WO2012026501A1 - 熱可塑性重合体組成物および成形品 - Google Patents
熱可塑性重合体組成物および成形品 Download PDFInfo
- Publication number
- WO2012026501A1 WO2012026501A1 PCT/JP2011/069092 JP2011069092W WO2012026501A1 WO 2012026501 A1 WO2012026501 A1 WO 2012026501A1 JP 2011069092 W JP2011069092 W JP 2011069092W WO 2012026501 A1 WO2012026501 A1 WO 2012026501A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- polymer composition
- thermoplastic polymer
- parts
- resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- 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
-
- 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
- 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
- C09J123/02—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 not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
Definitions
- the present invention is a thermoplastic polymer composition that is excellent in flexibility, mechanical properties, molding processability, and particularly heat resistance, and can be bonded to ceramics, metals, or synthetic resins at low temperatures without being subjected to primer treatment or the like. And a molded article formed using the thermoplastic polymer composition.
- 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 can be bonded or combined with highly flexible elastomer members 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 having excellent flexibility and mechanical properties, and further excellent 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 has been 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 excellent in flexibility, mechanical properties, molding processability, and adhesiveness, but in a manufacturing process of a molded product formed by bonding to ceramics, metal or synthetic resin. It is bonded after heat treatment at a high temperature of 200 ° C. or higher (particularly 240 ° C. or higher when bonding ceramics or metals).
- the thermoplastic polymer composition disclosed in Patent Document 7 does not have sufficient adhesive strength at a temperature of 180 ° C. or lower. By the way, in the injection molding machine or the extruder, even if the thermoplastic polymer composition is heated and melted at 200 ° C. or higher, the surface temperature is immediately cooled to 200 ° C.
- thermoplastic polymer composition specifically disclosed in the Examples of Patent Document 7 to ceramics, metal, or synthetic resin is 60 ° C. or higher (more specifically 80 ° C.
- thermoplastic polymer specifically disclosed in Patent Document 7 is also disclosed. There was room for further improvement in the compositions and molded articles.
- the present invention has been made in view of the above circumstances, and is excellent in flexibility, mechanical properties, molding processability, and particularly heat resistance, and ceramics, metals and synthetic resins can be obtained without performing primer treatment or the like. It is an object of the present invention to provide a thermoplastic polymer composition that can be bonded by a heat treatment at a low temperature (for example, 190 ° C. or less), and a molded article using the thermoplastic polymer composition.
- a polymer block containing an aromatic vinyl compound unit, an isoprene unit and a butadiene unit in which the amount of 1,2-bond and 3,4-bond is 40 mol% or more in total a block copolymer having a polymer block containing an isoprene / butadiene unit or a hydrogenated product of the thermoplastic elastomer (A) and the polyvinyl acetal resin (B), and further a polar group-containing polypropylene resin (C) It has been found that the above-mentioned problems can be solved by a thermoplastic polymer composition containing each of the above in a specific compounding ratio.
- thermoplastic polymer composition by specific compounding ratio. That is, the present invention provides the following [1] to [11].
- thermoplastic polymer composition containing 5 to 100 parts by mass.
- thermoplastic polymer composition according to the above [1] or [2], further comprising 0.1 to 300 parts by mass of the softening agent (D) with respect to 100 parts by mass of the thermoplastic elastomer (A).
- the polyvinyl acetal resin (B) is obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 100 to 4,000, and the acetalization degree is 55 to 88 mol%.
- thermoplastic polymer composition according to any one of the above [1] to [5], wherein the polyvinyl acetal resin (B) is polyvinyl butyral.
- C polar group-containing polypropylene resin
- thermoplastic polymer composition is adhered to at least one selected from ceramics, metals and synthetic resins.
- thermoplastic polymer composition adhered to at least one selected from ceramics and metals.
- thermoplastic polymer composition is formed by bonding at least two kinds selected from ceramics, metals, or synthetic resins, or ceramics, metals, and synthetic resins. .
- thermoplastic polymer composition of the present invention is excellent in flexibility, mechanical properties, molding processability and particularly heat resistance, and is a molded product obtained by bonding the thermoplastic polymer composition of the present invention to ceramics, metal or synthetic resin. However, even if it is placed in a temperature environment of, for example, 60 ° C. or higher, it has practically sufficient adhesiveness and can be used in a wide range of applications. At the same time, the thermoplastic polymer composition of the present invention can be bonded to at least one selected from ceramics, metals, and synthetic resins even at a temperature of 190 ° C. or lower, and is a molded article bonded to these. Can be provided. Further, there is no need to perform primer treatment on the adherend when bonding.
- thermoplastic polymer composition of the present invention comprises a polymer block containing an aromatic vinyl compound unit, an isoprene unit in which the amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, butadiene 100 parts by mass of a thermoplastic elastomer (A) (hereinafter abbreviated as thermoplastic elastomer (A)) which is a block copolymer having a unit or a polymer block containing isoprene / butadiene units or a hydrogenated product thereof And a thermoplastic polymer composition containing 1 to 100 parts by mass of the polyvinyl acetal resin (B) and 5 to 100 parts by mass of the polar group-containing polypropylene resin (C).
- A thermoplastic elastomer
- thermoplastic polymer composition of the present invention may further contain a softening agent (D).
- thermoplastic polymer composition of the present invention may further contain a tackifier resin (E) in order to improve moldability.
- a softening agent D
- thermoplastic polymer composition of the present invention may further contain a tackifier resin (E) in order to improve moldability.
- thermoplastic elastomer (A) imparts flexibility, good mechanical properties, moldability, and the like to the thermoplastic polymer composition of the present invention, and plays a role of a matrix in the composition.
- the amount of 1,2-bond and 3,4-bond are combined to be 40 mol% or more.
- the compatibility with the polar group-containing polypropylene resin (C) is enhanced, and the obtained thermoplastic polymer composition has high adhesiveness in a temperature environment of 60 ° C. or higher, further 80 ° C. or higher.
- aromatic vinyl compound constituting the polymer block containing an aromatic vinyl compound unit examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, Examples include 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like.
- the polymer block containing the aromatic vinyl compound unit may be composed of a structural unit derived from only one of these aromatic vinyl compounds, or may be composed of a structural unit derived from two or more types. . Of these, styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
- the “polymer block containing an aromatic vinyl compound unit” is preferably a polymer block containing 80% by mass or more of an aromatic vinyl compound unit, more preferably an aromatic vinyl compound unit 90.
- the polymer block containing the aromatic vinyl compound unit may have only the aromatic vinyl compound unit. However, as long as the effect of the present invention is not impaired, other copolymerizable units may be used together with the aromatic vinyl compound unit. It may have a monomer unit.
- Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and the like.
- the proportion thereof is preferably 20% by mass or less, more preferably 10%, based on the total amount of the aromatic vinyl compound unit and other copolymerizable monomer units. It is not more than mass%, more preferably not more than 5 mass%.
- the polymer block includes a polymer block containing an isoprene unit or an isoprene / butadiene unit from the viewpoint of adhesiveness at 190 ° C. or lower and heat resistance (adhesive property in a temperature environment of 60 ° C. or higher). preferable.
- the “isoprene unit” is a structural unit derived from isoprene
- the “butadiene unit” is derived from butadiene such as butadiene and 2,3-dimethyl-1,3-butadiene. It is a structural unit.
- the “isoprene / butadiene unit” is a structural unit derived from both isoprene and butadiene such as butadiene and 2,3-dimethyl-1,3-butadiene.
- the bonding form of the compound constituting the polymer block containing the isoprene unit, butadiene unit or isoprene / butadiene unit is described above from the viewpoint of heat resistance.
- the total amount of 1,2-bonds and 3,4-bonds needs to be 40 mol% or more.
- the total amount of 1,2-bond and 3,4-bond is preferably 45 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 50 to 80 mol%. is there.
- a bond form other than 1,2-bond and 3,4-bond is 1,4-bond.
- the 1,2-bond amount and 3,4-bond amount can be calculated by 1 H-NMR measurement. Specifically, the integrated value of the peak present at 4.2 to 5.0 ppm derived from 1,2-bond units and 3,4-bond units and 5.0 to 5 derived from 1,4-bond units. It can be calculated from the ratio with the integrated value of the peak existing at .45 ppm.
- the “polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit” is preferably an isoprene unit, a butadiene unit or an isoprene / butadiene unit of 80% by mass or more, more preferably 90% by mass or more.
- it is a polymer block containing 95% by mass or more (both are values in terms of raw material charge amount).
- the polymer block containing a conjugated diene compound unit may have only an isoprene unit, a butadiene unit, or an isoprene / butadiene unit, but isoprene unit, butadiene unit or isoprene / You may have another copolymerizable monomer unit with a butadiene unit.
- examples of other copolymerizable monomers include styrene monomers such as styrene, ⁇ -methylstyrene, and 4-methylstyrene.
- the ratio thereof is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less with respect to all structural units.
- the bonding form of the polymer block containing the aromatic vinyl compound unit and the polymer block containing the isoprene unit, butadiene unit or isoprene / butadiene unit in the thermoplastic elastomer (A) is not particularly limited, and is linear, It may be any of branched, radial, or a combined form in which two or more of these are combined, but a linear combined form is preferred.
- a linear bond form when a polymer block containing an aromatic vinyl compound unit is represented by a and a polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit is represented by b, a A diblock copolymer represented by -b, a triblock copolymer represented by aba or b-a-b, a tetrablock copolymer represented by abbab, a pentablock copolymer represented by abababa or bababa, an ( perennial-b) nX copolymer (X represents a coupling residue, and n Represents an integer of 2 or more), and mixtures thereof.
- a triblock copolymer is preferable, and a triblock copolymer represented by aba is more preferable.
- thermoplastic elastomer (A) from the viewpoint of improving heat resistance and weather resistance, a part or all of the polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit is hydrogenated (hereinafter referred to as “hydrogenation”). (It may be abbreviated as “.”).
