WO2015087955A1 - 熱可塑性エラストマー組成物、成形体及び接着剤 - Google Patents
熱可塑性エラストマー組成物、成形体及び接着剤 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Definitions
- the present invention relates to a thermoplastic elastomer composition, a molded article and an adhesive containing a block copolymer composed of a polymer block comprising a structural unit derived from an aromatic vinyl compound and a polymer block comprising a structural unit derived from farnesene.
- a block copolymer composed of a polymer block comprising a structural unit derived from an aromatic vinyl compound and a polymer block comprising a structural unit derived from farnesene.
- Ceramics, metals, and synthetic resins with excellent durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, machine parts, and automobile parts.
- these members are bonded or combined with elastomer members with excellent flexibility for the purpose of fixing to other structural members or for purposes such as shock absorption, damage prevention or sealing. There are cases where it is used.
- a styrenic thermoplastic elastomer excellent in flexibility and mechanical properties, and further in molding processability may be suitably used.
- the styrenic thermoplastic elastomer refers to a block copolymer having a polymer block composed of an aromatic vinyl compound unit and a polymer block composed of a conjugated diene compound unit or a hydrogenated product thereof.
- styrenic thermoplastic elastomer is a material having low polarity, it has a problem that its adhesive strength to ceramics, metal, etc. is not sufficient, and melt adhesion is difficult as it is.
- Patent Documents 1 to 6 a method of applying an adhesive or preliminarily treating the surface of ceramics, metal, or synthetic resin is disclosed (Patent Documents 1 to 6). 6).
- Patent Documents 1 to 6 have problems that not only the process is complicated but also the productivity is low and the manufacturing cost is high.
- a thermoplastic polymer composition containing a styrene-based thermoplastic elastomer and polyvinyl acetal having excellent adhesion to ceramics, metals and synthetic resins is disclosed (see Patent Document 7). .
- This thermoplastic polymer composition can be adhered to ceramics, metal and synthetic resin only by heat treatment without applying an adhesive or applying a primer.
- thermoplastic polymer composition disclosed in Patent Document 7 is 200 ° C. or higher (particularly 240 when ceramics or metals are bonded) in the manufacturing process of a molded body bonded to ceramics, metals or synthetic resins. Bonding after heat treatment at a high temperature of °C or higher.
- many synthetic resin members melt and deform at a high temperature of 200 ° C. or higher, there is a problem in that the synthetic resin members around the bonded portions that are heated at the same time are destroyed.
- the adhesive molded body of a thermoplastic elastomer and a base material it is said that the interfacial peeling does not occur during the peeling test, and the cohesive failure is superior in the performance as an adhesive.
- the thermoplastic polymer composition disclosed in Patent Document 7 may cause interfacial peeling, and there has been a demand for a thermoplastic elastomer having a more excellent adhesive force and a fracture mode of cohesive failure.
- the present invention has been made in view of the above circumstances, and is excellent in flexibility and moldability, and can be used at a low temperature (for example, 190 ° C. or less) with ceramics, metal, resin, etc. without performing primer treatment.
- An object of the present invention is to provide a thermoplastic elastomer composition that can be bonded by heat treatment and has a cohesive failure in a peel test and has a strong adhesive force, and a molded product and an adhesive made thereof.
- thermoplastic elastomer composition containing a specific hydrogenated block copolymer and a polar group-containing olefin-based polymer can solve the above-mentioned problems, leading to the present invention.
- the gist of the present invention is the following [1] to [3].
- a polymer block (a) composed of a structural unit derived from an aromatic vinyl compound and 1 to 100% by mass of a structural unit (b1) derived from farnesene, and a structural unit derived from a conjugated diene other than farnesene (b2) And a polymer block (b) containing 99 to 0% by mass, wherein the mass ratio [(a) / (b)] of the polymer block (a) to the polymer block (b) is 1/99 to 70.
- thermoplastic elastomer composition containing 5 to 300 parts by mass of a polar group-containing olefin polymer (B) with respect to 100 parts by mass of the hydrogenated block copolymer (A) that is / 30.
- An adhesive comprising the thermoplastic elastomer composition according to [1].
- a molded article comprising the thermoplastic elastomer composition according to [1].
- the present invention has excellent flexibility and moldability, and can be bonded to ceramics, metals, resins, etc. by heat treatment at a low temperature (eg, 190 ° C. or less) without being subjected to primer treatment, and a peel test.
- a low temperature eg, 190 ° C. or less
- thermoplastic elastomer composition comprises 1 to 100% by mass of a polymer block (a) comprising a structural unit derived from an aromatic vinyl compound and a structural unit (b1) derived from farnesene.
- the hydrogenated block copolymer (A) used in the thermoplastic elastomer composition of the present invention comprises a polymer block (a) composed of a structural unit derived from an aromatic vinyl compound and a structural unit (b1) derived from farnesene.
- a hydrogenated product of a block copolymer hereinafter sometimes referred to as “block copolymer (P)”) having a mass ratio [(a) / (b)] of 1/99 to 70/30 (hereinafter referred to as “block copolymer (P)”) And “hydrogenated block copolymer (A)”).
- thermoplastic elastomer composition of the present invention contains the hydrogenated block copolymer (A) containing a specific amount of the structural unit (b1) derived from farnesene, it does not contain a structural unit derived from farnesene. Compared to the above, it is superior in flexibility and moldability, can be bonded to ceramics, metals, resins, etc. by heat treatment at low temperature (eg 190 ° C or less) without being subjected to primer treatment, etc. The form is cohesive failure and has a strong adhesive force. Moreover, since the heat shrinkage rate after the heat treatment is also small, the generation of thermal stress due to the heat treatment is suppressed, and the adhesive force becomes stronger.
- the polymer block (a) is composed of a structural unit derived from an aromatic vinyl compound.
- the aromatic vinyl compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2- Examples thereof include vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethyl styrene, vinyl pyridine, 4-methoxy s
- the polymer block (b) contains 1 to 100% by mass of farnesene-derived structural units (b1) and 99 to 0% by mass of structural units (b2) derived from conjugated dienes other than farnesene.
- the structural unit (b1) may be either ⁇ -farnesene or a ⁇ -farnesene-derived structural unit represented by the following formula (I), but from the viewpoint of ease of production of the block copolymer (P), ⁇ - A structural unit derived from farnesene is preferred. Note that ⁇ -farnesene and ⁇ -farnesene may be used in combination.
- Examples of the conjugated diene constituting the structural unit (b2) derived from a conjugated diene other than farnesene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1 , 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, etc. . These may be used alone or in combination of two or more. Of these, butadiene, isoprene and myrcene are more preferred, butadiene and / or isoprene are more preferred, and butadiene is most preferred.
- the polymer block (b) contains 1 to 100% by mass of the structural unit (b1) derived from farnesene and 99 to 0% by mass of the structural unit (b2) derived from conjugated dienes other than farnesene.
- the content of the structural unit (b1) derived from farnesene is less than 1% by mass, it is excellent in flexibility and molding processability, and can be bonded to ceramics and the like even by low-temperature heat treatment, and the fracture mode is aggregated in the peel test It is a failure and a thermoplastic elastomer composition having a strong adhesive force cannot be obtained.
- the content of the structural unit (b1) derived from farnesene is 1% by mass or more, the heat shrinkage rate after the heat treatment is small, so that the generation of thermal stress due to the heat treatment is suppressed, and the adhesive strength is stronger. It will be something.
- the content of the structural unit (b1) in the polymer block (b) is preferably 30 to 100% by mass, and more preferably 45 to 100% by mass.
- the content of the structural unit (b2) is preferably 70% by mass or less, more preferably 55% by mass or less. preferable.
- the content of the structural unit (b1) in the polymer block (b) is flexibility, moldability, and low-temperature adhesiveness. From the viewpoint of low heat shrinkability, 60 to 100% by mass is preferable, 80 to 100% by mass is more preferable, 90 to 100% by mass is further preferable, and substantially 100% by mass is still more preferable. Further, when the thermoplastic elastomer composition contains the softening agent (D) described later, the content of the structural unit (b1) in the polymer block (b) is 30 to 90% by mass from the same viewpoint. It is preferably 30 to 80% by mass, more preferably 45 to 75% by mass.
- the total content of the structural unit (b1) and the structural unit (b2) in the polymer block (b) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and 90% by mass. % Or more is most preferable.
- the hydrogenated block copolymer (A) is a hydrogenated product of a block copolymer (P) containing at least one polymer block (a) and each polymer block (b).
- the hydrogenated block copolymer (A) is preferably a hydrogenated product of a block copolymer (P) containing two or more polymer blocks (a) and one or more polymer blocks (b).
- the bonding form of the polymer block (a) and the polymer block (b) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof.
- each block is linearly bonded
- a form in which each block is linearly bonded is preferable, and when the polymer block (a) is represented by a and the polymer block (b) is represented by b, (ab) l , a- (ba ) Preferred is a bond form represented by m or b- (ab) n .
- said l, m, and n represent an integer greater than or equal to 1 each independently.
- the bonding form is preferably a triblock copolymer represented by aba from the viewpoints of flexibility, molding processability, handleability, and the like.
- each polymer block is a polymer comprising the same structural unit. It may be a block or a polymer block composed of different structural units.
- each aromatic vinyl compound may be the same or different in type. Good.
- the mass ratio [(a) / (b)] of the polymer block (a) and the polymer block (b) in the block copolymer (P) is 1/99 to 70/30.
- the thermoplastic elastomer composition has excellent flexibility and moldability, can be bonded to ceramics and the like even by low-temperature heat treatment, and has a cohesive failure in the peel test and has a strong adhesive force. You can get things.
- the mass ratio [(a) / (b)] of the polymer block (a) and the polymer block (b) is preferably 1/99 to 60/40, and preferably 10/90 to 55/45. More preferably, 10/90 to 45/55 is still more preferable, and 15/85 to 45/55 is still more preferable.
- the peak top molecular weight (Mp) of the hydrogenated block copolymer (A) is preferably from 4,000 to 1,500,000, more preferably from 9,000 to 1,200,000, from the viewpoint of moldability. , 1,000 to 1,000,000 are more preferred, and 50,000 to 800,000 are even more preferred.
- the peak top molecular weight (Mp) in this specification means the value measured by the method described in the Example mentioned later.
- the molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (A) is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When the molecular weight distribution is within the above range, the viscosity variation of the hydrogenated block copolymer (A) is small and easy to handle.
- the block copolymer (P) is a polymer block (c) composed of other monomers in addition to the polymer block (a) and the polymer block (b) as long as the effects of the present invention are not impaired. May be contained.
- examples of such other monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- Unsaturated hydrocarbon compounds such as tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene; acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate Acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid,
- the hydrogenated block copolymer (A) includes, for example, a polymerization step for obtaining the block copolymer (P) by anionic polymerization, and a carbon-carbon dimer in the polymer block (b) in the block copolymer (P). It can be preferably produced by a process of hydrogenating a heavy bond.
