to 1% by mass with respect to the total mass of the organohydrogenpolysiloxane and the organopolysiloxane having an alkenyl group. Preferably, it is about 10 to 500 mass ppm.
  • the curable silicone composition may be a silicone-based adhesive or printing ink.
  • the composite molded body of the present invention having a silicone-based member, one or two or more members (X) and only one or two or more silicone-based members, or a member ( X) and a member made of a material different from that of the silicone-based member may be hereinafter referred to as “other material member”.
  • the number of other material members may be one, or two or more.
  • the composite molded body of the present invention is preferably abbreviated as a layered member (X) (hereinafter sometimes abbreviated as “layer (X ′)”) and a layered silicone-based member (hereinafter abbreviated as “silicone layer”).
  • X layered member
  • silicon layer a layered silicone-based member
  • the number of layers in such a laminated structure is not particularly limited, and may be any of two layers, three layers, four layers, five layers or more.
  • the layer (X ′) and the silicone layer further has another material member in the form of a layer (hereinafter sometimes abbreviated as “other material layer”)
  • the layer (X ′) And / or the silicone layer and the other material layer may be bonded and laminated on the entire surface of one surface, or may be bonded or laminated continuously or intermittently (for example, line bonding, point bonding, partial bonding, etc.) Surface adhesion, etc.).
  • a laminated structure having a layer (X ′) and a silicone layer for example, a two-layer structure comprising layer (X ′) / silicone layer; silicone layer / layer (X ′) / 3-layer structure consisting of silicone layer; 3-layer structure consisting of layer (X ′) / silicone layer / layer (X ′); layer (X ′) / silicone layer / layer (X ′) / silicone layer Four-layer structure; three-layer structure composed of another material layer / silicone layer / layer (X ′); three-layer structure composed of silicone layer / layer (X ′) / other material layer; silicone layer / layer ( Examples thereof include a 5-layer structure comprising X ′) / silicone layer / layer (X ′) / other material layers.
  • the two or more layers (X ′) are layers containing the polyurethane-based block copolymer of the present invention
  • the layers may be the same layer or may be different in the type, content, layer thickness, and the like of the polyurethane block copolymer contained.
  • the two or more silicone layers may be the same layer or different layers.
  • the total thickness of the laminated structure, the thickness of the layer (X ′), and the thickness of the silicone layer are not particularly limited. It can adjust according to the use etc. of a structure.
  • the thickness of the layer (X ′) (one layer) is generally 10 ⁇ m or more, preferably in the range of 20 to 3,000 ⁇ m, more preferably in the range of 50 to 2,000 ⁇ m.
  • the thickness of the layer) is generally 10 ⁇ m or more, preferably in the range of 20 to 3,000 ⁇ m, more preferably in the range of 50 to 2,000 ⁇ m. If the layer (X ′) and the silicone layer having such a thickness are used, a laminated structure having excellent adhesion between these layers can be easily produced.
  • the layer (X ′) is preferably formed from a film from the viewpoints of ease of production, heat resistance, post-processing passability, and the like.
  • the thickness of the film is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 200 ⁇ m, and still more preferably in the range of 40 to 150 ⁇ m.
  • a silicone type member is formed on member (X) by hardening a curable silicone composition on member (X).
  • the manufacturing method including the process to make is preferable. According to the said manufacturing method, even if it does not perform a surface activation process, the composite molded object which is excellent in the adhesive strength of member (X) and a silicone type member is obtained easily.
  • the method for curing the curable silicone composition on the polyurethane-based member is not particularly limited, and for example, the following methods (1) to (5) can be employed: (1) A method in which a curable silicone composition is coated on the member (X), and then the curable silicone composition is cured to produce a composite molded body.
  • the member (X) is placed (inserted) in the mold, and then the molten curable silicone composition is filled into the mold to cure the curable silicone composition.
  • (3) A method of extruding a curable silicone composition that is thermoplastic onto the member (X), curing the curable silicone composition, and bonding / integrating the member (X) and the silicone-based member.
  • (4) A method of applying a silicone-based adhesive or printing ink as a curable silicone composition on the member (X) and curing them.
  • a curable silicone composition that is thermoplastic and the thermoplastic polymer composition of the present invention are co-extruded to cure the curable silicone composition and to form a member (X) and a silicone-based member.
  • the composite molded body of the present invention can be used for various applications depending on the properties of the member (X) and member (Y) (silicone-based member etc.) constituting the composite molded body.
  • automotive interior parts for example, instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers, etc.
  • automotive exterior parts for example, moldings, etc.