- the hydrogenation rate of the polymer block containing isoprene units, butadiene units or isoprene / butadiene units at that time is preferably 80% or more, more preferably 90% or more.
- the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.
- the content of the polymer block containing the aromatic vinyl compound unit in the thermoplastic elastomer (A) is preferably 5 to 75 mass with respect to the entire thermoplastic elastomer (A) from the viewpoint of flexibility and mechanical properties. %, More preferably 5 to 60% by mass, still more preferably 10 to 40% by mass.
- the weight average molecular weight of the thermoplastic elastomer (A) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, from the viewpoint of its mechanical properties and molding processability.
- the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
- GPC gel permeation chromatography
- a thermoplastic elastomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the thermoplastic polymer composition of the present invention contains the specific thermoplastic elastomer (A).
- a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol%, or hydrogenation thereof is preferably 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A).
- thermoplastic elastomer (A) More preferably 40 parts by mass or less, more preferably 25 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, particularly preferred. Substantially to 0 parts by weight. When the content is 100 parts by mass or less, more preferably 40 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A), mechanical properties such as tensile breaking strength and tensile breaking elongation are improved, In a molded product formed by bonding to ceramics, metal, or synthetic resin, it has excellent adhesion under a temperature environment of 60 ° C. or higher and does not peel easily. This is presumed to be related to compatibility with the component (C) described later. Each term in the above “” is explained in the same manner as described above except for the term “polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol%”. Is.
- examples of the conjugated diene compound from which the conjugated diene compound unit is derived include isoprene, butadiene, 2, 3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like.
- the polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol% may be composed of a structural unit derived from only one of the above conjugated diene compounds, or derived from two or more types.
- the 1,4-bond amount can be calculated by the 1 H-NMR measurement described above.
- thermoplastic elastomer (A) (Method for producing thermoplastic elastomer (A))
- the manufacturing method of a thermoplastic elastomer (A) is not specifically limited, For example, it can manufacture by an anionic polymerization method.
- (I) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using an alkyl lithium compound as an initiator;
- an alkyl lithium compound is used as an initiator, the aromatic vinyl compound and the conjugated diene compound are sequentially polymerized, and then a coupling agent is added to perform coupling;
- a coupling agent is added to perform coupling;
- a method of sequentially polymerizing the conjugated diene compound and then the aromatic vinyl compound using a dilithium compound as an initiator (I) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using a dilithium compound as an initiator.
- Examples of the alkyl lithium compound in the above (i) and (ii) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium and the like.
- Examples of the coupling agent in (ii) include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like.
- Examples of the dilithium compound in (iii) include naphthalenedilithium and dilithiohexylbenzene.
- the amounts of initiators and coupling agents such as these alkyllithium compounds and dilithium compounds are determined by the weight average molecular weight of the target thermoplastic elastomer (A), and the aromatic vinyl compound used in the anionic polymerization method and In general, 0.01 to 0.2 parts by mass of an initiator such as an alkyl lithium compound or a dilithium compound is usually used for 100 parts by mass of the conjugated diene compound.
- the coupling agent is usually used in an amount of 0.001 to 0.8 parts by mass with respect to 100 parts by mass in total of the aromatic vinyl compound and the conjugated diene compound used in the anionic polymerization method.
- the anionic polymerization is preferably performed in the presence of a solvent.
- the solvent is not particularly limited as long as it is inert to the initiator and does not adversely affect the polymerization.
- saturated aliphatic hydrocarbons such as hexane, heptane, octane, decane; toluene, benzene, xylene, etc.
- aromatic hydrocarbons such as hexane, heptane, octane, decane; toluene, benzene, xylene, etc.
- the polymerization is usually preferably carried out at 0 to 80 ° C. for 0.5 to 50 hours.
- the amount of 1,2-bonds and 3,4-bonds of the thermoplastic elastomer (A) can be increased, and depending on the amount of the organic Lewis base added, The 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) can be easily controlled.
- the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA) and N-methylmorpholine; nitrogen-containing heterocyclic groups such as pyridine.
- Aromatic compounds Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulfoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone Can be mentioned.
- These organic Lewis bases may be used individually by 1 type, and may be used in combination of 2 or more type.
- the organic Lewis base is used in an amount of, for example, lithium ions contained in the initiator from the viewpoint of setting the 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) to 40 mol% or more.
- the stoichiometric ratio is preferably 0.01 to 1000 times, more preferably 0.1 to 100 times, and still more preferably 0.1 to 50 times.
- the block copolymer contained in the reaction solution is solidified by pouring it into a poor solvent of the block copolymer such as methanol, or the reaction solution is poured into hot water together with steam. After removing the solvent by azeotropic distillation (steam stripping), the unhydrogenated thermoplastic elastomer (A) can be isolated by drying. Furthermore, the hydrogenated thermoplastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) obtained above to a hydrogenation reaction.
- the unhydrogenated styrene thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated styrene thermoplastic is obtained.
- the elastomer (A) can be used as it is without being isolated from the reaction solution and reacted with hydrogen in the presence of a hydrogenation catalyst.
- the hydrogenation catalyst examples include Raney nickel; heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth; transition metal compound, alkylaluminum compound, alkyllithium compound Ziegler catalysts composed of a combination with the above; metallocene catalysts and the like.
- the hydrogenation reaction can usually be carried out under conditions of a hydrogen pressure of 0.1 to 20 MPa, a reaction temperature of 20 to 250 ° C., and a reaction time of 0.1 to 100 hours.
- the hydrogenation reaction liquid is poured into a poor solvent such as methanol to solidify, or the hydrogenation reaction liquid is poured into hot water together with steam and the solvent is removed azeotropically (steam stripping).
- a poor solvent such as methanol to solidify
- the hydrogenation reaction liquid is poured into hot water together with steam and the solvent is removed azeotropically (steam stripping).
- steam stripping By drying, the hydrogenated styrenic thermoplastic elastomer (A) can be isolated.
- the polyvinyl acetal resin (B) imparts adhesiveness to the thermoplastic polymer composition of the present invention, and is usually dispersed in islands in the composition. With the polyvinyl acetal resin (B), the thermoplastic polymer composition of the present invention can be adhered well without subjecting the surface of an adherend such as ceramic, metal or synthetic resin to primer treatment.
- the polyvinyl acetal resin (B) usually has a repeating unit represented by the following formula (I).
- 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 of aldehyde 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 (B) 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 (B) is usually preferably 100 to 4,000, more preferably 100 to 3,000, still more preferably 100 to 2,000, particularly preferably. Is 250 to 2,000. If the average degree of polymerization of polyvinyl alcohol is 100 or more, the production of the polyvinyl acetal resin (B) becomes easy and the handleability is good.
- the average degree of polymerization of polyvinyl alcohol is 4,000 or less, the melt viscosity at the time of melt-kneading does not become too high, and the production of the thermoplastic polymer composition of the present invention is easy.
- 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 further 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 (B) 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 (B) obtained by acetalization using n-butyraldehyde is particularly referred to as polyvinyl butyral (PVB).
- the proportion of butyral units (see the following formula) among the acetal units present in the polyvinyl acetal resin (B) is preferably 0.8 or more, more preferably 0.9 or more, and still more preferably 0.8. 95 or more, particularly preferably substantially 1. That is, in the structural formula of the polyvinyl acetal resin (B) represented by the above formula (I), when only R 1 is nC 3 H 7 , 0.8 ⁇ k (1) / (k (1) + k (2) +... + K (n) ) is preferred.
- the degree of acetalization of the polyvinyl acetal resin (B) used in the present invention is preferably 55 to 88 mol%.
- the polyvinyl acetal resin (B) having an acetalization degree of 55 mol% or more is low in production cost, easily available, and has good melt processability.
- the polyvinyl acetal resin (B) having an acetalization degree 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 (B) is more preferably 60 to 88 mol%, further preferably 70 to 88 mol%, and particularly preferably 75 to 85 mol%.
- the affinity and compatibility with the thermoplastic elastomer (A) are improved, the mechanical properties of the thermoplastic polymer composition are excellent, and the adhesive strength with ceramics, metal and synthetic resin is increased.
- ⁇ k (1) + k (2) + ... + k (n) ⁇ ⁇ 2 / ⁇ k (1) + k (2) + ... + k (n) ⁇ ⁇ 2 + l + m ⁇ ⁇ 100 Can determine the degree of acetalization (mol%).
- the degree of acetalization of the polyvinyl acetal resin (B) is determined by dissolving the polyvinyl acetal resin (B) in a suitable deuterated solvent such as deuterated dimethyl sulfoxide, and measuring 1 H-NMR or 13 C-NMR. May be calculated.
- vinyl alcohol units are preferably 12 to 45 mol% (0.12 ⁇ l ⁇ 0.45), more preferably 17 to 45 mol% (0.17 ⁇ l ⁇ 0). .45), and preferably contains 0 to 5 mol% (0 ⁇ m ⁇ 0.05), more preferably 0 to 3 mol% (0 ⁇ m ⁇ 0.03) of vinyl acetate units.
- 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 (B); polyvinyl alcohol is dispersed in an organic solvent, and an acid catalyst Solvent method for precipitating polyvinyl acetal resin (B) 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 (B). Etc.
- the acid catalyst is not particularly limited.
- 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 even more 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 (B) 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 (B) used in the present invention a resin obtained by reducing the aldehyde reaction residue or moisture by degassing under reduced pressure when processed into a powder, granule or pellet is preferable. .
- the thermoplastic polymer composition of the present invention contains 1 to 100 parts by mass of the polyvinyl acetal resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A).
- the polyvinyl acetal resin (B) is less than 1 part by mass, it is difficult to obtain sufficient adhesion with ceramics, metal and synthetic resin. More preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more.
- the amount of the polyvinyl acetal resin (B) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited.
- the content of the polyvinyl acetal resin (B) is preferably 1 to 70 parts by weight, more preferably 5 to 70 parts by weight, and more preferably 10 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer (A). Part by mass, more preferably 10 to 50 parts by mass, particularly preferably 15 to 45 parts by mass.