- the block copolymer (P) can be produced by a solution polymerization method or a method described in JP-A-2012-502135 and JP-A-2012-502136.
- the solution polymerization method is preferable, and known methods such as an ion polymerization method such as anion polymerization and cation polymerization, and a radical polymerization method can be applied. Of these, the anionic polymerization method is preferred.
- an aromatic vinyl compound, farnesene and / or conjugated dienes other than farnesene are sequentially added in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base, to form a block copolymer (P )
- the anionic polymerization initiator include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium; And compounds containing earth metals and lanthanoid rare earth metals.
- alkali metals such as lithium, sodium and potassium
- alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium
- lanthanoid rare earth metals such as lanthanum and neodymium
- compounds containing earth metals and lanthanoid rare earth metals are preferable, and an organic alkali metal compound is more preferable
- organic alkali metal compound examples include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium, dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane.
- Organic lithium compounds such as 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Of these, organic lithium compounds are preferred, n-butyllithium and sec-butyllithium are more preferred, and sec-butyllithium is particularly preferred.
- the organic alkali metal compound may be used as an organic alkali metal amide by reacting with a secondary amine such as diisopropylamine, dibutylamine, dihexylamine, and dibenzylamine.
- a secondary amine such as diisopropylamine, dibutylamine, dihexylamine, and dibenzylamine.
- the amount of the organic alkali metal compound used for the polymerization varies depending on the molecular weight of the block copolymer (P), but is usually 0.01 to 3 with respect to the total amount of aromatic vinyl compound, farnesene and conjugated dienes other than farnesene. It is the range of mass%.
- the solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction.
- saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, isooctane; cyclopentane, cyclohexane, methylcyclopentane And saturated alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene.
- saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, isooctane
- saturated alicyclic hydrocarbons such as benzene, toluene and xylene.
- Lewis base plays a role in controlling the microstructure of structural units derived from farnesene and structural units derived from conjugated dienes other than farnesene.
- the Lewis base include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol diethyl ether; pyridine; tertiary amines such as N, N, N ′, N′-tetramethylethylenediamine and trimethylamine; potassium Examples include alkali metal alkoxides such as t-butoxide; phosphine compounds.
- the amount is usually preferably in the range of 0.01 to 1000 molar equivalents relative to 1 mole of the anionic polymerization initiator.
- the temperature of the polymerization reaction is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C.
- the polymerization reaction may be carried out batchwise or continuously. Each monomer is continuously or intermittently supplied into the polymerization reaction solution so that the amount of aromatic vinyl compound, farnesene and / or conjugated diene other than farnesene in the polymerization reaction system falls within a specific range, Or a block copolymer (P) can be manufactured by superposing
- the polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
- the block copolymer (P) is obtained by pouring the obtained polymerization reaction liquid into a poor solvent such as methanol to precipitate the block copolymer (P), or washing the polymerization reaction liquid with water, separating, and drying. Can be isolated.
- an unmodified block copolymer (P) may be obtained as described above, but before the hydrogenation step described later, a functional group is introduced into the block copolymer (P).
- a modified block copolymer (P) may be obtained.
- functional groups that can be introduced include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, mercapto groups, isocyanate groups, and acid anhydrides.
- Examples of the modification method of the block copolymer (P) include, for example, tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, and tetramethoxysilane that can react with a polymerization active terminal before adding a polymerization terminator.
- Examples thereof include a method of adding a modifying agent or other modifying agents described in JP2011-132298A.
- maleic anhydride or the like can be grafted onto the isolated copolymer.
- the position where the functional group is introduced may be the polymerization terminal of the block copolymer (P) or the side chain.
- the said functional group may be used individually by 1 type or in combination of 2 or more types.
- the modifying agent is usually preferably in the range of 0.01 to 10 molar equivalents relative to the anionic polymerization initiator.
- the hydrogenated block copolymer (A) can be obtained by subjecting the block copolymer (P) obtained by the above method or the modified block copolymer (P) to a hydrogenation step.
- a known method can be used for the hydrogenation.
- a Ziegler catalyst nickel, platinum, palladium, ruthenium supported on carbon, silica, diatomaceous earth, etc.
- Rhodium metal catalyst An organic metal complex having cobalt, nickel, palladium, rhodium or ruthenium metal is present as a hydrogenation catalyst to carry out a hydrogenation reaction.
- the hydrogenation reaction may be performed by adding a hydrogenation catalyst to the polymerization reaction solution containing the block copolymer (P) obtained by the method for producing the block copolymer (P). .
- a hydrogenation catalyst in which palladium is supported on carbon is preferable.
- the hydrogen pressure is preferably 0.1 to 20 MPa
- the reaction temperature is preferably 100 to 200 ° C.
- the reaction time is preferably 1 to 20 hours.
- the hydrogenation rate of the carbon-carbon double bond in the polymer block (b) is preferably 50 to 100 mol% from the viewpoint of obtaining a thermoplastic elastomer composition excellent in flexibility and moldability.
- the hydrogenation rate is more preferably 70 to 100 mol%, further preferably 80 to 100 mol%, and still more preferably 85 to 100 mol%.
- the hydrogenation rate can be calculated by measuring 1 H-NMR of the block copolymer (P) and the hydrogenated block copolymer (A) after hydrogenation.
- thermoplastic elastomer composition of the present invention contains the polar group-containing olefin polymer (B), so that it has appropriate flexibility and molding processability, and is not subjected to primer treatment. Further, it can be bonded to resin, concrete, asphalt, etc. by heat treatment at a low temperature. Further, in the peel test, the fracture mode is cohesive failure, and a strong adhesive force can be exhibited.
- thermoplastic elastomer composition of the invention is improved, and when the adherend has a polar group, the polar group and the adherend contained in the polar group-containing olefin polymer (B) Possible reasons include chemical bonding with the polar group on the surface.
- an olefin having 2 to 10 carbon atoms is preferable, and an olefin having 2 to 8 carbon atoms is preferable.
- examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. These olefins may be used individually by 1 type, and the copolymer which combined 2 or more types may be sufficient as them. Among these, ethylene and propylene are preferable, and propylene is more preferable.
- Examples of the polar group possessed by the polar group-containing olefin polymer (B) include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; ester group; Is mentioned.
- a (meth) acryloyloxy group, a carboxyl group, an ester group, and an acid anhydride group are preferable from the viewpoint of improving adhesive strength, and a carboxyl group and an acid anhydride group are more preferable.
- polar group containing compound react and modify
- the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid or ester or acid anhydride thereof. Of these, unsaturated carboxylic acids or their esters or acid anhydrides are preferred.
- the unsaturated carboxylic acid or its ester or acid anhydride include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, highmic acid, anhydrous Himic acid and the like can be mentioned. Of these, maleic acid and maleic anhydride are more preferable.
- These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
- (meth) acrylic acid ester exemplified as the polar group-containing copolymerizable monomer
- Alkyl acrylates such as isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate
- methyl methacrylate, ethyl methacrylate, n-propyl methacrylate Such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, etc.
- Acid alkyl esters These (meth) acrylic acid esters may be used alone or in combination of two or
- the polar group-containing olefin polymer (B) is a polyolefin containing a carboxyl group or an acid anhydride group as a polar group, that is, a carboxylic acid-modified olefin polymer or a carboxylic acid anhydride-modified olefin system.
- a polymer is preferable, and a maleic acid-modified olefin polymer and a maleic anhydride-modified olefin polymer are more preferable.
- the polar group of the polar group-containing olefin polymer (B) may be post-treated after polymerization.
- a (meth) acryloyloxy group or a carboxyl group may be neutralized with a metal ion to form an ionomer, or may be esterified with methanol or ethanol. Further, hydrolysis of vinyl acetate or the like may be performed.
- the melt flow rate (MFR) of the polar group-containing olefin polymer (B) at 230 ° C. and a load of 2.16 kg (21 N) is preferably 0.1 to 300 g / 10 minutes, more preferably 0.1 To 100 g / 10 min, more preferably 0.1 to 80 g / 10 min, even more preferably 0.1 to 50 g / 10 min, and particularly preferably 1 to 30 g / 10 min. If the MFR of the polar group-containing olefin polymer (B) under the above conditions is 0.1 g / 10 min or more, good moldability can be obtained. On the other hand, if the MFR is 300 g / 10 min or less, the mechanical characteristics are easily developed.
- the melting point of the polar group-containing olefin polymer (B) is preferably 100 ° C. or higher, more preferably 110 to 170 ° C., and further preferably 120 to 145 ° C. from the viewpoint of heat resistance. The melting point is measured by the method described in the examples.
- the ratio of the polar group-containing structural unit of the polar group-containing olefin polymer (B) to the total structural unit is preferably 0.01 to 10% by mass. If it is 0.01% by mass or more, a thermoplastic elastomer composition having a strong adhesive force can be obtained, which can be bonded to ceramics or the like by low-temperature heat treatment, and the fracture mode is cohesive failure in the peel test. If the proportion of the polar group-containing structural unit is 10% by mass or less, the affinity with the hydrogenated block copolymer (A) is improved, the mechanical properties are improved, and the resulting thermoplastic elastomer composition is flexible. It is excellent in molding processability.
- the above ratio is more preferably 0.01 to 7% by mass, still more preferably 0.01 to 5% by mass.
- Polar group-containing olefins that are prepared by diluting a polyolefin resin containing a polar group-containing structural unit at a high concentration with a polyolefin resin that does not have a polar group-containing structural unit so that the proportion of the polar group-containing structural unit is optimized. You may use as a polymer (B).
- the total content of the polar group-containing structural unit and the olefin-derived structural unit with respect to the structural unit of the polar group-containing olefin polymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more. Preferably it is 95 mass% or more, More preferably, it is 100 mass%.
- thermoplastic elastomer composition of the present invention contains 5 to 300 parts by mass of the polar group-containing olefin polymer (B) with respect to 100 parts by mass of the hydrogenated block copolymer (A). If the polar group-containing olefin polymer (B) is 5 parts by mass or more, it can be bonded to ceramics and the like even by low-temperature heat treatment, and the fracture mode is cohesive failure in the peel test, and has a strong adhesive force. A plastic elastomer composition can be obtained.
- the content of the polar group-containing olefin polymer (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, with respect to 100 parts by mass of the hydrogenated block copolymer (A). It is preferably 250 parts by mass or less, more preferably 200 parts by mass or less. Accordingly, the content of the polar group-containing olefin polymer (B) is preferably 10 to 250 parts by mass, more preferably 15 to 200 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (A). It is.
- the thermoplastic elastomer composition of the present invention may contain a polyvinyl acetal resin (C).
- a polyvinyl acetal resin (C) By containing the polyvinyl acetal resin (C), the adhesive strength of the thermoplastic elastomer composition of the present invention, particularly to ceramics such as glass, can be improved.
- the polyvinyl acetal resin (C) is usually a resin having a repeating unit represented by the following formula (II).
- n represents the number of types of aldehyde used in the acetalization reaction.