  • Vacuum cleaner bumper for example, Refrigerator door; Camera grip; Electric tool grip; Household cooking utensils; Remote control switch;
  • Various key tops for OA equipment Various key sheets and keyboards used for push button switches (cell phones, household appliances, automobiles) Parts, parts used in communication equipment, etc.); household appliance parts (for example, housings); sports equipment (for example, underwater glasses); various covers; various industrial parts with packing (for example, wear resistance, airtightness, soundproofing, prevention) For vibration and other purposes); Wire coatings; belt; hose; tube; sole; watchband; silencing gear
  • Adhesiveness with silicone Using the laminated structures obtained in the following examples or comparative examples, a member containing a polyurethane block copolymer or polyurethane and a material other than polyurethane (silicone, ABS resin or polypropylene) in a 180 ° C. peel test The resistance value (adhesive strength) at the time of peeling was measured using “Instron 5566” manufactured by Instron Japan, at room temperature and at a tensile rate of 100 mm / min. This adhesive strength was used as an index of adhesiveness.
  • Polyester diol produced by reacting 1,4-butanediol with adipic acid and having a number of hydroxyl groups per molecule of 2.00 and a number average molecular weight of 1,000
  • F-TPS Hydrogenated product of a triblock copolymer having a polystyrene block-poly (isoprene / butadiene) block-polystyrene block type structure and having a hydroxyl group at one end of the molecule [number average molecular weight: 50,000, styrene content: 30% by mass, hydrogenation rate in hydrogenated poly (isoprene / butadiene) block: 98 mol%, ratio of isoprene to butadiene: 50/50 (mass ratio), average number of hydroxyl groups per molecule: 0.9 ]
  • the f-TPS was produced using styrene, isoprene and butadiene as raw materials according to the method described in Reference Example 1 of JP-A-10-139963.
  • TPS-OH [number average molecular weight: 50,000, styrene content: 30 mass%, hydrogenation rate in hydrogenated poly (isoprene / butadiene) block: 98 mol%, ratio of isoprene to butadiene: 50 / 50 (mass ratio)
  • Data of the TPS [number average molecular weight: 50,000, styrene content: 30% by mass, hydrogenation rate in poly (isoprene / butadiene) block: 98 mol%, ratio of isoprene to butadiene: 50/50 (mass ratio) ].
  • thermoplastic polyurethane (C1)
  • POH polymer polyol
  • TI urethanization reaction catalyst
  • BD chain extender
  • MDI organic polyisocyanate
  • thermoplastic polyurethane (C1) The obtained polyurethane melt was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets. The pellet was dehumidified and dried at 80 ° C. for 4 hours to obtain a thermoplastic polyurethane (C1). It was 2,010 Pa.s when the melt viscosity of the obtained thermoplastic polyurethane (C1) was measured by the above-mentioned method on 200 degreeC conditions.
  • Example 1 Production of Polyurethane Block Copolymer Polyolefin polyol (POG) having structural unit (I) containing 100 mass ppm of urethanization reaction catalyst (TI), 10 mass ppm of urethanization reaction catalyst (TI)
  • f-TPS functional group-containing addition polymerization block copolymer
  • the obtained melt was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets.
  • the pellets were dehumidified and dried at 80 ° C. for 4 hours to obtain a polymer composition containing a polyurethane block copolymer. It was 1,540 Pa.s when the melt viscosity of the obtained polymer composition was measured on the conditions of 220 degreeC by the above-mentioned method.
  • polyurethane block copolymer was a diblock copolymer.
  • One block is a polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type block [addition polymerization block ( ⁇ )], and the other block is a POG unit.
  • Polyurethane block [polyurethane block ( ⁇ )] composed of POH units, MDI units and BD units.
  • the extract of cyclohexane contained a triblock copolymer, which was also recovered.
  • the two blocks are polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type block [addition polymerization block ( ⁇ )], and the other block is a unit of POG.
  • Polyurethane block [polyurethane block ( ⁇ )] composed of POH units, MDI units and BD units.
  • each content of the diblock copolymer contained in the polymer composition, polyurethane extracted using dimethylformamide, and TPS-OH, TPS extracted using cyclohexane, and the triblock copolymer When the polymer composition is 100% by mass, the diblock copolymer is 14% by mass, the polyurethane is 33% by mass, the TPS-OH is 0% by mass, the TPS is 5% by mass, the triblock copolymer. It was 48 mass%.
  • the content of the structural unit (I) of the polyurethane block ( ⁇ ) in the total mass of the polyurethane block copolymer (the diblock copolymer and the triblock copolymer) is 6.8% by mass. there were.
  • Example 2 Production of a laminated structure Sheet Production
  • the polymer composition containing the polyurethane block copolymer obtained in Example 1 was subjected to a T-die type single screw extruder (25 mm ⁇ , cylinder temperature: 200 to 210 ° C., die temperature: 210 ° C.). After being melt melt-kneaded, the kneaded product is extruded onto a 30 ° C. cooling roll, cooled, and wound up at a winding speed of about 0.2 m / min. A sheet (thickness 1 mm) composed of the combined composition was produced.