- the thermoplastic polymer composition of the present invention contains the polar group-containing polypropylene resin (C), so that the thermoplastic heavyweight of the present invention is contained.
- the thermoplastic polymer composition of the present invention contains the polar group-containing polypropylene resin (C), so that the thermoplastic heavyweight of the present invention is contained.
- Examples of the polar group of the polar group-containing polypropylene resin (C) include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group;
- the method for producing the polar group-containing polypropylene resin (C), but propylene (an ⁇ -olefin as necessary) and a polar group-containing copolymerizable monomer are randomly copolymerized by a known method. It can be obtained by polymerization, block copolymerization or graft copolymerization. In addition, it can also be obtained by subjecting a polypropylene resin to a reaction such as oxidation or chlorination by a known method.
- Examples of the ⁇ -olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like.
- the proportion of units derived from ⁇ -olefins other than propylene to the total structural units of the polar group-containing polypropylene resin (C) is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, Preferably, it is 0 to 25 mol%.
- Examples of the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid, ester or anhydride thereof.
- unsaturated carboxylic acid or its ester or anhydride is preferable.
- unsaturated carboxylic acid or ester or anhydride thereof include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, highmic acid, and hymic anhydride. An acid etc. are mentioned. Among these, maleic anhydride is more preferable.
- These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
- the polar group-containing polypropylene resin (C) is preferably a polypropylene containing a carboxyl group as a polar group, that is, a carboxylic acid-modified polypropylene resin, from the viewpoint of compatibility with the polyvinyl acetal resin (B).
- a modified polypropylene resin is more preferable.
- (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 polymerization form of the polar group-containing polypropylene resin (C) used in the present invention is not particularly limited, and a random copolymer, a block copolymer, a graft copolymer, and the like can be used. Among these, a random copolymer and a graft copolymer are preferable, and a graft copolymer is more preferable.
- the polar group of the polar group-containing polypropylene resin (C) used in the present invention may be post-treated after polymerization.
- it may be neutralized with a metal ion of a (meth) acrylic acid group or a carboxyl group 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 polypropylene resin (C) used in the present invention under the conditions of 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 100 g / 10 min. More preferably 0.1 to 70 g / 10 minutes, more preferably 0.1 to 50 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, still more preferably 1 to 20 g / 10 minutes, and particularly preferably 1 to 15 g. / Min. If the MFR of the polar group-containing polypropylene resin (C) under the above conditions is 0.1 g / 10 min or more, sufficient adhesive strength at 190 ° C. or less can be obtained.
- the melting point of the polar group-containing polypropylene resin (C) is preferably 100 ° C. or higher, more preferably 110 to 170 ° C., and further preferably 120 to 140 ° C. from the viewpoint of heat resistance.
- the ratio of the polar group-containing structural unit of the polar group-containing polypropylene resin (C) to the total structural unit of the polar group-containing polypropylene resin (C) is preferably 0.01 to 10% by mass, more preferably 0. 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.1 to 2% by mass.
- the proportion of the polar group-containing structural unit is within this range, the affinity and compatibility with the thermoplastic elastomer (A) and the compatibility with the polyvinyl acetal resin (B) are good, and the heat
- the mechanical properties of the plastic polymer composition are improved, and the adhesiveness to ceramics, metals and synthetic resins and the adhesive strength at 190 ° C. or lower are increased.
- the polypropylene resin having a polar group-containing structural unit at a high concentration may be diluted with a polypropylene resin having no polar group-containing structural unit so that the ratio of the polar group-containing structural unit is optimized.
- the thermoplastic polymer composition of the present invention contains 5 to 100 parts by mass of the polar group-containing polypropylene resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A).
- the polar group-containing polypropylene resin (C) is less than 5 parts by mass, it is difficult to adhere to ceramics, metal or synthetic resin at 190 ° C. or lower, and a molded product formed by adhering to ceramic, metal or synthetic resin is 60 ° C. When exposed to the above temperature environment, the adhesive strength is practically insufficient and the film is easily peeled off.
- the amount of the polar group-containing polypropylene resin (C) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited.
- the content of the polar group-containing polypropylene resin (C) is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less, Most preferably, it is 30 mass parts or less.
- the content of the polar group-containing polypropylene resin (C) is preferably 5 to 70 parts by mass, more preferably 10 to 70 parts by mass, and more preferably 100 parts by mass of the thermoplastic elastomer (A).
- the amount is 10 to 60 parts by mass, more preferably 10 to 30 parts by mass, and particularly preferably 20 to 30 parts by mass.
- Softener (D) As the softener (D) which may be contained in the thermoplastic polymer composition of the present invention, for example, softeners generally used for rubber and plastics can be used.
- softeners generally used for rubber and plastics
- paraffinic, naphthenic and aromatic process oils phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate
- white oil mineral oil, ethylene and ⁇ -olefin oligomers
- paraffin wax liquid paraffin, polybutene, low molecular weight polybutadiene And low molecular weight polyisoprene.
- process oil is preferable, and 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 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.
- 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.
- thermoplastic polymer composition of the present invention may not contain the softening agent (D), but from the viewpoints of flexibility, moldability and adhesiveness, the thermoplastic elastomer (A) 100 may be used as necessary.
- the amount is preferably 0.1 to 300 parts by weight, more preferably 1 to 200 parts by weight, more preferably 10 to 200 parts by weight, still more preferably 50 to 200 parts by weight, particularly preferably 50 to 150 parts by weight with respect to parts by weight. A part may be contained.
- thermoplastic polymer composition of the present invention can further improve molding processability while maintaining adhesive properties by containing a tackifier resin (E) as necessary.
- tackifier resins (E) include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, water Hydrogenated aromatic hydrocarbon resin, rosin ester resin, hydrogenated rosin ester resin, terpene phenol resin, hydrogenated terpene phenol resin, terpene resin, hydrogenated terpene resin, aromatic hydrocarbon modified terpene resin, coumarone / indene resin, phenol resin And xylene resin.
- Tackifying resin (E) may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, aliphatic saturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, and hydrogenated terpene resins are preferable.
- the softening point of the tackifier resin (E) is preferably 50 to 200 ° C, more preferably 65 to 180 ° C, and further preferably 80 to 160 ° C. If the softening point is 50 ° C. or higher, the adhesive property with respect to the environmental temperature can be maintained. On the other hand, if the softening point is 200 ° C. or lower, the adhesive properties with respect to the heat treatment temperature can be maintained.
- the softening point is a value measured according to ASTM 28-67.
- thermoplastic polymer composition of the present invention contains the tackifier resin (E), it is preferably 1 to 100 parts by weight, more preferably 5 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer (A). Part, more preferably 5 to 50 parts by weight, particularly preferably 10 to 45 parts by weight. If the content of the tackifying resin (E) is 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A), the thermoplastic polymer composition does not become hard, and flexibility and mechanical properties are easily exhibited. .
- thermoplastic polymer composition of the present invention can be used as long as it does not significantly impair the effects of the present invention, as required by other thermoplastic heavy polymers such as olefin polymers, styrene polymers, polyphenylene ether resins, and polyethylene glycol. It may contain a coalescence.
- thermoplastic heavy polymers such as olefin polymers, styrene polymers, polyphenylene ether resins, and polyethylene glycol. It may contain a coalescence.
- olefin polymer include polyethylene, polypropylene, polybutene, block copolymers of propylene and other ⁇ -olefins such as ethylene and 1-butene, and random copolymers.
- the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).
- it is more preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less.
- the thermoplastic polymer composition of the present invention may contain an inorganic filler as necessary.
- the inorganic filler is useful for improving the physical properties such as heat resistance and weather resistance of the thermoplastic polymer composition of the present invention, adjusting the hardness, and improving the economical efficiency as an extender.
- Such inorganic filler is not particularly limited, and examples thereof 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. Examples include fibers.
- 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 within a range in which the flexibility of the thermoplastic polymer composition is not impaired, and is generally preferably 100 with respect to 100 parts by mass of the thermoplastic elastomer (A). It is not more than part by mass, more preferably not more than 70 parts by mass, still more preferably not more than 30 parts by mass, particularly preferably not more than 10 parts by mass.
- the thermoplastic polymer composition of the present invention is an antioxidant, a lubricant, a light stabilizer, a processing aid, a colorant such as a pigment or a dye, a flame retardant, and the like, as long as the effects of the invention are not significantly impaired. It may contain an antistatic agent, a matting agent, silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antibacterial agent, an antifungal agent, a fragrance and the like.
- the antioxidant 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 polymer composition is melt-kneaded, and preferably with respect to 100 parts by mass of the thermoplastic elastomer (A). Is 0.1 to 5 parts by mass.
- the method for preparing the thermoplastic polymer composition of the present invention is not particularly limited, and any method can be used as long as the above components can be uniformly mixed.
- a melt-kneading method is 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 the melt kneading is usually performed preferably 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 the melt kneading is usually performed preferably at 170 to 270 ° C.
- the thermoplastic polymer composition of the present invention can be obtained.
- thermoplastic polymer composition of the present invention has a hardness according to the JIS-A method of JIS K 6253 (hereinafter sometimes referred to as “A hardness”), preferably 93 or less, more preferably 30 to 90, more preferably 40 to 85. If the A hardness is too high, flexibility, elasticity, and mechanical properties are hardly exhibited, and a thermoplastic resin having excellent adhesion to synthetic resins, particularly resins, ceramics, and metals containing inorganic fillers (glass fibers, etc.). There exists a tendency for the suitable use as a union composition to become difficult.
- a hardness JIS-A method of JIS K 6253
- melt flow rate (MFR) of the thermoplastic polymer composition measured by a method according to JIS K 7210 at 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 1 to It is in the range of 20 g / 10 min, more preferably 1 to 10 g / 10 min, still more preferably 2 to 10 g / min.
- MFR melt flow rate
- the present invention also provides a molded article using the above-described thermoplastic polymer composition of the present invention. Since the thermoplastic polymer composition of the present invention is excellent in moldability, various molded articles can be produced.