- R 1, R 2, ⁇ , R n represents an alkyl residue or a hydrogen atom aldehydes used for the acetalization reaction
- k (1), k ( 2), ⁇ , k (n) is ,
- Each represents a ratio (molar ratio) of structural units represented by [].
- L represents the proportion (molar ratio) of vinyl alcohol units
- m represents the proportion (molar ratio) of vinyl acetate units.
- Each repeating unit is not particularly limited by the above-described arrangement order, and may be arranged at random, may be arranged in a block shape, or may be arranged in a taper shape.
- the polyvinyl acetal resin (C) can be obtained, for example, by reacting polyvinyl alcohol and an aldehyde.
- the average degree of polymerization of the polyvinyl alcohol used for the production of the polyvinyl acetal resin (C) is preferably 100 to 4,000, more preferably 100 to 3,000, more preferably 100 to 2,000, and still more preferably 250. ⁇ 2,000.
- the average degree of polymerization of polyvinyl alcohol is measured according to JIS K 6726. Specifically, it is a value determined from the intrinsic viscosity measured in 30 ° C. water after re-saponifying and purifying polyvinyl alcohol.
- the method for producing polyvinyl alcohol is not particularly limited, and for example, a product produced by saponifying polyvinyl acetate or the like with alkali, acid, aqueous ammonia, or the like can be used. Moreover, you may use a commercial item. Examples of commercially available products include “Kuraray Poval” series manufactured by Kuraray Co., Ltd. Polyvinyl alcohol may be completely saponified or partially saponified. The saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.
- polyvinyl alcohol a copolymer of vinyl alcohol such as ethylene-vinyl alcohol copolymer or partially saponified ethylene-vinyl alcohol copolymer and a monomer copolymerizable with vinyl alcohol can be used. Furthermore, modified polyvinyl alcohol in which carboxylic acid or the like is partially introduced can be used. These polyvinyl alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.
- the aldehyde used for the production of the polyvinyl acetal resin (C) is not particularly limited.
- formaldehyde including paraformaldehyde
- acetaldehyde including paraacetaldehyde
- propionaldehyde n-butyraldehyde
- isobutyraldehyde pentanal, hexanal, heptanal, n-octanal, 2-ethylhexylaldehyde, cyclohexanecarbaldehyde, furfural
- Examples include glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde and the like.
- aldehydes may be used individually by 1 type, and may be used in combination of 2 or more type. Of these aldehydes, butyraldehyde is preferable and n-butyraldehyde is more preferable from the viewpoint of ease of production.
- the polyvinyl acetal resin (C) obtained by acetalization using butyraldehyde is particularly referred to as polyvinyl butyral (PVB).
- PVB polyvinyl butyral
- the degree of acetalization of the polyvinyl acetal resin (C) used in the present invention is preferably 55 to 88 mol%.
- the polyvinyl acetal resin (C) having an acetalization degree of 55 mol% or more is low in production cost, easily available, and has good moldability.
- the polyvinyl acetal resin (C) having a degree of acetalization of 88 mol% or less is very easy to produce, and is economical because it does not require a long time for the acetalization reaction.
- the degree of acetalization of the polyvinyl acetal resin (C) is more preferably 60 to 88 mol%, still more preferably 70 to 88 mol%, and particularly preferably 75 to 85 mol%.
- the degree of acetalization of the polyvinyl acetal resin (C) can be determined according to the method described in JIS K 6728 (1977).
- the degree of acetalization of the polyvinyl acetal resin (C) is determined by dissolving the polyvinyl acetal resin (C) in a suitable deuterated solvent such as deuterated dimethyl sulfoxide, and measuring 1 H-NMR or 13 C-NMR. May be calculated.
- the reaction (acetalization reaction) between polyvinyl alcohol and aldehyde can be performed by a known method.
- aqueous solution method in which an aqueous solution of polyvinyl alcohol and an aldehyde are acetalized in the presence of an acid catalyst to precipitate particles of the polyvinyl acetal resin (C); polyvinyl alcohol is dispersed in an organic solvent, and an acid catalyst Solvent method for precipitating polyvinyl acetal resin (C) by acetalization reaction with aldehyde in the presence, and mixing the obtained reaction mixture with water, which is a poor solvent for polyvinyl acetal resin (C). Etc.
- the acid catalyst is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; gases which show acidity when made into an aqueous solution such as carbon dioxide; cation exchange Examples thereof include solid acid catalysts such as resins and metal oxides.
- the slurry produced in the aqueous medium method or the solvent method is usually acidic by an acid catalyst.
- the slurry is repeatedly washed with water, and the pH is preferably adjusted to 5 to 9, more preferably 6 to 9, and further preferably 6 to 8; a neutralizing agent is added to the slurry.
- Examples of the compound used for adjusting the pH include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal acetates such as sodium acetate; alkali metal such as sodium carbonate and potassium carbonate; Examples thereof include carbonates; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; ammonia and aqueous ammonia solutions.
- alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.
- the removal method is not particularly limited, and methods such as repeated dehydration and water washing are usually used.
- the water-containing polyvinyl acetal resin (C) from which residues and the like have been removed is dried as necessary and processed into powder, granules, or pellets as necessary.
- the polyvinyl acetal resin (C) is contained in the thermoplastic elastomer composition of the present invention
- the polyvinyl acetal resin (C) is added in an amount of 0.1 with respect to 100 parts by mass of the hydrogenated block copolymer (A). It is preferably contained in an amount of ⁇ 100 parts by mass.
- the content of the polyvinyl acetal resin (C) is within this range, the adhesive strength with ceramics (for example, glass) can be further improved, and the thermoplastic elastomer composition can be prevented from becoming hard and flexible. Sex is also expressed.
- the content of the polyvinyl acetal resin (C) is more preferably 1 to 70 parts by weight, still more preferably 5 to 70 parts by weight, and still more preferably 10 to 100 parts by weight of the hydrogenated block copolymer (A). ⁇ 50 parts by mass.
- the thermoplastic elastomer composition of the present invention may further contain a softening agent (D).
- a softening agent D
- softeners generally used for rubber and plastics can be used.
- paraffinic, naphthenic and aromatic process oils phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate
- white oil mineral oil
- liquid co-oligomer of ethylene and ⁇ -olefin liquid paraffin
- polybutene low molecular weight poly Isobutylene: liquid polybutadiene, liquid polyisoprene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid polydiene such as liquid styrene / isoprene copolymer, and hydrogenated products thereof.
- paraffinic process oil from the viewpoint of compatibility with the hydrogenated block copolymer (A), paraffinic process oil; liquid co-oligomer of ethylene and ⁇ -olefin; liquid paraffin; low molecular weight polyisobutylene and hydrogenated product thereof are preferable.
- a hydrogenated product of paraffinic process oil is more preferable.
- organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters
- organic phosphate esters organic phosphorus Phosphoric plasticizers
- acid esters can also be used.
- monobasic organic acid esters include triethylene glycol-dicaproic acid ester, triethylene glycol-di-2-ethylbutyric acid ester, triethylene glycol-di-n-octylic acid ester, and triethylene glycol-di-2.
- -Glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol typified by ethyl hexyl ester and the like, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid And glycol esters obtained by reaction with monobasic organic acids such as pelargonic acid (n-nonyl acid) and decyl acid.
- monobasic organic acids such as pelargonic acid (n-nonyl acid) and decyl acid.
- polybasic acid organic esters examples include linear or linear polybasic organic acids such as adipic acid, sebacic acid, azelaic acid and the like represented by sebacic acid dibutyl ester, azelaic acid dioctyl ester, adipic acid dibutyl carbitol ester and the like.
- examples include esters of branched alcohols.
- examples of the organic phosphate ester include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- a softener (D) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the softening agent (D) is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, still more preferably 100 parts by weight of the hydrogenated block copolymer (A). 50 to 200 parts by mass.
- thermoplastic elastomer composition of the present invention is within the range that does not impair the effects of the present invention, and if necessary, other thermoplastic polymers, inorganic fillers, tackifier resins, antioxidants, lubricants, light stabilizers. , Processing aids, colorants such as pigments and pigments, flame retardants, antistatic agents, matting agents, silicone oil, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, perfumes It may contain.
- the other thermoplastic polymer include an olefin polymer having no polar group, a styrene polymer, a polyphenylene ether resin, and polyethylene glycol.
- thermoplastic elastomer composition of the present invention contains an olefin polymer having no polar group
- examples of such an olefin polymer having no polar group include polyethylene, polypropylene, polybutene, block copolymers of propylene and other ⁇ -olefins such as ethylene and 1-butene, and random copolymers. 1 type (s) or 2 or more types can be used.
- the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (A). It is 20 mass parts or less, More preferably, it is 10 mass parts or less.
- the inorganic filler can be contained for the purpose of improving the physical properties such as heat resistance and weather resistance of the thermoplastic elastomer composition of the present invention, adjusting the hardness, and improving the economy as an extender.
- examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass balloon, and glass fiber. It is done.
- An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content thereof is preferably in a range in which the flexibility of the thermoplastic elastomer composition is not impaired, and preferably 100 parts by weight of the hydrogenated block copolymer (A). 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.
- the tackifying resin examples include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone / indene resins. , Phenolic resins, xylene resins and the like.
- the content thereof is preferably in a range in which the mechanical properties of the thermoplastic elastomer composition are not impaired, preferably with respect to 100 parts by mass of the hydrogenated block copolymer (A). 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.
- antioxidants examples include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable.
- the content thereof is preferably in a range not colored when the resulting thermoplastic elastomer composition is melt-kneaded, and is based on 100 parts by mass of the hydrogenated block copolymer (A). The amount is preferably 0.1 to 5 parts by mass.
- the polyvinyl acetal resin (A hydrogenated block copolymer (A), a polar group containing olefin type polymer (B), and as needed added) C), the softening agent (D), and other components may be produced by any method as long as they can be uniformly mixed, and a melt-kneading method is preferably used.
- the melt kneading can be performed using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and preferably by melt kneading at 170 to 270 ° C.
- a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and preferably by melt kneading at 170 to 270 ° C.
- the thermoplastic elastomer composition of the present invention can be obtained.
- thermoplastic elastomer composition of the present invention has a hardness according to JIS-A method of JIS K 6253 (hereinafter sometimes referred to as “A hardness”), preferably 93 or less, more preferably 85 or less, More preferably, it is 75 or less. If the A hardness is too high, it is difficult to obtain good flexibility, elasticity, and mechanical properties, and it has excellent adhesion to synthetic resins, especially resins containing inorganic fillers (glass fibers, etc.), ceramics and metals. There exists a tendency for the suitable use as a thermoplastic elastomer composition to become difficult.
- a hardness JIS-A method of JIS K 6253
- the present invention also provides an adhesive including the above-described thermoplastic elastomer composition of the present invention. Since the thermoplastic elastomer composition of the present invention has good adhesion to ceramics, concrete, asphalt, metal, polar resin, polyolefin resin, etc., it is suitable as an adhesive for bonding not only the same kind of materials but also different kinds of materials. Used for. In addition, since it has flexibility, it also has a buffering action against a difference in thermal expansion coefficient between different materials. 80 mass% or more is preferable, as for content of the said thermoplastic elastomer composition in an adhesive agent, 90 mass% or more is more preferable, 95 mass% or more is further more preferable, and 100 mass% is still more preferable.