  • This molded body and the above-mentioned cut-out test piece were superposed and pressure-treated using a manual press device (manufactured by Marushichi Co., Ltd., M4A type) (temperature: 135 ° C., pressure: attached gauge pressure gauge) 1 kg / cm 2 , time: 3 minutes), a laminated structure having a two-layer structure composed of a member containing a polyurethane block copolymer and a member made of ABS resin was obtained.
  • the adhesive strength between the member containing the polyurethane block copolymer in the obtained laminated structure and the member composed of ABS resin was measured by the above evaluation method, it was 1,000 g / cm or more. It was.
  • laminated structure (3) In the same manner as in the production of the laminated structure (2) described above, a laminated structure having a two-layer structure comprising a member containing a polyurethane block copolymer and a member composed of an ABS resin is produced. Apply a liquid curable silicone composition (“Shin-Etsu Silicone KE-2000” manufactured by Shin-Etsu Chemical Co., Ltd.) (mixed liquid A and liquid B) to a thickness of about 100 ⁇ m on the side containing the polymer. These were left in a 120 ° C.
  • a liquid curable silicone composition (“Shin-Etsu Silicone KE-2000” manufactured by Shin-Etsu Chemical Co., Ltd.) (mixed liquid A and liquid B)
  • This molded body and the above-mentioned cut-out test piece were superposed and pressure-treated using a manual press device (manufactured by Marushichi Co., Ltd., M4A type) (temperature: 135 ° C., pressure: attached gauge pressure gauge) 1 kg / cm 2 , time: 3 minutes), a laminated structure having a two-layer structure composed of a member containing a polyurethane block copolymer and a member made of polypropylene was obtained. It was 700 g / cm when the adhesive strength between the member containing the polyurethane-type block copolymer in the obtained laminated structure and the member comprised from a polypropylene was measured by said evaluation method.
  • a laminated structure having a two-layer structure comprising a member containing a polyurethane block copolymer and a member made of polypropylene is produced.
  • a liquid curable silicone composition (“Shin-Etsu Silicone KE-2000” manufactured by Shin-Etsu Chemical Co., Ltd.) (mixed liquid A and liquid B) to a thickness of about 100 ⁇ m on the member side including the coalescence, These were allowed to stand in a hot air dryer at 120 ° C.
  • thermoplastic polyurethane (C1) obtained in Production Example 1 was melt-kneaded using a T-die type single screw extruder (25 mm ⁇ , cylinder temperature: 195 to 205 ° C., die temperature: 200 ° C.) Then, the kneaded product is extruded onto a cooling roll at 30 ° C., cooled, and wound at a winding speed of about 2 m / min, whereby a film (thickness 100 ⁇ m) composed of thermoplastic polyurethane (C1) is obtained. Manufactured.
  • a test piece having a width of 25 mm and a length of 100 mm was cut out from the film (rolled film) obtained in the manufacture of the film.
  • a liquid curable silicone composition (“Shin-Etsu Silicone KE-2000” manufactured by Shin-Etsu Chemical Co., Ltd.) (mixed liquid A and B) was applied to the test piece to a thickness of about 100 ⁇ m.
  • a laminated structure in which both members were bonded was not obtained (adhesive strength was evaluated as 0 g / cm).
  • thermoplastic Polyurethane obtained in Production Example 1 ( C1) was dry blended in the proportions shown in Table 1 below.
  • the obtained mixture was melt-kneaded using a T-die type single screw extruder (25 mm ⁇ , cylinder temperature: 205 to 215 ° C., die temperature: 205 ° C.), and then the kneaded product was extruded onto a 30 ° C. cooling roll.
  • the film (thickness 100 ⁇ m) composed of the thermoplastic polymer composition was produced by cooling and winding it at a winding speed of about 2 m / min.
  • This molded body and the above-described cut specimen are superposed and pressure-treated using a manual press device (manufactured by Marushichi Co., Ltd., M4A type) (temperature: 135 ° C., pressure: attached gauge) 2 layers consisting of a member composed of a thermoplastic polymer composition (a member including a polyurethane block copolymer) and a member composed of an ABS resin based on a pressure gauge of 1 kg / cm 2 , time: 3 minutes) A laminated structure having a structure was obtained.
  • the adhesive strength between the member composed of the thermoplastic polymer composition and the member composed of the ABS resin was measured by the above evaluation method, it was 1,000 g / cm or more.
  • Two-layer structure comprising a member composed of a thermoplastic polymer composition (a member including a polyurethane block copolymer) and a member composed of an ABS resin in the same manner as in the production of the laminated structure (2) described above.
  • a liquid curable silicone composition (“Shin-Etsu Silicone KE-2000” manufactured by Shin-Etsu Chemical Co., Ltd.) (liquid A and liquid B) is produced on the side of the member composed of the thermoplastic polymer composition.