- the molded product may be a sheet or a film.
- various molding methods generally used for thermoplastic polymer 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.
- a preferred embodiment of the present invention is a molded article in which the thermoplastic polymer composition is bonded to at least one selected from ceramics, metals and synthetic resins, and further, the thermoplastic polymer composition
- it is a molded article formed by bonding ceramics, metals or synthetic resins, or at least two selected from ceramics, metals and synthetic resins.
- a molded article formed by bonding to at least one selected from ceramics (particularly glass) and metal (particularly aluminum) is preferable.
- the adhesive strength of the thermoplastic polymer composition in the molded article is preferably 20 N / 25 mm or more, which is usually not easily peeled by human hands.
- the adhesive strength is a value measured according to JIS K 6854-2 by the method described in the examples.
- thermoplastic polymer composition of the present invention is excellent in flexibility, mechanical properties, molding processability and particularly heat resistance, and is a molded product obtained by bonding the thermoplastic polymer composition of the present invention to ceramics, metal or synthetic resin. However, even if it is exposed to a temperature environment of, for example, 60 ° C. or higher, it has practically sufficient adhesiveness. In addition, ceramics, metal, or synthetic resin can be bonded at 190 ° C. or lower without performing primer treatment or the like. Therefore, in the production process of a molded article bonded to at least one selected from ceramics, metals and synthetic resins, the surface temperature of this thermoplastic polymer composition discharged from an injection molding machine or an extruder is 190 ° C.
- Adequate adhesion is possible even in the following cases, so 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 members around the bonded portions that are heated at the same time.
- the ceramic that can be used in the molded article of the present invention means a nonmetallic inorganic material, 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.
- molded product having a metal surface formed by plating such as copper plating, nickel plating, chrome plating, tin plating, galvanization, platinum plating, gold plating, or silver plating.
- Synthetic resins that can be used in the molded article of the present invention include, for example, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, (meth) acrylonitrile-butadiene-styrene resin, (meth) acrylonitrile-styrene resin, (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, polyetheretherketone resin, polystyrene resin, syndiotactic polystyrene resin, poly Such as olefin resin, and the like. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
- the synthetic 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 in which the molding processability and mechanical strength of the resin containing the inorganic filler are not impaired, and is generally 0.1% relative to 100 parts by mass of the synthetic resin. To 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 3 to 40 parts by mass.
- the method for producing a molded article in which the thermoplastic polymer composition is bonded to ceramics or metal is not particularly limited, and any method may be adopted as long as it is a method for producing a molded article by melt bonding, Examples thereof include molding methods such as injection insert molding, extrusion lamination, press molding, and melt casting.
- molding methods such as injection insert molding, extrusion lamination, press molding, and melt casting.
- an adherend that has been formed in a predetermined shape and size in advance is placed in a mold, and the thermoplastic polymer composition of the present invention is placed there.
- a method of manufacturing a molded body by injection molding is adopted.
- a molded body is manufactured by the extrusion lamination method
- a predetermined shape attached to the extruder is applied to the surface of the adherend that has been previously formed into a predetermined shape and dimensions, or the edge thereof.
- a molded product can also be produced by directly extruding a molten thermoplastic polymer composition extruded from a die having the same.
- a molded product made of the thermoplastic polymer 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.
- a nonpolar resin layer such as an olefin-based resin or a cyclic olefin-based resin may be provided on the outermost layer on the surface that does not adhere to the adherend as necessary for protection or decoration.
- the method for producing a molded product obtained by bonding the thermoplastic polymer composition of the present invention to the synthetic resin is not particularly limited. Both can be melted at the same time and co-extruded or co-injected. Further, it may be melt-coated on one of the previously molded products, or may be solution-coated. In addition, two-color molding or insert molding can be employed.
- thermoplastic polymer composition of the present invention can be widely applied as the above molded article.
- the shape, structure, use, etc. are not particularly limited, and the thermoplastic polymer composition of the present invention is bonded to ceramics, metal or synthetic resin. Any structure is included in the scope of the present invention.
- synthetic resins, synthetic resins containing glass fibers, and light metals such as aluminum and magnesium alloys are used for housing materials such as electronic / electrical equipment, OA equipment, home appliances, and automobile members. And a molded article to which the thermoplastic polymer composition of the present invention is adhered.
- 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.
- the junction part of the glass in the window of a motor vehicle or a building an aluminum sash, a metal opening part, etc., the connection part of the glass in a solar cell module etc., and a metal frame.
- it can be suitably used for various information terminal devices such as notebook computers, mobile phones, and video cameras, as well as secondary battery separators used in hybrid vehicles and fuel cell vehicles.
- thermoplastic polymer composition of the present invention is also suitably used as an adhesive.
- the thermoplastic polymer composition of the present invention has good adhesiveness to any of ceramics, metals and synthetic resins, and thus bonds not only the same kind of materials but also different kinds of materials to each other. It is also suitably used as an adhesive.
- it since it has flexibility, it also has a buffering action against a difference in thermal expansion coefficient between different materials.
- Thermoplastic elastomer (A1) A pressure-resistant container purged with nitrogen and dried was charged with 64 L of cyclohexane as a solvent and 0.20 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran (lithium atoms in the initiator) as a Lewis base. The equivalent of 15 times the stoichiometric ratio). After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, then 23 L of isoprene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours.
- the obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
- 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer.
- the reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C.
- thermoplastic elastomer (A1) has a weight average molecular weight of 107,000, a styrene content of 21% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, a 1,2-bond amount and 3,4. -The total amount of binding was 60 mol%.
- Thermoplastic elastomer (A2) A pressure-resistant container purged with nitrogen and dried was charged with 150 L of cyclohexane as a solvent and 0.22 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator). In contrast, the stoichiometric ratio was 14 times equivalent). After raising the temperature to 50 ° C., 0.72 L of styrene is added and polymerized for 3 hours.
- thermoplastic elastomer (A2) has a weight average molecular weight of 165,000, a styrene content of 13% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.02, 1,2-bond amount and 3,4. -The total amount of binding was 63 mol%.
- Thermoplastic elastomer (A3) A pressure-resistant container purged with nitrogen and dried was charged with 120 L of cyclohexane as a solvent, 0.12 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator). The stoichiometric ratio is equivalent to 26 times). After the temperature was raised to 50 ° C., 3.6 L of styrene was added for polymerization for 3 hours, then 20.0 L of isoprene was added for polymerization for 4 hours, and further 3.6 L of styrene was added for polymerization for 3 hours.
- the obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
- 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer.
- the reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C.
- thermoplastic elastomer (A3) has a weight average molecular weight of 320,000, a styrene content of 33% by mass, a hydrogenation rate of 90%, a molecular weight distribution of 1.07, 1,2-bond amount and 3,4. -The total amount of binding was 54 mol%.
- Thermoplastic elastomer (A4) A pressure-resistant container purged with nitrogen and dried was charged with 86 L of cyclohexane as a solvent and 0.22 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.02 L of ethylene glycol dimethyl ether as a Lewis base (in the initiator). The equivalent of 0.7 times the stoichiometric ratio with respect to lithium atoms).
- reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polybutadiene-polystyrene.
- thermoplastic elastomer (A4) has a weight average molecular weight of 126,000, a styrene content of 21% by mass, a hydrogenation rate of 95%, a molecular weight distribution of 1.11 and a total of 1,2-bonds of 78. Mol%.
- Thermoplastic elastomer (A'5) A pressure-resistant vessel purged with nitrogen and dried was charged with 80 L of cyclohexane as a solvent and 0.17 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator. After the temperature was raised to 50 ° C., 3.9 L of styrene was added and polymerized for 3 hours. Subsequently, a mixture of 12.1 L of isoprene and 10.9 L of butadiene was added for polymerization for 4 hours, and 3.9 L of styrene was further added. For 3 hours.
- the obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. It was. Subsequently, 20 kg of a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5 mass%) was used as a hydrogenation catalyst.
- thermoplastic elastomer (A′5) has a weight average molecular weight of 170,000, a styrene content of 32% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.04, a 1,2-bond amount and 3, 4- The total amount of bonds was 5 mol%.
- Polypropylene resin (C'2) Polypropylene “Prime Polypro F327” (MFR [230 ° C., load 2.16 kg (21.18 N)]: 7 g / 10 min, manufactured by Prime Polymer Co., Ltd.)
- thermoplastic polymer composition sheets prepared in the following examples and comparative examples were stacked to a thickness of 6 mm, and the A hardness was measured with a type A durometer according to JIS K 6253.
- dumbbell-shaped test piece (dumbbell-shaped No. 5) was prepared from a sheet of the thermoplastic polymer composition prepared according to the following examples and comparative examples according to JIS K 6251. The tensile rupture strength and tensile rupture elongation were measured in minutes.
- ⁇ Preparation of laminate with glass plate> The surfaces of both surfaces of a glass plate having a length of 75 mm, a width of 25 mm, and a thickness of 1 mm were washed using a surfactant aqueous solution, methanol, acetone, and distilled water in this order as a washing solution and dried.
- the glass plate, the thermoplastic polymer composition sheet prepared according to the following examples and comparative examples, and a polyethylene terephthalate (PET) sheet having a thickness of 50 ⁇ m are stacked in this order.
- the metal spacer having a thickness of 2 mm was disposed at the center.
- This stacked sheet and a metal spacer are sandwiched between polytetrafluoroethylene sheets, and further sandwiched between metal plates from the outside.
- the load is 20 kgf / cm under the temperature conditions shown in Table 1 or Table 2.
- a laminate composed of PET / thermoplastic polymer composition / glass plate was obtained by compression molding at 2 (2 N / mm 2 ) for 3 minutes.
- ⁇ Production of laminate with aluminum plate> Lamination with the above glass plate except that the surfaces of both sides of an aluminum plate 75 mm long x 25 mm wide x 1 mm thick were washed using a surfactant aqueous solution and distilled water in this order as a washing liquid and dried.