- the strength of the adhesive strength of the thermoplastic elastomer composition of the present invention can also be evaluated, for example, by looking at the fracture form of the specimen after the peel test.
- the thermoplastic elastomer composition of the present invention mainly causes cohesive failure in a peel test.
- the cohesive failure means an embodiment in which the adhesive layer itself containing the thermoplastic elastomer composition of the present invention is destroyed.
- cohesive failure is more firmly adhered to a substrate than interfacial delamination, and is considered to have high reliability as an adhesive. Therefore, the adhesive containing the thermoplastic elastomer composition of the present invention can be suitably used for various applications that require adhesive strength.
- the present invention also provides a molded body comprising the above-described thermoplastic elastomer composition of the present invention. Since the thermoplastic elastomer composition of the present invention is excellent in molding processability, various molded articles can be produced.
- the molded body may be a sheet or a film.
- various molding methods generally used for thermoplastic elastomer compositions can be used. Specifically, an arbitrary molding method such as an injection molding method, an extrusion molding method, a press molding method, a blow molding method, a calendar molding method, or a casting molding method can be employed. In addition, a general T-die method, a calendar method, an inflation method, a belt method, etc. can be employed for forming a film or a sheet.
- the thermoplastic elastomer composition of the present invention is at least one selected from ceramics, metals, polar resins and polyolefin resins (hereinafter sometimes referred to as adherends). It is a molded article that is bonded to the substrate.
- the molded body of the present invention may be a multilayer molded body in which the thermoplastic elastomer composition is bonded to two or more of the adherends.
- the adhesive strength of the thermoplastic elastomer composition in the molded body is a value measured according to JIS K-6854-2, and is preferably 20 N / 25 mm or more. It can be said that it has fully adhere
- This adhesive force is more preferably 50 N / 25 mm or more, still more preferably 70 N / 25 mm or more, and still more preferably 80 N / 25 mm or more.
- thermoplastic elastomer composition of the present invention can be bonded to the adherend by heat treatment at a low temperature (190 ° C. or less) without performing primer treatment or the like. Therefore, in the manufacturing process of the molded body in which the adherend is bonded to the thermoplastic elastomer composition of the present invention, the surface temperature of the thermoplastic elastomer composition discharged from an injection molding machine or an extruder is 190 ° C. or lower. Adequate adhesion is possible even when cooled down, so that existing equipment can be used as it is without installing a separate heater. Moreover, since many synthetic resin members are not melted or deformed at 190 ° C. or lower, it is possible to avoid the destruction of the synthetic resin member around the bonded portion that is heated at the same time.
- the heat treatment is preferably performed at 150 ° C. or higher, more preferably 160 ° C. or higher.
- Ceramics that can be used in the molded body of the present invention mean non-metallic inorganic materials, and examples thereof include metal oxides, metal carbides, and metal nitrides. Examples thereof include glass, cements, alumina, zirconia, zinc oxide ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites. Examples of the metal that can be used in the molded article of the present invention include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing them as components.
- polar resins that can be used in the molded article of the present invention include polyamide resins, polyester resins, polycarbonate resins, polyphenylene sulfide resins, (meth) acrylonitrile-butadiene-styrene resins, (meth) acrylonitrile-styrene resins, (meth).
- Acrylate ester-butadiene-styrene resin (meth) acrylate ester-styrene resin, butadiene-styrene resin, epoxy resin, phenol resin, diallyl phthalate resin, polyimide resin, melamine resin, polyacetal resin, polysulfone resin, polyethersulfone resin , Polyetherimide resin, polyphenylene ether resin, polyarylate resin, polyether ether ketone resin, polystyrene resin, syndiotactic polystyrene resin, etc. And the like. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
- As the polyamide resin for example, polyamide 6 (PA6), polyamide 66 (PA66) or the like is preferably used.
- the polar resin may contain an inorganic filler.
- the inorganic filler include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass fiber, and glass balloon. It is done.
- An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, glass fiber is preferable.
- the blending amount of the inorganic filler is preferably within a range where the processability and mechanical strength of the resin containing the inorganic filler are not impaired, and is generally 0.1 to 100 parts by mass with respect to 100 parts by mass of the polar resin. The amount is 100 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 3 to 40 parts by mass.
- polystyrene resin examples include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, and ethylene.
- ⁇ -olefins having 3 to 20 carbon atoms for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1 -Pentene, 6-methyl-1-heptene, isooctene, isooctadiene, decadiene and the like
- ethylene / propylene / diene copolymer EPDM
- ethylene-vinyl acetate copolymer Polymers, ethylene-acrylic acid copolymers and the like are preferably used.
- the method for producing the molded product of the present invention is not particularly limited, and any method may be adopted as long as it is a method for producing an adhesive molded product by melt bonding.
- an injection insert molding method, an extrusion lamination method examples of the molding method include a press molding method and a melt casting method.
- an adhesive molded body is manufactured by an injection insert molding method, an adherend that has been formed in a predetermined shape and size in advance is placed in a mold, and the thermoplastic elastomer composition of the present invention is placed there.
- a method of manufacturing an adhesive molded body by injection molding is adopted.
- the predetermined shape attached to the extruder is applied to the surface of the adherend formed in advance in the predetermined shape and dimensions, or the edge thereof. It is also possible to produce an adhesive-molded article by directly extruding a molten thermoplastic elastomer composition extruded from a die having
- a molded body made of the thermoplastic elastomer composition of the present invention is molded in advance by an injection molding method or an extrusion molding method, and the molded body is previously It can also be produced by heating and pressurizing an adherend that has been formed into a shape and size using a press molding machine or the like. Such a forming method is particularly suitable when the adherend is ceramic or metal.
- the adherend when the adherend is a polar resin or a polyolefin resin, both can be melted at the same time and co-extrusion molding or co-injection molding can be performed. Alternatively, one of them may be formed in advance and melt coated thereon or solution coated. In addition, two-color molding or insert molding can be employed. The above-mentioned melt coating and solution coating are also suitable when the adherend is concrete or asphalt.
- thermoplastic elastomer composition of the present invention and the molded article of the present invention can be widely applied to various uses.
- light metals such as synthetic resin, synthetic resin containing glass fiber, aluminum, and magnesium alloy are used for housing materials such as electronic / electrical equipment, OA equipment, home appliances, and automobile members.
- a molded body to which the thermoplastic elastomer composition of the invention is adhered can be used. More specifically, such as large displays, notebook computers, portable telephones, PHS, PDAs (portable information terminals such as electronic notebooks), electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, inverters, etc.
- a shock-absorbing material such as a shock-absorbing material, a coating material having an anti-slip function, a waterproof material, and a design material, which are bonded to the housing.
- a molded body or a structure bonded to glass such as window moldings and gaskets for automobiles and buildings, glass sealing materials, and anticorrosive materials.
- it can be suitably used as a sealant for a joint between glass and an aluminum sash or a metal opening in a window of an automobile or a building, or a connection between a glass and a metal frame in a solar cell module or the like.
- it can be suitably used for various information terminal devices such as notebook computers, mobile phones, video cameras, and secondary battery separators used in hybrid vehicles, fuel cell vehicles, and the like. Furthermore, it can be suitably used for adhesives for road pavement concrete layers and asphalt layers such as bridges, and also has an effect as a waterproof material.
- ⁇ -farnesene purity 97.6% by mass Amiris, Inc., manufactured by Incorporated
- ⁇ -farnesene purified by 3 ⁇ molecular sieve and distilled under a nitrogen atmosphere to obtain gingivalene, bisabolene, farnesene epoxide, farnesol isomerism.
- hydrocarbon impurities such as dimer, E, E-farnesol, squalene, ergosterol and some of the dimers of farnesene, it was used for the following polymerization.
- each measuring method in a manufacture example is as follows.
- the peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer are converted to standard polystyrene by GPC (gel permeation chromatography).
- the molecular weight was obtained, and the peak top molecular weight (Mp) was obtained from the position of the peak of the molecular weight distribution peak.
- the measuring apparatus and conditions are as follows.
- GPC device GPC device “GPC8020” manufactured by Tosoh Corporation Separation column: “TSKgel G4000HXL” manufactured by Tosoh Corporation ⁇ Detector: “RI-8020” manufactured by Tosoh Corporation ⁇ Eluent: Tetrahydrofuran ⁇ Eluent flow rate: 1.0 ml / min ⁇ Sample concentration: 5 mg / 10 ml -Column temperature: 40 ° C
- a block copolymer (referred to as A-1)) was obtained.
- the hydrogenated block copolymer (A-1) was evaluated as described above. The results are shown in Table 1.
- a hydrogenated block copolymer (A′-1) was prepared in the same manner as in Production Example 1 except that 288 g of tetrahydrofuran was mixed with 50.0 kg of cyclohexane as a solvent and the formulation shown in Table 1 was followed. A polymer (A′-1) was produced. The obtained hydrogenated block copolymer (A′-1) was evaluated as described above. The results are shown in Table 1.
- a hydrogenated block copolymer (A′-2) was produced in the same manner as in Production Example 1, except that the composition described in Table 1 was followed. The obtained hydrogenated block copolymer (A′-2) was evaluated as described above. The results are shown in Table 1.
- MFR [230 ° C., 21N] of the obtained (B-1) was 6 g / 10 minutes, the proportion of the maleic anhydride group-containing structural unit was 0.3% by mass, and the melting point was 138 ° C.
- the ratio of the maleic anhydride group-containing structural unit is a value obtained by titrating the obtained (B-1) with a methanol solution of potassium hydroxide, and so on.
- the melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min, and so on.
- thermoplastic elastomer composition [Examples 1 to 12 and Comparative Examples 1 to 6] Each component shown in Table 2 to Table 4 was melt kneaded at a ratio shown in Table 2 to Table 4 at 230 ° C. and a screw rotation speed of 200 rpm using a batch mixer to prepare a thermoplastic elastomer composition. . The physical properties of the obtained thermoplastic elastomer composition were evaluated as follows. The results are shown in Tables 2-4.
- thermoplastic elastomer compositions obtained in the examples and comparative examples were used in a compression press molding machine “NF” manufactured by Shindo Metal Industries, Ltd. -37 ", using a" Teflon (registered trademark) "coated metal frame as a spacer and compression press-molding for 5 minutes at a load of 230 ° C and 100 kgf / cm 2 , followed by 18 ° C and 15 kgf / cm 2
- a sheet of a thermoplastic elastomer composition having a thickness of 1 mm was obtained by compression press molding with a load for 1 minute.
- test piece according to JIS K 6251 was punched from this sheet to obtain a test piece.
- measurement was performed according to JIS K 6253-3 using a type A durometer indenter. The lower the hardness, the better the flexibility.