  • liquid A and liquid B is produced on the side of the member composed of the thermoplastic polymer composition.
  • a laminated structure having a three-layer structure of member / member containing silicone was obtained.
  • the adhesive strength between the member composed of the thermoplastic polymer composition and the member containing silicone was measured and found to be 1,000 g / cm or more.
  • thermoplastic polymer composition containing the polyurethane-based block copolymer of the present invention is excellent in adhesiveness to various materials (particularly silicone). Therefore, if the thermoplastic polymer composition of the present invention is used, a member containing the thermoplastic polymer composition and silicone or other material can be used without prior surface activation treatment (primer treatment, etc.). It is possible to easily manufacture a composite molded body in which the containing member is sufficiently adhered. Furthermore, from the results of Examples 3 and 4, thermoplastic polymer compositions obtained by blending a masterbatch containing the polyurethane block copolymer of the present invention with thermoplastic polyurethane (thermoplastic polymer) are also various materials.
  • the polyurethane block copolymer, polyurethane block copolymer composition, and thermoplastic polymer composition of the present invention are excellent in adhesiveness to various materials (particularly silicone) and are subjected to prior surface activation treatment (primer). Even if it does not carry out a process etc., it can fully be made to adhere to the above-mentioned various materials. Therefore, these can be suitably used for various applications, for example, in the form of a molded body or a composite molded body.
  • the present invention is based on Japanese Patent Application No. 2009-111318 filed in Japan, the contents of which are all included in this specification.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un copolymère bloc de polyuréthane constitué de blocs de polymérisation par addition (α), et de blocs de polyuréthane (β). Les blocs de polymérisation par addition (α) sont dérivés, soit d'un copolymère bloc comportant des blocs de polymère (A) contenant, d'une part des unités de composés aromatiques vinyliques, et d'autre part des blocs de polymère (B) qui contiennent des unités diène conjuguées, soit dudit copolymère bloc auquel de l'hydrogène a été ajouté. Ces blocs de polyuréthane (β) comportent une unité structurelle (I) représentée par la formule générale (I).
PCT/JP2010/057610 2009-04-30 2010-04-28 Copolymère bloc de polyuréthane WO2010126098A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020054348A1 (fr) * 2018-09-10 2020-03-19 三洋化成工業株式会社 Composition de résine de polyuréthane
JP2022507949A (ja) * 2018-12-29 2022-01-18 シャンドン ブランデン メディカル デバイス カンパニー リミテッド 高機械特性の医療用シリコーンゴムおよびその調製方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5285297A (en) * 1976-01-02 1977-07-15 Atlantic Richfield Co Process for producing polyurethane elastomer
JPS57147512A (en) * 1981-03-09 1982-09-11 Hisao Motomura Water-swelling composition
JPS5876414A (ja) * 1981-10-30 1983-05-09 Okura Ind Co Ltd 嫌気硬化性組成物及びその製造方法
JPS6136315A (ja) * 1984-07-30 1986-02-21 Nisshinbo Ind Inc 防振材料
JPH0413793A (ja) * 1990-05-02 1992-01-17 Sumitomo Rubber Ind Ltd 保冷材
WO2002057332A1 (fr) * 2001-01-22 2002-07-25 Toyo Ink Manufacturing Co., Ltd. Composition de resine, feuille obtenue a partir de cette composition, procede de production de feuille et objet forme

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5285297A (en) * 1976-01-02 1977-07-15 Atlantic Richfield Co Process for producing polyurethane elastomer
JPS57147512A (en) * 1981-03-09 1982-09-11 Hisao Motomura Water-swelling composition
JPS5876414A (ja) * 1981-10-30 1983-05-09 Okura Ind Co Ltd 嫌気硬化性組成物及びその製造方法
JPS6136315A (ja) * 1984-07-30 1986-02-21 Nisshinbo Ind Inc 防振材料
JPH0413793A (ja) * 1990-05-02 1992-01-17 Sumitomo Rubber Ind Ltd 保冷材
WO2002057332A1 (fr) * 2001-01-22 2002-07-25 Toyo Ink Manufacturing Co., Ltd. Composition de resine, feuille obtenue a partir de cette composition, procede de production de feuille et objet forme

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020054348A1 (fr) * 2018-09-10 2020-03-19 三洋化成工業株式会社 Composition de résine de polyuréthane
CN112654676A (zh) * 2018-09-10 2021-04-13 三洋化成工业株式会社 聚氨酯树脂组合物
CN112654676B (zh) * 2018-09-10 2022-12-06 三洋化成工业株式会社 聚氨酯树脂组合物
JP2022507949A (ja) * 2018-12-29 2022-01-18 シャンドン ブランデン メディカル デバイス カンパニー リミテッド 高機械特性の医療用シリコーンゴムおよびその調製方法

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