- thermoplastic polymer composition / aluminum plate The same operation as the production of the body was performed to obtain a laminate comprising PET / thermoplastic polymer composition / aluminum plate. (Measurement of adhesive strength) About the laminate of PET / thermoplastic polymer composition / glass plate and the laminate of PET / thermoplastic polymer composition / aluminum plate produced above, respectively, between the thermoplastic polymer composition layer and the glass plate The peel strength between the thermoplastic polymer composition layer and the aluminum plate was measured according to JIS K 6854-2 under the conditions of a peel angle of 180 °, a tensile speed of 50 mm / min, and 23 ° C. Furthermore, among the laminates described above, the laminates obtained by compression molding at 180 ° C. or 240 ° C.
- Examples 1 to 11 and Comparative Examples 1 to 4 (Preparation of Sheet of Thermoplastic Polymer Composition)
- the raw materials listed in Table 1 or 2 were melt-kneaded at a ratio shown in Table 1 or 2 using a batch mixer at 230 ° C. and a screw rotational speed of 200 rpm.
- the obtained kneaded material is compression-molded for 3 minutes under the conditions of 230 ° C. and a load of 100 kgf / cm 2 (9.8 N / mm 2 ) using a compression molding machine, so that the thickness of the thermoplastic polymer composition is increased.
- a 1 mm sheet was obtained.
- the physical properties and characteristics of the obtained thermoplastic polymer composition sheet were evaluated. The results are shown in Tables 1 and 2.
- thermoplastic polymer compositions obtained in Examples 1 to 11 are excellent in flexibility, mechanical properties, molding processability and particularly heat resistance, and without performing primer treatment, It can be seen that it has excellent adhesion to metals and synthetic resins, and in particular can be bonded to ceramics and metals even in a compression molding process of 190 ° C. or lower, and further 180 ° C. or 160 ° C. It can also be seen that the adhesive strength is good and the heat resistance is excellent even when the laminate bonded at 180 ° C. is placed in a temperature environment of 60 ° C. or higher.
- Example 1 and Example 2 the content of the polar group-containing polypropylene resin (C) is increased from 15 parts by mass to 25 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It can be seen that the adhesive strength in compression molding at 0 ° C. is remarkably improved and the heat resistance is further increased. From Examples 6 to 11, it can be seen that by containing the tackifier resin (E), the moldability can be further improved while maintaining the adhesion to the compression molding temperature and the environmental temperature.
- the tackifier resin (E) the tackifier resin
- thermoplastic elastomer (A) instead of the thermoplastic elastomer (A), the sum of the 1,2-bond amount and the 3,4-bond amount in the isoprene unit, butadiene unit or isoprene / butadiene unit is less than 40 mol%.
- the adhesive strength was greatly reduced by compression molding below, and the adhesive strength (heat resistance) when the laminate was placed in a temperature environment of 60 ° C. or higher was also greatly reduced.
- Comparative Example 2 using a polypropylene resin (C′2) that does not contain a polar group instead of the polar group-containing polypropylene resin (C), only an adhesive force that is not practical is obtained under all conditions. I can't understand. Furthermore, in Comparative Example 4 in which the blending amount of the polar group-containing polypropylene resin (C) exceeds 100 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A), the adhesive force in compression molding at 160 ° C. is Although it was equivalent to an Example, it turns out that mechanical characteristics, such as tensile breaking strength and tensile breaking elongation, are inadequate, and heat resistance also falls significantly.
- thermoplastic polymer composition of the present invention is a bonding agent between a glass and an aluminum sash or a metal opening in a window of an automobile or a building, an adhesive in a connection between a glass and a metal frame in a solar cell module or the like. It is useful as such.
- a molded article using the thermoplastic polymer composition of the present invention is useful as a housing material for electronic / electrical equipment, OA equipment, home appliances, automobile members, and the like. 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. Useful as a housing material.
- 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.
- a separator for secondary batteries used in various information terminal devices such as notebook computers, mobile phones, video cameras, hybrid vehicles, and fuel cell vehicles.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
このような問題に対し、セラミックス、金属およ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、金属および合成樹脂に接着させることが可能である。
さらに、特許文献7の実施例で具体的に開示された熱可塑性重合体組成物がセラミックス、金属または合成樹脂に接着してなる成形品を60℃以上(さらには80℃以上、より具体的には80~90℃)の温度環境下に置くと、その接着性が実用的に不十分なほど低下することが判明した。例えば成形品が自動車部品として使われる場合、夏場には60℃以上の温度環境下におかれることも多いため、耐熱性の観点からも、特許文献7に具体的に開示された熱可塑性重合体組成物および成形品には、さらなる改良の余地があった。
本発明は、上記事情に鑑みてなされたものであって、柔軟性、力学特性、成形加工性および特に耐熱性に優れ、かつ、プライマー処理などを施さなくても、セラミックス、金属および合成樹脂を低温(例えば190℃以下)での加熱処理によって接着できる熱可塑性重合体組成物、および該熱可塑性重合体組成物を用いてなる成形品を提供することを課題とする。
即ち、本発明は、下記[1]~[11]を提供する。
[1]芳香族ビニル化合物単位を含有する重合体ブロックと、1,2-結合量および3,4-結合量が合わせて40モル%以上であるイソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックとを有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)100質量部に対して、ポリビニルアセタール樹脂(B)1~100質量部および極性基含有ポリプロピレン系樹脂(C)5~100質量部を含有する熱可塑性重合体組成物。
[2]熱可塑性エラストマー(A)100質量部に対して、成分(B)5~70質量部および成分(C)5~70質量部を含有する、上記[1]の熱可塑性重合体組成物。
[3]さらに軟化剤(D)を、熱可塑性エラストマー(A)100質量部に対して0.1~300質量部含有する、上記[1]または[2]の熱可塑性重合体組成物。
[4]さらに粘着付与樹脂(E)を、熱可塑性エラストマー(A)100質量部に対して1~100質量部含有する、上記[1]~[3]のいずれかの熱可塑性重合体組成物。
[5]ポリビニルアセタール樹脂(B)が、平均重合度100~4,000のポリビニルアルコールをアセタール化して得られるものであって、アセタール化度が55~88モル%である、上記[1]~[4]のいずれかの熱可塑性重合体組成物。
[6]ポリビニルアセタール樹脂(B)がポリビニルブチラールである、上記[1]~[5]のいずれかの熱可塑性重合体組成物。
[7]極性基含有ポリプロピレン系樹脂(C)がカルボン酸変性ポリプロピレン系樹脂である、上記[1]~[6]のいずれかの熱可塑性重合体組成物。
[8]上記[1]~[7]のいずれかの熱可塑性重合体組成物を用いた成形品。