- thermoplastic elastomer composition sheet prepared in (1-1) above was chopped and charged into a capillograph (manufactured by Toyo Seiki Co., Ltd.), 1 mm ⁇ ⁇ 10 mm size capillary, temperature 230 ° C., shear rate The melt viscosity at 1210 s ⁇ 1 was measured. The smaller this value, the better the moldability.
- the metal spacer having a thickness of 2 mm was disposed at the center.
- the overlapped sheet and the metal spacer are sandwiched between polytetrafluoroethylene sheets and further sandwiched between the metal plates from the outside.
- the load is 20 kgf / cm 2 (2 N / mm 2) at 160 ° C. )
- the load is 20 kgf / cm 2 (2 N / mm 2) at 160 ° C. )
- ⁇ Production of laminate with polypropylene (PP) plate> Except for using a polypropylene plate having a length of 75 mm, a width of 25 mm and a thickness of 1 mm obtained by injection molding of polypropylene (Novatech PP MA3 manufactured by Nippon Polypro Co., Ltd.), the same as the production of the laminate with the aluminum plate described above. The operation was carried out to obtain a laminate comprising PET / thermoplastic elastomer composition / polypropylene plate.
- the heat shrinkage rate was measured by a method based on JIS K 7133. That is, a test piece was cut out to a size of 120 mm ⁇ 120 mm from the sheet of the elastomer composition prepared in the above (1-1). A mark was marked at the center of the test piece, and the distance between the mark lines (L0) was measured at 23 ° C., and then the test piece was heated at 220 ° C. for 20 minutes. After taking out the test piece, it was allowed to cool at 23 ° C. for 30 minutes, and the distance between marked lines (L) was measured again.
- Example 8 and Comparative Example 5 both contain polyvinyl acetal resin (C) with the same composition, and both differ only in the type of hydrogenated block copolymer.
- Example 8 using the hydrogenated block copolymer (A) having the structural unit (b1) derived from farnesene does not have the structural unit (b1) derived from farnesene.
- Example 9 and Comparative Example 6 both contain the softener (D) in the same composition, and both differ only in the type of hydrogenated block copolymer.
- thermoplastic elastomer composition of the present invention is excellent in the above-mentioned various performances even when the content of the softening agent (D) is changed in a wide range.
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Abstract
Description
しかしながら、スチレン系熱可塑性エラストマーは極性が低い材料であるため、セラミックス、金属などに対する接着力が十分でなく、そのままでは溶融接着が困難であるという問題点を有する。そのため、セラミックスや金属とスチレン系熱可塑性エラストマーを接着させるために、接着剤を塗布したり、あらかじめセラミックス、金属、合成樹脂の表面をプライマー処理したりする方法が開示されている(特許文献1~6参照)。
このような問題に対し、セラミックス、金属及び合成樹脂に対して優れた接着性を有する、スチレン系熱可塑性エラストマーとポリビニルアセタールを含む熱可塑性重合体組成物が開示されている(特許文献7参照)。この熱可塑性重合体組成物は、接着剤を塗布したり、プライマー処理したりすることなく、加熱処理のみによってセラミックス、金属及び合成樹脂に接着させることが可能である。
また、熱可塑性エラストマーと基材との接着成形体においては、剥離試験の際に界面剥離を起こさず、凝集破壊を起こす方が接着剤としての性能に優れているとされている。しかしながら、特許文献7に開示された熱可塑性重合体組成物は界面剥離を生じる場合があり、より接着力に優れた、破壊形態が凝集破壊である熱可塑性エラストマーが求められていた。
[1]芳香族ビニル化合物由来の構造単位からなる重合体ブロック(a)と、ファルネセン由来の構造単位(b1)を1~100質量%含有し、ファルネセン以外の共役ジエン由来の構造単位(b2)を99~0質量%含有する重合体ブロック(b)とを含み、重合体ブロック(a)と重合体ブロック(b)との質量比[(a)/(b)]が1/99~70/30である水添ブロック共重合体(A)100質量部に対して、極性基含有オレフィン系重合体(B)5~300質量部を含有する熱可塑性エラストマー組成物。
[2]上記[1]に記載の熱可塑性エラストマー組成物を含む接着剤。
[3]上記[1]に記載の熱可塑性エラストマー組成物からなる成形体。
本発明の熱可塑性エラストマー組成物は、芳香族ビニル化合物由来の構造単位からなる重合体ブロック(a)と、ファルネセン由来の構造単位(b1)を1~100質量%含有し、ファルネセン以外の共役ジエン由来の構造単位(b2)を99~0質量%含有する重合体ブロック(b)とを含み、重合体ブロック(a)と重合体ブロック(b)との質量比[(a)/(b)]が1/99~70/30である水添ブロック共重合体(A)100質量部に対して、極性基含有オレフィン系重合体(B)5~300質量部を含有する熱可塑性エラストマー組成物である。
本発明の熱可塑性エラストマー組成物に用いられる水添ブロック共重合体(A)は、芳香族ビニル化合物由来の構造単位からなる重合体ブロック(a)と、ファルネセン由来の構造単位(b1)を1~100質量%含有し、ファルネセン以外の共役ジエン由来の構造単位(b2)を99~0質量%含有する重合体ブロック(b)とを含み、重合体ブロック(a)と重合体ブロック(b)との質量比[(a)/(b)]が1/99~70/30であるブロック共重合体(以下、「ブロック共重合体(P)」ということがある)の水素添加物(以下、「水添ブロック共重合体(A)」ということがある)である。
本発明の熱可塑性エラストマー組成物は、ファルネセン由来の構造単位(b1)を特定量含有する水添ブロック共重合体(A)を含有するため、ファルネセン由来の構成単位を含有しないスチレン系熱可塑性エラストマーと比べて、柔軟性、成形加工性に優れ、プライマー処理などを施さなくても、セラミックス、金属、樹脂等と低温(例えば190℃以下)での加熱処理によっても接着でき、かつ剥離試験において破壊形態が凝集破壊であり、強固な接着力を有する。また、加熱処理後における熱収縮率も小さいため、加熱処理による熱応力の発生が抑制され、接着力がより強固なものとなる。
例えば、熱可塑性エラストマー組成物が後述する軟化剤(D)を含有しない場合には、重合体ブロック(b)中の構造単位(b1)の含有量は、柔軟性、成形加工性、低温接着性、低熱収縮性の観点から、60~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましく、実質的に100質量%がより更に好ましい。また、熱可塑性エラストマー組成物が後述する軟化剤(D)を含有する場合には、重合体ブロック(b)中の構造単位(b1)の含有量は、同様の観点から、30~90質量%が好ましく、30~80質量%がより好ましく、45~75質量%が更に好ましい。
重合体ブロック(b)中の構造単位(b1)及び構造単位(b2)の合計含有量は、50質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上が更に好ましく、90質量%以上が最も好ましい。
重合体ブロック(a)及び重合体ブロック(b)の結合形態は特に制限されず、直線状、分岐状、放射状又はそれらの2つ以上の組み合わせであってもよい。中でも、各ブロックが直線状に結合した形態が好ましく、重合体ブロック(a)をa、重合体ブロック(b)をbで表したときに、(a-b)l、a-(b-a)m又はb-(a-b)nで表される結合形態が好ましい。なお、前記l、m及びnはそれぞれ独立して1以上の整数を表す。
前記結合形態としては、柔軟性、成形加工性及び取り扱い性等の観点から、a-b-aで表されるトリブロック共重合体が好ましい。
また、ブロック共重合体(P)が重合体ブロック(a)を2個以上又は重合体ブロック(b)を2個以上有する場合には、それぞれの重合体ブロックは、同じ構造単位からなる重合体ブロックであっても、異なる構造単位からなる重合体ブロックであってもよい。例えば、〔a-b-a〕で表されるトリブロック共重合体における2個の重合体ブロック(a)において、それぞれの芳香族ビニル化合物は、その種類が同じであっても異なっていてもよい。
かかる他の単量体としては、例えばプロピレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、1-ヘキセン、1-オクテン、1-デセン、1-ウンデセン、1-ドデセン、1-トリデセン、1-テトラデセン、1-ペンタデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-ノナデセン、1-エイコセン等の不飽和炭化水素化合物;アクリル酸、メタクリル酸、アクリル酸メチル、メタクリル酸メチル、アクリロニトリル、メタクリロニトリル、マレイン酸、フマル酸、クロトン酸、イタコン酸、2-アクリロイルエタンスルホン酸、2-メタクリロイルエタンスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸、2-メタクリルアミド-2-メチルプロパンスルホン酸、ビニルスルホン酸、酢酸ビニル、メチルビニルエーテル等の官能基含有不飽和化合物;等が挙げられる。これらは1種を単独で又は2種以上を併用してもよい。
ブロック共重合体(P)が重合体ブロック(c)を有する場合、その含有量は50質量%以下が好ましく、40質量%以下がより好ましく、30質量%以下が更に好ましい。
水添ブロック共重合体(A)は、例えばブロック共重合体(P)をアニオン重合により得る重合工程、及び該ブロック共重合体(P)中の重合体ブロック(b)中の炭素-炭素二重結合を水素添加する工程により好適に製造できる。
<重合工程>
ブロック共重合体(P)は、溶液重合法又は特表2012-502135号公報、特表2012-502136号公報に記載の方法等により製造することができる。中でも溶液重合法が好ましく、例えば、アニオン重合やカチオン重合等のイオン重合法、ラジカル重合法等の公知の方法を適用できる。中でもアニオン重合法が好ましい。アニオン重合法としては、溶媒、アニオン重合開始剤、及び必要に応じてルイス塩基の存在下、芳香族ビニル化合物、ファルネセン及び/又はファルネセン以外の共役ジエンを逐次添加して、ブロック共重合体(P)を得る。
アニオン重合開始剤としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属;ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム等のアルカリ土類金属;ランタン、ネオジム等のランタノイド系希土類金属;前記アルカリ金属、アルカリ土類金属、ランタノイド系希土類金属を含有する化合物等が挙げられる。中でもアルカリ金属及びアルカリ金属を含有する化合物が好ましく、有機アルカリ金属化合物がより好ましい。
重合に用いる有機アルカリ金属化合物の使用量は、ブロック共重合体(P)の分子量によっても異なるが、通常、芳香族ビニル化合物、ファルネセン及びファルネセン以外の共役ジエンの総量に対して0.01~3質量%の範囲である。
重合反応は、メタノール、イソプロパノール等のアルコールを重合停止剤として添加して停止できる。得られた重合反応液をメタノール等の貧溶媒に注いでブロック共重合体(P)を析出させるか、重合反応液を水で洗浄し、分離後、乾燥することによりブロック共重合体(P)を単離できる。
ブロック共重合体(P)の変性方法としては、例えば、重合停止剤を添加する前に、重合活性末端と反応し得る四塩化錫、テトラクロロシラン、ジメチルジクロロシラン、ジメチルジエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、3-アミノプロピルトリエトキシシラン、テトラグリシジル-1,3-ビスアミノメチルシクロヘキサン、2,4-トリレンジイソシアネート、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、N-ビニルピロリドン等の変性剤、又は特開2011-132298号公報に記載のその他の変性剤を添加する方法が挙げられる。また、単離後の共重合体に無水マレイン酸等をグラフト化して用いることもできる。
官能基が導入される位置はブロック共重合体(P)の重合末端でも、側鎖でもよい。また上記官能基は1種を単独で又は2種以上を組み合わせてもよい。上記変性剤は、アニオン重合開始剤に対して、通常、0.01~10モル当量の範囲であることが好ましい。
前記方法により得られたブロック共重合体(P)又は変性されたブロック共重合体(P)を水素添加する工程に付すことにより、水添ブロック共重合体(A)を得ることができる。水素添加する方法は公知の方法を用いることができる。例えば、水素添加反応に影響を及ぼさない溶媒にブロック共重合体(P)を溶解させた溶液に、チーグラー系触媒;カーボン、シリカ、けいそう土等に担持されたニッケル、白金、パラジウム、ルテニウム又はロジウム金属触媒;コバルト、ニッケル、パラジウム、ロジウム又はルテニウム金属を有する有機金属錯体等を、水素添加触媒として存在させて水素化反応を行う。水素添加工程においては、前記したブロック共重合体(P)の製造方法によって得られたブロック共重合体(P)を含む重合反応液に水素添加触媒を添加して水素添加反応を行ってもよい。本発明においては、パラジウムをカーボンに担持させたパラジウムカーボンが好ましい。
水素添加反応において、水素圧力は0.1~20MPaが好ましく、反応温度は100~200℃が好ましく、反応時間は1~20時間が好ましい。
本発明の熱可塑性エラストマー組成物は、極性基含有オレフィン系重合体(B)を含有することにより、適度な柔軟性と成形加工性を兼ね備え、かつプライマー処理などを施さなくても、セラミックス、金属、樹脂、コンクリート、アスファルト等と低温での加熱処理によっても接着でき、さらに剥離試験において破壊形態が凝集破壊であり、強固な接着力を発揮することができる。
このような効果が得られるのは、必ずしも詳細は明らかではないが、極性基含有オレフィン系重合体(B)を含有することにより、セラミックス、金属、樹脂、コンクリート、アスファルト等の被着体と本発明の熱可塑性エラストマー組成物との相容性が良好になること、また、被着体が極性基を有する場合は、極性基含有オレフィン系重合体(B)に含まれる極性基と被着体表面の極性基との間で化学結合を生じること、などの理由が考えられる。
また、極性基含有オレフィン系重合体(B)が有する極性基としては、例えば(メタ)アクリロイルオキシ基;水酸基;アミド基;塩素原子などのハロゲン原子;カルボキシル基;エステル基;酸無水物基などが挙げられる。これらの中でも、(メタ)アクリロイルオキシ基、カルボキシル基、エステル基、酸無水物基が接着力向上の観点から好ましく、カルボキシル基及び酸無水物基がより好ましい。
極性基含有共重合性単量体としては、例えば、酢酸ビニル、塩化ビニル、酸化エチレン、酸化プロピレン、アクリルアミド、不飽和カルボン酸またはそのエステルもしくは酸無水物が挙げられる。中でも、不飽和カルボン酸またはそのエステルもしくは酸無水物が好ましい。不飽和カルボン酸またはそのエステルもしくは酸無水物としては、例えば、(メタ)アクリル酸、(メタ)アクリル酸エステル、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、ハイミック酸、無水ハイミック酸などが挙げられる。中でも、マレイン酸、無水マレイン酸がより好ましい。これらの極性基含有共重合性単量体は、1種を単独で用いてもよいし、2種以上を組み合わせてもよい。
極性基含有オレフィン系重合体(B)の融点は、耐熱性の観点から、好ましくは100℃以上、より好ましくは110~170℃、さらに好ましくは120~145℃である。なお、融点は実施例記載の方法により測定される。
これらより、極性基含有オレフィン系重合体(B)の含有量は、水添ブロック共重合体(A)100質量部に対して、好ましくは10~250質量部、より好ましくは15~200質量部である。
本発明の熱可塑性エラストマー組成物は、ポリビニルアセタール樹脂(C)を含有していてもよい。ポリビニルアセタール樹脂(C)を含有することにより、本発明の熱可塑性エラストマー組成物の、特にガラス等のセラミックスに対する接着力を向上させることができる。
該ポリビニルアセタール樹脂(C)は、通常、下記式(II)で表される繰り返し単位を有する樹脂である。
ただし、k(1)+k(2)+・・・+k(n)+l+m=1であり、k(1)、k(2)、・・・、k(n)、l及びmは、いずれかがゼロであってもよい。
各繰返し単位は、特に上記配列順序によって制限されず、ランダムに配列されていてもよいし、ブロック状に配列されていてもよいし、テーパー状に配列されていてもよい。
ポリビニルアセタール樹脂(C)の製造に用いられるポリビニルアルコールは、平均重合度が、好ましくは100~4,000、より好ましくは100~3,000、より好ましくは100~2,000、更に好ましくは250~2,000である。
ここでポリビニルアルコールの平均重合度は、JIS K 6726に準じて測定したものである。具体的には、ポリビニルアルコールを再けん化し、精製した後、30℃の水中で測定した極限粘度から求めた値である。
ポリビニルアセタール樹脂(C)のアセタール化度は、より好ましくは60~88モル%であり、更に好ましくは70~88モル%であり、特に好ましくは75~85モル%である。ポリビニルアセタール樹脂(C)のアセタール化度が低いほど、ポリビニルアセタール樹脂(C)が有する水酸基の割合が大きくなり、セラミックス、金属及び樹脂等に対する接着性において有利となるが、上記範囲のアセタール化度とすることで、水添ブロック共重合体(A)との親和性や相容性が良好となり、本発明の熱可塑性エラストマー組成物の接着力がより向上する。
なお、ポリビニルアセタール樹脂(C)のアセタール化度は、JIS K 6728(1977年)に記載の方法に則って求めることができる。
また、ポリビニルアセタール樹脂(C)のアセタール化度は、ポリビニルアセタール樹脂(C)を重水素化ジメチルスルホキシドなどの適切な重水素化溶媒に溶解し、1H-NMRや13C-NMRを測定して算出してもよい。
上記酸触媒は特に限定されず、例えば、酢酸、p-トルエンスルホン酸などの有機酸類;硝酸、硫酸、塩酸などの無機酸類;二酸化炭素などの水溶液にした際に酸性を示す気体;陽イオン交換樹脂や金属酸化物などの固体酸触媒などが挙げられる。
pHを調整するために用いられる化合物としては、例えば、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物;酢酸ナトリウムなどのアルカリ金属の酢酸塩;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の炭酸塩;炭酸水素ナトリウムなどのアルカリ金属の炭酸水素塩;アンモニア、アンモニア水溶液などが挙げられる。また、前記アルキレンオキサイド類としては、例えば、エチレンオキサイド、プロピレンオキサイド;エチレングリコールジグリシジルエーテルなどのグリシジルエーテル類が挙げられる。
本発明の熱可塑性エラストマー組成物は、さらに軟化剤(D)を含有していてもよい。軟化剤(D)としては、一般にゴム、プラスチックスに用いられる軟化剤を使用できる。例えばパラフィン系、ナフテン系、芳香族系のプロセスオイル;ジオクチルフタレート、ジブチルフタレート等のフタル酸誘導体;ホワイトオイル;ミネラルオイル;エチレンとα-オレフィンとの液状コオリゴマー;流動パラフィン;ポリブテン;低分子量ポリイソブチレン;液状ポリブタジエン、液状ポリイソプレン、液状ポリイソプレン/ブタジエン共重合体、液状スチレン/ブタジエン共重合体、液状スチレン/イソプレン共重合体等の液状ポリジエン及びその水添物等が挙げられる。中でも、水添ブロック共重合体(A)との相容性の観点から、パラフィン系プロセスオイル;エチレンとα-オレフィンとの液状コオリゴマー;流動パラフィン;低分子量ポリイソブチレン及びその水添物が好ましく、パラフィン系プロセスオイルの水添物がより好ましい。
一塩基性有機酸エステルとしては、例えば、トリエチレングリコール-ジカプロン酸エステル、トリエチレングリコール-ジ-2-エチル酪酸エステル、トリエチレングリコール-ジ-n-オクチル酸エステル、トリエチレングリコール-ジ-2-エチルヘキシル酸エステルなどに代表されるトリエチレングリコール、テトラエチレングリコール、トリプロピレングリコールなどのグリコールと、酪酸、イソ酪酸、カプロン酸、2-エチル酪酸、ヘプチル酸、n-オクチル酸、2-エチルヘキシル酸、ペラルゴン酸(n-ノニル酸)、デシル酸などの一塩基性有機酸との反応によって得られたグリコール系エステルが挙げられる。
多塩基酸有機エステルとしては、例えばセバシン酸ジブチルエステル、アゼライン酸ジオクチルエステル、アジピン酸ジブチルカルビトールエステルなどに代表されるアジピン酸、セバシン酸、アゼライン酸などの多塩基性有機酸と直鎖状又は分岐状アルコールのエステルなどが挙げられる。