[9]前記熱可塑性重合体組成物が、セラミックス、金属および合成樹脂から選択される少なくとも1種に接着してなる、上記[8]の成形品。
[10]前記熱可塑性重合体組成物が、セラミックスおよび金属から選択される少なくとも1種に接着してなる、上記[9]の成形品。
[11]前記熱可塑性重合体組成物が、セラミックス同士、金属同士もしくは合成樹脂同士を、またはセラミックス、金属および合成樹脂から選択される少なくとも2種を接着してなる、上記[8]の成形品。
したがって、該成形品の製造工程において、射出成形機や押出機から吐出されたこの熱可塑性重合体組成物の表面温度が190℃以下になっても十分な接着が可能であるため、別途ヒーターを設置することなく既存の設備をそのまま使用できる。また、190℃以下では多くの合成樹脂部材が溶融・変形しないため、同時に加熱される接着部分周辺の合成樹脂部材の破壊を回避できる。
本発明の熱可塑性重合体組成物は、芳香族ビニル化合物単位を含有する重合体ブロックと、1,2-結合量および3,4-結合量が合わせて40モル%以上であるイソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックとを有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)(以下、熱可塑性エラストマー(A)と略称する)100質量部に対して、ポリビニルアセタール樹脂(B)1~100質量部および極性基含有ポリプロピレン系樹脂(C)5~100質量部を含有する熱可塑性重合体組成物である。また、本発明の熱可塑性重合体組成物は、さらに軟化剤(D)を含んでいてもよい。また、本発明の熱可塑性重合体組成物は、成形加工性を向上させるためにさらに粘着付与樹脂(E)を含んでいてもよい。
以下、上記成分(A)~(E)について順に説明する。
熱可塑性エラストマー(A)は、本発明の熱可塑性重合体組成物に柔軟性や、良好な力学特性および成形加工性などを付与するものであり、該組成物中でマトリックスの役割を果たす。本発明では、上記のように、イソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックにおいて1,2-結合量および3,4-結合量を合わせて40モル%以上とすることにより、特に極性基含有ポリプロピレン系樹脂(C)との相容性が高まり、得られる熱可塑性重合体組成物に、60℃以上、さらには80℃以上の温度環境下における高い接着性が備わるものと推測される。
-芳香族ビニル化合物単位を含有する重合体ブロック-
芳香族ビニル化合物単位を含有する重合体ブロックを構成する芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、2-メチルスチレン、3-メチルスチレン、4-メチルスチレン、4-プロピルスチレン、4-シクロヘキシルスチレン、4-ドデシルスチレン、2-エチル-4-ベンジルスチレン、4-(フェニルブチル)スチレン、1-ビニルナフタレン、2-ビニルナフタレンなどが挙げられる。芳香族ビニル化合物単位を含有する重合体ブロックは、これらの芳香族ビニル化合物の1種のみに由来する構造単位からなっていてもよいし、2種以上に由来する構造単位からなっていてもよい。これらの中でも、スチレン、α-メチルスチレン、4-メチルスチレンが好ましい。
他の共重合性単量体としては、例えば、1-ブテン、ペンテン、ヘキセン、ブタジエン、イソプレン、メチルビニルエーテルなどが挙げられる。他の共重合性単量体単位を有する場合、その割合は、芳香族ビニル化合物単位および他の共重合性単量体単位の合計量に対して、好ましくは20質量%以下、より好ましくは10質量%以下、さらに好ましくは5質量%以下である。
イソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックを構成する化合物としては、例えば、イソプレン、ブタジエン、2,3-ジメチル-1,3-ブタジエンが挙げられる。これらの中でも、イソプレン、ブタジエンが好ましい。
前記重合体ブロックとしては、190℃以下での接着性の観点、および耐熱性(60℃以上の温度環境下における接着性)の観点から、イソプレン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックが好ましい。
なお、本明細書において、「イソプレン単位」とは、イソプレンに由来する構造単位のことであり、「ブタジエン単位」とは、ブタジエンや2,3-ジメチル-1,3-ブタジエンなどのブタジエンに由来する構造単位のことである。また、「イソプレン/ブタジエン単位」とは、イソプレンと、ブタジエンや2,3-ジメチル-1,3-ブタジエンなどのブタジエンとの両方に由来する構造単位である。
なお、1,2-結合量および3,4-結合量は、1H-NMR測定によって算出できる。具体的には、1,2-結合単位および3,4-結合単位に由来する4.2~5.0ppmに存在するピークの積分値および1,4-結合単位に由来する5.0~5.45ppmに存在するピークの積分値との比から算出できる。
他の共重合性単量体としては、例えば、スチレン、α-メチルスチレン、4-メチルスチレンなどのスチレン系単量体などが挙げられる。他の共重合性単量体単位を有する場合、その割合は、全構成単位に対して、好ましくは20質量%以下、より好ましくは10質量%以下、さらに好ましくは5質量%以下である。
直鎖状の結合形態の例としては、芳香族ビニル化合物単位を含有する重合体ブロックをaで、イソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックをbで表したとき、a-bで表されるジブロック共重合体、a-b-aまたはb-а-bで表されるトリブロック共重合体、a-b-a-bで表されるテトラブロック共重合体、a-b-a-b-aまたはb-a-b-a-bで表されるペンタブロック共重合体、(а-b)nX型共重合体(Xはカップリング残基を表し、nは2以上の整数を表す)、およびこれらの混合物が挙げられる。これらの中でも、トリブロック共重合体が好ましく、a-b-aで表されるトリブロック共重合体であることがより好ましい。
また、熱可塑性エラストマー(A)の重量平均分子量は、その力学特性、成形加工性の観点から、好ましくは30,000~500,000、より好ましくは50,000~400,000である。ここで、重量平均分子量とは、ゲルパーミエーションクロマトグラフィー(GPC)測定によって求めたポリスチレン換算の重量平均分子量である。
熱可塑性エラストマー(A)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。
なお、上記「 」内の各文言については、『1,4-結合量が60モル%を超える共役ジエン化合物単位を含有する重合体ブロック』という文言を除き、前述の説明と同様に説明されるものである。
1,4-結合量が60モル%を超える共役ジエン化合物単位を含有する重合体ブロックは、上記共役ジエン化合物の1種のみに由来する構造単位からなっていてもよいし、2種以上に由来する構造単位からなっていてもよい。特に、ブタジエンもしくはイソプレンに由来する構造単位、またはブタジエンおよびイソプレンに由来する構造単位からなっていることが好ましい。
なお、1,4-結合量は、先述した1H-NMR測定によって算出できる。
熱可塑性エラストマー(A)の製造方法は特に限定されないが、例えばアニオン重合法により製造することができる。具体的には、
(i)アルキルリチウム化合物を開始剤として用い、前記芳香族ビニル化合物、前記共役ジエン化合物、次いで前記芳香族ビニル化合物を逐次重合させる方法;
(ii)アルキルリチウム化合物を開始剤として用い、前記芳香族ビニル化合物、前記共役ジエン化合物を逐次重合させ、次いでカップリング剤を加えてカップリングする方法;
(iii)ジリチウム化合物を開始剤として用い、前記共役ジエン化合物、次いで前記芳香族ビニル化合物を逐次重合させる方法などが挙げられる。
なお、上記のアニオン重合は、溶媒の存在下で行なうのが好ましい。溶媒としては、開始剤に対して不活性で、重合に悪影響を及ぼさないものであれば特に制限はなく、例えばヘキサン、ヘプタン、オクタン、デカンなどの飽和脂肪族炭化水素;トルエン、ベンゼン、キシレンなどの芳香族炭化水素などが挙げられる。また、重合は、上記したいずれの方法による場合も、通常、0~80℃で0.5~50時間行なうのが好ましい。
該有機ルイス塩基としては、例えば、酢酸エチルなどのエステル;トリエチルアミン、N,N,N’,N’-テトラメチルエチレンジアミン(TMEDA)、N-メチルモルホリンなどのアミン;ピリジンなどの含窒素複素環式芳香族化合物;ジメチルアセトアミドなどのアミド;ジメチルエーテル、ジエチルエーテル、テトラヒドロフラン(THF)、ジオキサンなどのエーテル;エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどのグリコールエーテル;ジメチルスルホキシドなどのスルホキシド;アセトン、メチルエチルケトンなどのケトンなどが挙げられる。これらの有機ルイス塩基は、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。
該有機ルイス塩基の使用量としては、熱可塑性エラストマー(A)の1,2-結合量および3,4-結合量を40モル%以上にする観点から、例えば開始剤中に含まれるリチウムイオンに対し、量論比で好ましくは0.01~1000倍、より好ましくは0.1~100倍、さらに好ましくは0.1~50倍である。この範囲内で有機ルイス塩基の使用量を調整することで、任意に熱可塑性エラストマー(A)の1,2-結合量および3,4-結合量を制御できる。
さらに、上記で得られた未水添の熱可塑性エラストマー(A)を水素添加反応に付すことによって、水添された熱可塑性エラストマー(A)を製造できる。水素添加反応は、反応および水素添加触媒に対して不活性な溶媒に上記で得られた未水添のスチレン系熱可塑性エラストマー(A)を溶解させるか、または、未水添のスチレン系熱可塑性エラストマー(A)を前記の反応液から単離せずにそのまま用い、水素添加触媒の存在下、水素と反応させることにより行うことができる。
水素添加触媒としては、例えばラネーニッケル;Pt、Pd、Ru、Rh、Niなどの金属をカーボン、アルミナ、珪藻土などの担体に担持させた不均一系触媒;遷移金属化合物とアルキルアルミニウム化合物、アルキルリチウム化合物などとの組み合わせからなるチーグラー系触媒;メタロセン系触媒などが挙げられる。
水素添加反応は、通常、水素圧力0.1~20MPa、反応温度20~250℃、反応時間0.1~100時間の条件で行なうことができる。この方法による場合、水素添加反応液をメタノールなどの貧溶媒に注いで凝固させるか、または水素添加反応液をスチームと共に熱水中に注いで溶媒を共沸によって除去(スチームストリッピング)した後、乾燥させることにより、水添されたスチレン系熱可塑性エラストマー(A)を単離できる。
ポリビニルアセタール樹脂(B)は、本発明の熱可塑性重合体組成物に接着性を付与するものであり、通常、組成物中にて島状に分散している。該ポリビニルアセタール樹脂(B)によって、本発明の熱可塑性重合体組成物は、セラミックス、金属または合成樹脂などの被着体の表面にプライマー処理を施さなくても良好に接着させることができる。
ポリビニルアセタール樹脂(B)は、通常、下記式(I)に表される繰り返し単位を有する。
ただし、k(1)+k(2)+・・・+k(n)+l+m=1であり、k(1)、k(2)、・・・、k(n)、lおよび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(B)は、例えば、ポリビニルアルコールとアルデヒドとを反応させることによって得ることができる。
ポリビニルアセタール樹脂(B)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、通常、好ましくは100~4,000、より好ましくは100~3,000、さらに好ましくは100~2,000、特に好ましくは250~2,000である。ポリビニルアルコールの平均重合度が100以上であれば、ポリビニルアセタール樹脂(B)の製造が容易となり、また取り扱い性が良好である。また、ポリビニルアルコールの平均重合度が4,000以下であると、溶融混練する際の溶融粘度が高くなり過ぎることがなく、本発明の熱可塑性重合体組成物の製造が容易である。
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。
本発明では、ポリビニルアセタール樹脂(B)中に存在するアセタール単位のうち、ブチラール単位の割合(下式参照)が、好ましくは0.8以上、より好ましくは0.9以上、さらに好ましくは0.95以上、特に好ましくは、実質的に1である。
すなわち、前記式(I)に示されるポリビニルアセタール樹脂(B)の構造式において、R1のみがn-C3H7であるとき、0.8≦k(1)/(k(1)+k(2)+・・・+k(n))であるものが好ましい。
ポリビニルアセタール樹脂(B)のアセタール化度は、より好ましくは60~88モル%であり、さらに好ましくは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(B)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(B)が有する水酸基の割合が大きくなり、セラミックス、金属および合成樹脂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、熱可塑性エラストマー(A)との親和性や相容性が良好となり、熱可塑性重合体組成物の力学特性に優れるとともに、セラミックス、金属および合成樹脂との接着強度が高くなる。
アセタール化度(モル%)={k(1)+k(2)+・・・+k(n)}×2/{{k(1)+k(2)+・・・+k(n)}×2+l+m}×100