有機リン酸エステルとしては、例えばトリブトキシエチルホスフェート、イソデシルフェニルホスフェート、トリイソプロピルホスフェートなどが挙げられる。
軟化剤(D)は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明の熱可塑性エラストマー組成物は、本発明の効果を阻害しない範囲で、必要に応じて、他の熱可塑性重合体、無機充填材、粘着性付与樹脂、酸化防止剤、滑剤、光安定剤、加工助剤、顔料や色素などの着色剤、難燃剤、帯電防止剤、艶消し剤、シリコンオイル、ブロッキング防止剤、紫外線吸収剤、離型剤、発泡剤、抗菌剤、防カビ剤、香料を含有してもよい。前記他の熱可塑性重合体としては、例えば極性基を有さないオレフィン系重合体、スチレン系重合体、ポリフェニレンエーテル系樹脂、ポリエチレングリコールなどが挙げられる。これらの中でも、本発明の熱可塑性エラストマー組成物に極性基を有さないオレフィン系重合体を含有させると、その成形加工性が更に向上する。このような極性基を有さないオレフィン系重合体としては、例えば、ポリエチレン、ポリプロピレン、ポリブテン、プロピレンとエチレンや1-ブテンなどの他のα-オレフィンとのブロック共重合体やランダム共重合体などの1種又は2種以上を使用することができる。
他の熱可塑性重合体を含有させる場合、その含有量は、水添ブロック共重合体(A)100質量部に対して、好ましくは100質量部以下、より好ましくは50質量部以下、より好ましくは20質量部以下、更に好ましくは10質量部以下である。
無機充填材を含有させる場合、その含有量は、熱可塑性エラストマー組成物の柔軟性が損なわれない範囲であることが好ましく、水添ブロック共重合体(A)100質量部に対して、好ましくは100質量部以下、より好ましくは70質量部以下、更に好ましくは30質量部以下、特に好ましくは10質量部以下である。
粘着付与樹脂を含有させる場合、その含有量は、熱可塑性エラストマー組成物の力学特性が損なわれない範囲であることが好ましく、水添ブロック共重合体(A)100質量部に対して、好ましくは100質量部以下、より好ましくは70質量部以下、更に好ましくは30質量部以下、特に好ましくは10質量部以下である。
本発明はまた、前記した本発明の熱可塑性エラストマー組成物を含む接着剤を提供する。本発明の熱可塑性エラストマー組成物は、セラミックス、コンクリート、アスファルト、金属、極性樹脂及びポリオレフィン樹脂等に対する接着性が良好であるので、同種材料同士のみならず、異種材料同士を接着する接着剤として好適に用いられる。しかも、柔軟性も有しているので、異種材料同士の熱膨張係数の相違などに対する緩衝作用も有している。接着剤中における当該熱可塑性エラストマー組成物の含有量は、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上が更に好ましく、100質量%がより更に好ましい。
本発明はまた、前記した本発明の熱可塑性エラストマー組成物からなる成形体を提供する。
本発明の熱可塑性エラストマー組成物は成形加工性に優れるので、種々の成形体を製造することができる。成形体は、シートやフィルムであってもよい。
成形方法としては、熱可塑性エラストマー組成物に対して一般に用いられている各種の成形方法が使用できる。具体的には、射出成形法、押出成形法、プレス成形法、ブロー成形法、カレンダー成形法、流延成形法などの任意の成形法を採用できる。また、フィルム、シートの成形に、一般的な、Tダイ法、カレンダー法、インフレーション法、ベルト法なども採用できる。
本発明の成形体に使用し得る金属は、例えば、鉄、銅、アルミニウム、マグネシウム、ニッケル、クロム、亜鉛、及びそれらを成分とする合金が挙げられる。また、銅メッキ、ニッケルメッキ、クロムメッキ、錫メッキ、亜鉛メッキ、白金メッキ、金メッキ、銀メッキなどメッキによって形成された金属の表面を持つ成形体であってもよい。
本発明の成形体に使用し得る極性樹脂としては、例えば、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンサルファイド樹脂、(メタ)アクリロニトリル-ブタジエン-スチレン樹脂、(メタ)アクリロニトリル-スチレン樹脂、(メタ)アクリル酸エステル-ブタジエン-スチレン樹脂、(メタ)アクリル酸エステル-スチレン樹脂、ブタジエン-スチレン樹脂、エポキシ樹脂、フェノール樹脂、ジアリルフタレート樹脂、ポリイミド樹脂、メラミン樹脂、ポリアセタール樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリフェニレンエーテル樹脂、ポリアリレート樹脂、ポリエーテルエーテルケトン樹脂、ポリスチレン樹脂、シンジオタクティックポリスチレン樹脂、などが挙げられる。これらの樹脂は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。上記ポリアミド樹脂としては、例えば、ポリアミド6(PA6)、ポリアミド66(PA66)等が好ましく用いられる。
無機充填材の配合量は、無機充填材を含有する樹脂の加工性と機械的強度が損なわれない範囲であることが好ましく、一般に前記極性樹脂100質量部に対して、好ましくは0.1~100質量部、より好ましくは1~50質量部、更に好ましくは3~40質量部である。
例えば、射出インサート成形法により接着成形体を製造する場合には、あらかじめ所定の形状及び寸法に形成しておいた被着体を金型内に配置し、そこに本発明の熱可塑性エラストマー組成物を射出成形して接着成形体を製造する方法が採用される。また、押出しラミネーション法により接着成形体を製造する場合には、あらかじめ所定の形状及び寸法に形成しておいた被着体の表面、又はその縁に対して、押出機に取り付けられた所定の形状を有するダイスから押出した溶融状態の熱可塑性エラストマー組成物を直接押出して接着成形体を製造することもできる。プレス成形法により接着成形体を製造する場合には、射出成形法や押出成形法により、予め本発明の熱可塑性エラストマー組成物からなる成形体を成形しておき、その成形体を、あらかじめ所定の形状及び寸法に形成しておいた被着体に、プレス成形機などを用いて、加熱・加圧して製造することもできる。このような成形法は、被着体がセラミックス、金属である場合に特に適している。
また、自動車や建築物のウィンドウモールやガスケット、ガラスのシーリング材、防腐蝕材など、ガラスと接着された成形体や構造体として広い範囲の用途に有用である。また、自動車や建築物の窓におけるガラスとアルミニウムサッシや金属開口部などとの接合部、太陽電池モジュールなどにおけるガラスと金属製枠体との接続部などのシーラントとしても好適に使用できる。更には、ノート型パソコン、携帯電話、ビデオカメラなどの各種情報端末機器や、ハイブリッド自動車、燃料電池自動車などに用いられる二次電池のセパレーターなどにも好適に使用できる。
更に橋梁などの道路舗装のコンクリート層とアスファルト層の接着剤の用途に好適に使用でき、防水材としても効果も兼ね備える。
<水添ブロック共重合体(A)>
後述の製造例1~4の水添ブロック共重合体(A-1)~(A-4)
<水添ブロック共重合体(A’)>
後述の製造例5、6の水添ブロック共重合体(A’-1)~(A’-2)
<極性基含有オレフィン系重合体(B)>
後述の製造例7、8の極性基含有オレフィン系重合体(B-1)~(B-2)
<ポリビニルアセタール樹脂(C)>
後述の製造例9のポリビニルブチラール(PVB)
<軟化剤(D)>
水添パラフィン系オイル(出光興産株式会社製「ダイアナプロセスオイルPW-90」)
(1)分子量分布及びピークトップ分子量(Mp)等の測定
水添ブロック共重合体のピークトップ分子量(Mp)及び分子量分布(Mw/Mn)は、GPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算分子量で求め、分子量分布のピークの頂点の位置からピークトップ分子量(Mp)を求めた。測定装置及び条件は、以下のとおりである。
・装置 :東ソー株式会社製GPC装置「GPC8020」
・分離カラム :東ソー株式会社製「TSKgelG4000HXL」
・検出器 :東ソー株式会社製「RI-8020」
・溶離液 :テトラヒドロフラン
・溶離液流量 :1.0ml/分
・サンプル濃度:5mg/10ml
・カラム温度 :40℃
各実施例及び比較例において、水素添加前のブロック共重合体及び水素添加後のブロック共重合体(水添ブロック共重合体)をそれぞれ重クロロホルム溶媒に溶解し、日本電子株式会社製「Lambda-500」を用いて50℃で1H-NMRを測定した。水添ブロック共重合体(A)中の重合体ブロック(b)の水素添加率は、得られたスペクトルの4.5~6.0ppmに現れる炭素-炭素二重結合が有するプロトンのピークから、下記式により算出した。
水素添加率={1-(水素添加後のブロック共重合体1モルあたりに含まれる炭素-炭素二重結合のモル数)/(水素添加前のブロック共重合体1モルあたりに含まれる炭素-炭素二重結合のモル数)}×100(モル%)
(3)メルトフローレート(MFR)の測定方法
試料をメルトインデクサL244(株式会社テクノ・セブン製)を用いて、230℃、21N、ノズル寸法=直径1mm×長さ10mmの条件で測定した。
〔製造例1〕
窒素置換し、乾燥させた耐圧容器に、溶媒としてシクロヘキサン50.0kg、アニオン重合開始剤としてsec-ブチルリチウム(10.5質量%シクロヘキサン溶液)35.1g(sec-ブチルリチウム3.7g)を仕込み、50℃に昇温した後、スチレン(1)1.87kgを加えて1時間重合させ、引き続いてβ-ファルネセン8.75kgを加えて2時間重合を行い、更にスチレン(2)1.87kgを加えて1時間重合することにより、ポリスチレン-ポリ(β-ファルネセン)-ポリスチレントリブロック共重合体を含む反応液を得た。この反応液に、水素添加触媒としてパラジウムカーボン(パラジウム担持量:5質量%)を前記ブロック共重合体に対して5質量%添加し、水素圧力2MPa、150℃の条件で10時間反応を行った。放冷、放圧後、濾過によりパラジウムカーボンを除去し、濾液を濃縮し、更に真空乾燥することにより、ポリスチレン-ポリ(β-ファルネセン)-ポリスチレントリブロック共重合体の水素添加物(以下、水添ブロック共重合体(A-1と称する))を得た。水添ブロック共重合体(A-1)について上記した評価を行った。結果を表1に示す。
表1に記載の配合にしたがったこと以外は、製造例1と同様にして水添ブロック共重合体(A-2)~(A-4)を製造した。得られた水添ブロック共重合体(A-2)~(A-4)について、上記した評価を行った。結果を表1に示す。
〔製造例5〕
水添ブロック共重合体(A’-1)は、溶媒のシクロヘキサン50.0kgにテトラヒドロフラン288gを混合し、表1に記載の配合にしたがった以外は、製造例1と同様にして水添ブロック共重合体(A’-1)を製造した。得られた水添ブロック共重合体(A’-1)について、上記した評価を行った。結果を表1に示す。
〔製造例6〕
表1に記載の配合にしたがったこと以外は、製造例1と同様にして水添ブロック共重合体(A’-2)を製造した。得られた水添ブロック共重合体(A’-2)について、上記した評価を行った。結果を表1に示す。
〔製造例7〕
ポリプロピレン「プライムポリプロF327」(MFR[230℃、荷重2.16kg(21N)]:7g/10分、株式会社プライムポリマー製)42g、無水マレイン酸160mg、2,5-ジメチル-2,5-ジ(ターシャルブチルパーオキシ)ヘキサン42mgを、バッチミキサーを用いて180℃およびスクリュー回転数40rpmの条件下で溶融混練し、無水マレイン酸基を含有するポリプロピレン(B-1)を得た。得られた(B-1)のMFR[230℃, 21N]は6g/10分、無水マレイン酸基含有構造単位の割合は0.3質量%であり、融点は138℃であった。なお、該無水マレイン酸基含有構造単位の割合は、得られた(B-1)を水酸化カリウムのメタノール溶液を用いて滴定して得られた値であり、以下同様である。また、融点は10℃/minで昇温した際の示差走査熱量測定曲線の吸熱ピークから読み取った値であり、以下同様である。
ポリプロピレン「ノバテックPP E111G(日本ポリプロ社製)」42g、無水マレイン酸8.4g、2,5-ジメチル-2,5-ジ(ターシャルブチルパーオキシ)ヘキサン126mgを、バッチミキサーを用いて200℃およびスクリュー回転数100rpmの条件下で溶融混練し、無水マレイン酸基を含有するポリプロピレン(B-2)を得た。得られた(B-2)のMFR[230℃, 21N]は80g/10分、無水マレイン酸基含有構造単位の割合は6.0質量%であり、融点は135℃であった。
〔製造例9〕
平均重合度500、けん化度99モル%のポリビニルアルコール樹脂を溶解した水溶液に、n-ブチルアルデヒド及び酸触媒(塩酸)を添加し、攪拌してアセタール化反応を行った。析出した樹脂をpH=6になるまで水洗し、次いで中和剤を添加して中和した後、中和により生じた塩を洗浄して除去した。脱水した後、生成物を揮発分が0.3%になるまで乾燥することにより、アセタール化度が80モル%のポリビニルアセタール樹脂を得た。
表2~表4に記載の各成分を表2~表4に示す割合にて、バッチミキサーを用いて230℃およびスクリュー回転数200rpmの条件下で溶融混練し、熱可塑性エラストマー組成物を作製した。得られた熱可塑性エラストマー組成物について下記の通り物性評価を行った。結果を表2~表4に示す。
(1-1)熱可塑性エラストマー組成物のシートの作製
実施例及び比較例で得られた熱可塑性エラストマー組成物を、株式会社新藤金属工業所製圧縮プレス成形機「NF-37」を使用して、「テフロン(登録商標)」コーティング金属枠をスペーサーとして用い、230℃、100kgf/cm2の荷重で5分間、圧縮プレス成形した後、18℃、15kgf/cm2の荷重で1分間、圧縮プレス成形することで厚さ1mmの熱可塑性エラストマー組成物のシートを得た。
(1-2)硬度の測定
このシートからJIS K 6251に準拠したダンベル5号型の試験片を打ち抜いて試験片を得た。
得られた試験片を用い、タイプAデュロメータの圧子を用い、JIS K 6253-3に準拠して測定した。なお、硬度が低いほど柔軟性に優れる。
上記(1-1)で作成した熱可塑性エラストマー組成物のシートを細断した後に、キャピログラフ(東洋精機社製)に仕込み、1mmφ×10mmサイズのキャピラリー、温度230℃、せん断速度1210s-1での溶融粘度を測定した。この値が小さいほど、成形性に優れる。
(3-1)測定用試料(積層体)の作製
<アルミニウム板との積層体の作製>
長さ75mm×幅25mm×厚さ1mmのアルミニウム板の両面の表面を、洗浄液として、界面活性剤水溶液、蒸留水をこの順に用いて洗浄し、乾燥させた。該アルミニウム板と、上記(1-1)で作製した熱可塑性エラストマー組成物のシートと、厚さ50μmのポリエチレンテレフタレート(PET)シートをこの順で重ね、外寸200mm×200mm、内寸150mm×150mm、厚さ2mmの金属製スペーサーの中央部に配置した。
この重ねたシートと金属製スペーサーをポリテトラフルオロエチレン製シートで挟み、さらに外側から金属板で挟み、圧縮成形機を用いて、160℃の温度条件下、荷重20kgf/cm2(2N/mm2)で3分間圧縮成形することで、PET/熱可塑性エラストマー組成物/アルミニウム板からなる積層体を得た。
<ガラス板との積層体の作製>
長さ75mm×幅25mm×厚さ1mmのガラス板の両面の表面を、洗浄液として界面活性剤水溶液、メタノール、アセトン、蒸留水をこの順に用いて洗浄し、乾燥させた以外は、上記したアルミニウム板との積層体の作製と同様の操作を行い、PET/熱可塑性エラストマー組成物/ガラス板からなる積層体を得た。
<ポリプロピレン(PP)板との積層体の作製>
ポリプロピレン(ノバテックPP MA3 日本ポリプロ社製)を射出成形して得られた、長さ75mm×幅25mm×厚さ1mmのポリプロピレン板を用いた以外は上記したアルミニウム板との積層体の作製と同様の操作を行い、PET/熱可塑性エラストマー組成物/ポリプロピレン板からなる積層体を得た。
<ナイロン板との積層体の作製>
ナイロン(UBE Nylon6 1013B、宇部興産社製)を射出成形して得られた長さ75mm×幅25mm×厚さ1mmのナイロン板を用いた以外は上記したアルミニウム板との積層体の作製と同様の操作を行い、PET/熱可塑性エラストマー組成物/ナイロン板からなる積層体を得た。
上記で作製した積層体について、インストロン社製「インストロン5566」を使用して、JIS K6854-2に準じて、剥離角度180°、引張速度50mm/minの条件で剥離接着強さ試験を行い、接着強さ(剥離強度)を測定した。
また、剥離接着強さ試験後の積層体を目視観察し、凝集破壊及び界面剥離のいずれの破壊形態であるかを評価した。破壊形態が凝集破壊であるものをAで表し、界面剥離であるものをBで表した。
熱収縮率の測定はJIS K 7133に準拠した方法により測定した。すなわち上記(1-1)で作製したエラストマー組成物のシートから120mm×120mmの寸法に試験片を切り出した。試験片中央部に標線の印をつけ、23℃にて標線間距離(L0)を測定した後、220℃で20分間試験片を加熱した。試験片を取り出した後23℃にて30分間放冷し、標線間距離(L)を再度測定した。熱収縮率(ΔL)は以下の計算方法に従って算出した。熱収縮率の値が小さいほど、得られた熱可塑性エラストマー組成物は耐熱性に優れることを示す。
ΔL=(L0-L)/L×100
また、表2において、水添ブロック共重合体(A)に対する極性基含有オレフィン系重合体(B)の含有量が異なっている実施例2,4~6と比較例2~4とを比較すると、極性基含有オレフィン系重合体(B)の割合が本発明の範囲内である実施例2,4~6は、柔軟性、成形加工性及び接着性に優れている。一方、極性基含有オレフィン系重合体(B)の割合が本発明の範囲よりも多い比較例2、3は、柔軟性及び成形加工性に劣る。また、極性基含有オレフィン系重合体(B)の割合が本発明の範囲よりも少ない比較例4は、接着性に劣る。
表3において、実施例8と比較例5は、ともにポリビニルアセタール樹脂(C)を同様の組成で含んでおり、両者は、水添ブロック共重合体の種類のみが異なっている。実施例8と比較例5とを比較すると、ファルネセン由来の構造単位(b1)を有する水添ブロック共重合体(A)を用いた実施例8は、ファルネセン由来の構造単位(b1)を有しない水添ブロック共重合体(A’)を用いた比較例5と比べて、柔軟性、成形加工性及び接着性に優れ、特にガラスに対する接着力がより向上していることが分かる。また、実施例8は熱収縮率が小さいことから、耐熱性にも優れていることがわかる。
表4において、実施例9と比較例6は、ともに軟化剤(D)を同様の組成で含んでおり、両者は、水添ブロック共重合体の種類のみが異なっている。実施例9と比較例6とを比較すると、ファルネセン由来の構造単位(b1)を有する水添ブロック共重合体(A)を用いた実施例9は、ファルネセン由来の構造単位(b1)を有しない水添ブロック共重合体(A’)を用いた比較例6と比べて、柔軟性、成形加工性及び接着性に優れている。さらに、実施例9は熱収縮率が小さく良好な耐熱性を示したが、比較例6は測定中にシートが溶融し、測定できなかった。また、実施例9~12の結果から、軟化剤(D)の含有量を広い範囲で変化させても、本発明の熱可塑性エラストマー組成物は上記の各種性能に優れることが分かる。
Claims (14)
- 芳香族ビニル化合物由来の構造単位からなる重合体ブロック(a)と、ファルネセン由来の構造単位(b1)を1~100質量%含有し、ファルネセン以外の共役ジエン由来の構造単位(b2)を99~0質量%含有する重合体ブロック(b)とを含み、重合体ブロック(a)と重合体ブロック(b)との質量比[(a)/(b)]が1/99~70/30である水添ブロック共重合体(A)100質量部に対して、極性基含有オレフィン系重合体(B)5~300質量部を含有する熱可塑性エラストマー組成物。
- 前記ファルネセンがβ-ファルネセンである、請求項1に記載の熱可塑性エラストマー組成物。
- 前記重合体ブロック(b)中の炭素-炭素二重結合の水素添加率が50モル%以上である、請求項1又は2に記載の熱可塑性エラストマー組成物。
- 前記水添ブロック共重合体(A)のピークトップ分子量(Mp)が4,000~1,500,000である、請求項1~3のいずれかに記載の熱可塑性エラストマー組成物。
- 前記水添ブロック共重合体(A)の分子量分布(Mw/Mn)が1~4である、請求項1~4のいずれかに記載の熱可塑性エラストマー組成物。
- 前記芳香族ビニル化合物がスチレンである、請求項1~5のいずれかに記載の熱可塑性エラストマー組成物。
- 前記ファルネセン以外の共役ジエンが、イソプレン、ブタジエン及びミルセンの少なくとも1種である、請求項1~6のいずれかに記載の熱可塑性エラストマー組成物。
- 前記極性基含有オレフィン系重合体(B)が有する極性基が、(メタ)アクリロイルオキシ基、水酸基、アミド基、ハロゲン原子、カルボキシル基及び酸無水物基から選ばれる少なくとも1種である、請求項1~7のいずれかに記載の熱可塑性エラストマー組成物。
- 前記熱可塑性エラストマー組成物が、更にポリビニルアセタール樹脂(C)を、前記水添ブロック共重合体(A)100質量部に対し、0.1~100質量部含有する、請求項1~8のいずれかに記載の熱可塑性エラストマー組成物。
- 前記ポリビニルアセタール樹脂(C)がポリビニルブチラールである、請求項9に記載の熱可塑性エラストマー組成物。
- 前記熱可塑性エラストマー組成物が、更に軟化剤(D)を、前記水添ブロック共重合体(A)100質量部に対して0.1~300質量部含有する、請求項1~10のいずれかに記載の熱可塑性エラストマー組成物。
- 請求項1~11のいずれかに記載の熱可塑性エラストマー組成物を含む接着剤。
- 請求項1~11のいずれかに記載の熱可塑性エラストマー組成物からなる成形体。
- 前記熱可塑性エラストマー組成物が、セラミックス、金属、極性樹脂及びポリオレフィン樹脂から選ばれる少なくとも1種に接着されてなる、請求項13に記載の成形体。
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EP14869642.0A EP3081594A4 (en) | 2013-12-11 | 2014-12-11 | Thermoplastic elastomer composition, molded article, and adhesive agent |
US15/103,218 US9994705B2 (en) | 2013-12-11 | 2014-12-11 | Thermoplastic elastomer composition, molded article, and adhesive agent |
CN201480067838.0A CN105934479A (zh) | 2013-12-11 | 2014-12-11 | 热塑性弹性体组合物、成形体和粘接剂 |
JP2015552501A JP6504461B2 (ja) | 2013-12-11 | 2014-12-11 | 熱可塑性エラストマー組成物、成形体及び接着剤 |
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JPWO2015087955A1 (ja) | 2017-03-16 |
CN105934479A (zh) | 2016-09-07 |
EP3081594A4 (en) | 2017-07-12 |
KR20160098234A (ko) | 2016-08-18 |
US20160312023A1 (en) | 2016-10-27 |
EP3081594A1 (en) | 2016-10-19 |
TW201529692A (zh) | 2015-08-01 |
CA2933267A1 (en) | 2015-06-18 |
US9994705B2 (en) | 2018-06-12 |
JP6504461B2 (ja) | 2019-04-24 |
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