(上記式中、n、k(1)、k(2)、・・・、k(n)、lおよびmは、前記定義の通りである。)
また、ポリビニルアセタール樹脂(B)のアセタール化度は、ポリビニルアセタール樹脂(B)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;硝酸、硫酸、塩酸などの無機酸;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。
除去方法は特に制限されず、脱水と水洗を繰り返すなどの方法が通常用いられる。残渣などが除去された含水状態のポリビニルアセタール樹脂(B)は、必要に応じて乾燥され、必要に応じてパウダー状、顆粒状あるいはペレット状に加工される。
本発明で用いるポリビニルアセタール樹脂(B)としては、パウダー状、顆粒状あるいはペレット状に加工される際に、減圧状態で脱気することにより、アルデヒドの反応残渣や水分などを低減したものが好ましい。
本発明の熱可塑性重合体組成物に、前記熱可塑性エラストマー(A)およびポリビニルアセタール樹脂(B)に加えて、極性基含有ポリプロピレン系樹脂(C)を含有させることにより、本発明の熱可塑性重合体組成物へより良好な成形加工性が付与されるのみならず、190℃以下の温度でも、セラミックス、金属または合成樹脂などと良好に接着することが可能となり、かつセラミックス、金属または合成樹脂に本発明の熱可塑性重合体組成物を接着してなる成形品が60℃以上の温度環境下にさらされても、高い接着性が維持される。
極性基含有ポリプロピレン系樹脂(C)の極性基としては、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;酸無水物基などが挙げられる。該極性基含有ポリプロピレン系樹脂(C)の製造方法に特に制限はないが、プロピレン(必要に応じてさらにα-オレフィン)および極性基含有共重合性単量体とを、公知の方法でランダム共重合・ブロック共重合またはグラフト共重合することによって得られる。このほかにも、ポリプロピレン系樹脂を公知の方法で酸化または塩素化など反応に付することによっても得られる。
上記α-オレフィンとしては、エチレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテン、シクロヘキセンなどが挙げられる。これらプロピレン以外のα-オレフィンを由来とする単位の、極性基含有ポリプロピレン系樹脂(C)が有する全構造単位に対する割合は、好ましくは0~45モル%、より好ましくは0~35モル%、さらに好ましくは0~25モル%である。
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無水物が挙げられる。これらの中でも、不飽和カルボン酸またはそのエステルもしくは無水物が好ましい。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。これらの中でも、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。
極性基含有ポリプロピレン系樹脂(C)としては、ポリビニルアセタール樹脂(B)との相容性の観点から、極性基としてカルボキシル基を含有するポリプロピレン、つまりカルボン酸変性ポリプロピレン系樹脂が好ましく、無水マレイン酸変性ポリプロピレン系樹脂がより好ましい。
本発明に用いられる極性基含有ポリプロピレン系樹脂(C)が有する極性基は、重合後に後処理されていてもよい。例えば、(メタ)アクリル酸基やカルボキシル基の金属イオンによる中和を行ってアイオノマーとしていてもよいし、メタノールやエタノールなどによってエステル化していてもよい。また、酢酸ビニルの加水分解などを行っていてもよい。
極性基含有ポリプロピレン系樹脂(C)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120~140℃である。
極性基含有ポリプロピレン系樹脂(C)の含有量は、熱可塑性エラストマー(A)100質量部に対して、より好ましくは10質量部以上、さらに好ましくは15質量部以上、特に好ましくは20質量部以上であり、より好ましくは70質量部以下、さらに好ましくは60質量部以下、特に好ましくは30質量部以下である。
これらより、極性基含有ポリプロピレン系樹脂(C)の含有量は、熱可塑性エラストマー(A)100質量部に対して、好ましくは5~70質量部、より好ましくは10~70質量部、より好ましくは10~60質量部、より好ましくは10~30質量部、特に好ましくは20~30質量部である。
本発明の熱可塑性重合体組成物に含有させてもよい軟化剤(D)としては、例えば、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などのフタル酸誘導体;ホワイトオイル、ミネラルオイル、エチレンとα-オレフィンのオリゴマー、パラフィンワックス、流動パラフィン、ポリブテン、低分子量ポリブタジエン、低分子量ポリイソプレンなどが挙げられる。これらの中でもプロセスオイルが好ましく、パラフィン系プロセスオイルがより好ましい。
また、一般的にポリビニルアセタール樹脂と併せて使用される公知の軟化剤、例えば一塩基性有機酸エステル、多塩基性有機酸エステルなどの有機酸エステル系可塑剤;有機リン酸エステル、有機亜リン酸エステルなどのリン酸系可塑剤なども使用できる。
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る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、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。
本発明の熱可塑性重合体組成物は、必要に応じて粘着付与樹脂(E)を含有させることにより、接着特性を維持しつつ、成形加工性をさらに向上させることができる。
ここで、軟化点はASTM28-67に準拠して測定した値である。
本発明の熱可塑性重合体組成物は、本発明の効果を著しく損なわない範囲で、必要に応じて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、他の熱可塑性重合体を含有していてもよい。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が挙げられる。
他の熱可塑性重合体を含有させる場合、その含有量は、熱可塑性エラストマー(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、さらに好ましくは10質量部以下、特に好ましくは5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、熱可塑性重合体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、一般に熱可塑性エラストマー(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、さらに好ましくは30質量部以下、特に好ましくは10質量部以下である。
酸化防止剤としては、例えばヒンダードフェノール系、リン系、ラクトン系、ヒドロキシル系の酸化防止剤などが挙げられる。これらの中でも、ヒンダードフェノール系酸化防止剤が好ましい。酸化防止剤を含有させる場合、その含有量は、得られる熱可塑性重合体組成物を溶融混練する際に着色しない範囲であることが好ましく、熱可塑性エラストマー(A)100質量部に対して、好ましくは0.1~5質量部である。
本発明はまた、前記した本発明の熱可塑性重合体組成物を用いた成形品を提供する。
本発明の熱可塑性重合体組成物は成形加工性に優れるので、種々の成形品を製造することができる。成形品は、シートやフィルムであってもよい。
成形方法としては、熱可塑性重合体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。
本発明の成形品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、およ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品であってもよい。
本発明の成形品に使用し得る合成樹脂としては、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、ポリオレフィ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。
無機充填材の配合量は、無機充填材を含有する樹脂の成形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、一般に前記合成樹脂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、さらに好ましくは3~40質量部である。
例えば、射出インサート成形法により成形体を製造する場合には、あらかじめ所定の形状およ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重合体組成物を射出成形して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成形体を製造する場合には、あらかじめ所定の形状および寸法に形成しておいた被着体の表面、またはその縁に対して、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重合体組成物を直接押出して成形体を製造することもできる。プレス成形法により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重合体組成物からなる成形品を成形しておき、その成形体を、あらかじめ所定の形状およ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。このとき、被着体と接着しない面には、必要に応じて、保護や加飾のため、最外層にオレフィン系樹脂や環状オレフィン系樹脂などの非極性樹脂の層を設けてもよい。
例えば、電子・電気機器、OA機器、家電機器、自動車用部材などのハウジング材に、合成樹脂、ガラス繊維を含有する合成樹脂や、アルミニウム、マグネシウム合金などの軽金属が用いられるが、これらのハウジング材に本発明の熱可塑性重合体組成物が接着された成形品が挙げられる。より具体的には、大型ディスプレイ、ノート型パソコン、携帯用電話機、PHS、PDA(電子手帳などの携帯情報端末)、電子辞書、ビデオカメラ、デジタルスチルカメラ、携帯用ラジオカセット再生機、インバーターなどのハウジングに接着され、衝撃緩和材、滑り止め防止機能を持った被覆材、防水材、意匠材などの用途に好ましい。
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にも好適に使用できる。さらには、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。
なお、以下の実施例および比較例で用いた各成分は以下の通りである。
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64L、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.20Lを仕込み、ルイス塩基としてテトラヒドロフラン0.3L(開始剤中のリチウム原子に対して、量論比で15倍相当)を仕込んだ。50℃に昇温した後、スチレン2.3Lを加えて3時間重合させ、引き続いてイソプレン23Lを加えて4時間重合を行い、さらにスチレン2.3Lを加えて3時間重合を行った。得られた反応液をメタノール80Lに注ぎ、析出した固体を濾別して50℃で20時間乾燥することにより、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体を得た。
続いて、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体10kgをシクロヘキサン200Lに溶解し、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%)を該共重合体に対して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、さらに真空乾燥することにより、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体の水添物(A1)を得た。得られた熱可塑性エラストマー(A1)の重量平均分子量は107,000、スチレン含有量は21質量%、水素添加率は85%、分子量分布は1.04、1,2-結合量および3,4-結合量の合計は60モル%であった。
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150L、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.22Lを仕込み、ルイス塩基としてテトラヒドロフラン0.3L(開始剤中のリチウム原子に対して、量論比で14倍相当)を仕込んだ。50℃に昇温した後、スチレン0.72Lを加えて3時間重合させ、引き続いてイソプレン12.6Lおよびブタジエン14.0Lの混合液を加えて4時間重合を行い、さらにスチレン2.2Lを加えて3時間重合を行った。得られた反応液をメタノール80Lに注ぎ、析出した固体を濾別して50℃で20時間乾燥することにより、ポリスチレン-ポリ(イソプレン/ブタジエン)-ポリスチレンからなるトリブロック共重合体を得た。
続いて、ポリスチレン-ポリ(イソプレン/ブタジエン)-ポリスチレンからなるトリブロック共重合体10kgをシクロヘキサン200Lに溶解し、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%)を該共重合体に対して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、さらに真空乾燥することにより、ポリスチレン-ポリ(イソプレン/ブタジエン)-ポリスチレンからなるトリブロック共重合体の水添物(A2)を得た。得られた熱可塑性エラストマー(A2)の重量平均分子量は165,000、スチレン含有量は13質量%、水素添加率は85%、分子量分布は1.02、1,2-結合量および3,4-結合量の合計は63モル%であった。
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120L、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.12Lを仕込み、ルイス塩基としてテトラヒドロフラン0.3L(開始剤中のリチウム原子に対して、量論比で26倍相当)を仕込んだ。50℃に昇温した後、スチレン3.6Lを加えて3時間重合させ、引き続いてイソプレン20.0Lを加えて4時間重合を行い、さらにスチレン3.6Lを加えて3時間重合を行った。得られた反応液をメタノール80Lに注ぎ、析出した固体を濾別して50℃で20時間乾燥することにより、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体を得た。
続いて、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体10kgをシクロヘキサン200Lに溶解し、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%)を該共重合体に対して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、さらに真空乾燥することにより、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体の水添物(A3)を得た。得られた熱可塑性エラストマー(A3)の重量平均分子量は320,000、スチレン含有量は33質量%、水素添加率は90%、分子量分布は1.07、1,2-結合量および3,4-結合量の合計は54モル%であった。
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86L、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.22Lを仕込み、ルイス塩基としてエチレングリコールジメチルエーテル0.02L(開始剤中のリチウム原子に対して、量論比で0.7倍相当)を仕込んだ。50℃に昇温した後、スチレン2.3Lを加えて3時間重合させ、引き続いてブタジエン25.5Lを加えて4時間重合を行い、さらにスチレン2.3Lを加えて3時間重合を行った。得られた反応液をメタノール80Lに注ぎ、析出した固体を濾別して50℃で20時間乾燥することにより、ポリスチレン-ポリブタジエン-ポリスチレンからなるトリブロック共重合体を得た。
続いて、ポリスチレン-ポリブタジエン-ポリスチレンからなるトリブロック共重合体10kgをシクロヘキサン200Lに溶解し、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%)を該共重合体に対して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、さらに真空乾燥することにより、ポリスチレン-ポリブタジエン-ポリスチレンからなるトリブロック共重合体の水添物(A4)を得た。得られた熱可塑性エラストマー(A4)の重量平均分子量は126,000、スチレン含有量は21質量%、水素添加率は95%、分子量分布は1.11、1,2-結合量の合計は78モル%であった。
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80L、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.17Lを仕込んだ。50℃に昇温した後、スチレン3.9Lを加えて3時間重合させ、引き続いてイソプレン12.1Lおよびブタジエン10.9Lの混合液を加えて4時間重合を行い、さらにスチレン3.9Lを加えて3時間重合を行った。得られた反応液をメタノール80L中に注ぎ、析出した固体を濾別して50℃で20時間乾燥することにより、ポリスチレンブロック-ポリ(イソプレン/ブタジエン)ブロック-ポリスチレンブロックからなるトリブロック共重合体を得た。
続いて、ポリスチレンブロック-ポリ(イソプレン/ブタジエン)ブロック-ポリスチレンブロックからなるトリブロック共重合体20kgをシクロヘキサン200Lに溶解し、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%)を該共重合体に対して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、さらに真空乾燥することにより、ポリスチレンブロック-ポリ(イソプレン/ブタジエン)ブロック-ポリスチレンブロックからなるトリブロック共重合体の水添物(A'5)を得た。得られた熱可塑性エラストマー(A'5)の重量平均分子量は170,000、スチレン含量は32質量%、水添率は97%、分子量分布は1.04、1,2-結合量および3,4-結合量の合計は5モル%であった。
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-ブチルアルデヒドならびに酸触媒(塩酸)を添加し、攪拌してアセタール化し、樹脂を析出させた。公知の方法に従ってpH=6になるまで洗浄し、次いでアルカリ性にした水性媒体中に懸濁させて攪拌しながら後処理をし、pH=7になるまで洗浄し、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(B1)を得た。
ポリプロピレン「プライムポリプロF327」(MFR[230℃、荷重2.16kg(21.18N)]: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た。得られた混練物の無水マレイン酸濃度は0.3%であった。
なお、該無水マレイン酸濃度は、得られた混練物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。
ポリプロピレン「プライムポリプロF327」(MFR[230℃、荷重2.16kg(21.18N)]:7g/10分、株式会社プライムポリマー製)
ポリエチレン「ネオゼックス0434N」(MFR[190℃、荷重2.16kg(21.18N)]:4g/10分、株式会社プライムポリマー製)42g、無水マレイン酸160mg、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た。得られた混練物の無水マレイン酸濃度は0.3%であった。
〔軟化剤(D1)〕
パラフィン系プロセスオイル「ダイアナプロセスPW-90」(出光興産株式会社製)
〔粘着付与樹脂(E1)〕
水添芳香族炭化水素樹脂「Regalite1100」(イーストマンケミカル社製)、軟化点100℃
〔粘着付与樹脂(E2)〕
水添芳香族炭化水素樹脂「Regalite1125」(イーストマンケミカル社製)、軟化点123℃
〔粘着付与樹脂(E3)〕
水添テルペン樹脂「クリアロンM115」(ヤスハラケミカル株式会社製)、軟化点115℃
〔粘着付与樹脂(E4)〕
水添テルペン樹脂「クリアロンP150」(ヤスハラケミカル株式会社製)、軟化点152℃
(メルトフローレート(MFR)の測定)
以下の実施例および比較例により作製した熱可塑性重合体組成物のシートを細かくカットし、JIS K 7210に準じた方法で、230℃、荷重2.16kg(21.18N)の条件下でMFRを測定し、成形加工性の指標とした。MFRの値が大きいほど、成形加工性に優れる。
以下の実施例および比較例により作製した熱可塑性重合体組成物のシートを重ねて厚さ6mmとし、JIS K 6253に準じたタイプAデュロメータによりA硬度を測定した。
以下の実施例および比較例により作製した熱可塑性重合体組成物のシートより、JIS K 6251に準じた方法でダンベル型試験片(ダンベル状5号形)を作製し、23℃、引張速度500mm/分で、引張破断強度および引張破断伸度を測定した。
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。該ガラス板、以下の実施例および比較例により作製した熱可塑性重合体組成物のシート、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、第1表または第2表に示す温度条件下、荷重20kgf/cm2(2N/mm2)で3分間圧縮成形することで、PET/熱可塑性重合体組成物/ガラス板からなる積層体を得た。
<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、乾燥させた以外は、上記したガラス板との積層体の作製と同様の操作を行い、PET/熱可塑性重合体組成物/アルミニウム板からなる積層体を得た。
(接着力の測定)
上記で作製した、PET/熱可塑性重合体組成物/ガラス板の積層体と、PET/熱可塑性重合体組成物/アルミニウム板の積層体について、それぞれ、熱可塑性重合体組成物層とガラス板間、熱可塑性重合体組成物層とアルミニウム板間の剥離強度をJIS K 6854-2に準じて、剥離角度180°、引張速度50mm/分、23℃の条件で測定した。
さらに、上記積層体のうち、180℃または240℃で、荷重20kgf/cm2(2N/mm2)で3分間圧縮成形することで得た積層体について、それぞれ、熱可塑性重合体組成物層とガラス板間、熱可塑性重合体組成物層とアルミニウム板間の剥離強度を、剥離角度180°、引張速度50mm/分、および第1表または第2表に記載の温度の条件で測定し、耐熱性の指標とした。
第1表または第2表に記載の原料を第1表または第2表に示す割合にて、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た。得られた混練物を、圧縮成形機を用いて230℃、荷重100kgf/cm2(9.8N/mm2)の条件下で3分間圧縮成形することで、熱可塑性重合体組成物の厚さ1mmのシートを得た。
上記測定方法に従って、得られた熱可塑性重合体組成物のシートの物性および特性を評価した。結果を第1表および第2表に示す。
一方、第2表より、熱可塑性エラストマー(A)の代わりに、イソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位における1,2-結合量と3,4-結合量の合計が40モル%未満である熱可塑性エラストマー(A'5)を用いた比較例1や、極性基含有ポリプロピレン系樹脂(C)の代わりに極性基含有ポリエチレン系樹脂(C'3)を用いた比較例3においては、180℃以下で圧縮成形することによって接着力は大幅に低下し、また、積層体を60℃以上の温度環境下に置いた場合における接着力(耐熱性)も大幅に低下した。また、極性基含有ポリプロピレン系樹脂(C)の代わりに、極性基を含有しないポリプロピレン系樹脂(C'2)を用いた比較例2においては、全ての条件下において実用性に乏しい接着力しか得られないことがわかる。
さらに、極性基含有ポリプロピレン系樹脂(C)の配合量が熱可塑性エラストマー(A)100質量部に対して100質量部を超えている比較例4においては、160℃での圧縮成形における接着力は実施例と同等であったが、引張破断強度や引張破断伸度などの力学特性が不十分であり、また、耐熱性も大幅に低下することがわかる。
本発明の熱可塑性重合体組成物が用いられた成形品は、電子・電気機器、OA機器、家電機器、自動車用部材などのハウジング材として有用である。より具体的には、大型ディスプレイ、ノート型パソコン、携帯用電話機、PHS、PDA(電子手帳などの携帯情報端末)、電子辞書、ビデオカメラ、デジタルスチルカメラ、携帯用ラジオカセット再生機、インバーターなどのハウジング材として有用である。
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。
さらには、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としても有用である。
Claims (11)
- 芳香族ビニル化合物単位を含有する重合体ブロックと、1,2-結合量および3,4-結合量が合わせて40モル%以上であるイソプレン単位、ブタジエン単位またはイソプレン/ブタジエン単位を含有する重合体ブロックとを有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)100質量部に対して、ポリビニルアセタール樹脂(B)1~100質量部および極性基含有ポリプロピレン系樹脂(C)5~100質量部を含有する熱可塑性重合体組成物。
- 熱可塑性エラストマー(A)100質量部に対して、成分(B)5~70質量部および成分(C)5~70質量部を含有する、請求項1に記載の熱可塑性重合体組成物。
- さらに軟化剤(D)を、熱可塑性エラストマー(A)100質量部に対して0.1~300質量部含有する、請求項1または2に記載の熱可塑性重合体組成物。
- さらに粘着付与樹脂(E)を、熱可塑性エラストマー(A)100質量部に対して1~100質量部含有する、請求項1~3のいずれかに記載の熱可塑性重合体組成物。
- ポリビニルアセタール樹脂(B)が、平均重合度100~4,000のポリビニルアルコールをアセタール化して得られるものであって、アセタール化度が55~88モル%である、請求項1~4のいずれかに記載の熱可塑性重合体組成物。
- ポリビニルアセタール樹脂(B)がポリビニルブチラールである、請求項1~5のいずれかに記載の熱可塑性重合体組成物。
- 極性基含有ポリプロピレン系樹脂(C)がカルボン酸変性ポリプロピレン系樹脂である、請求項1~6のいずれかに記載の熱可塑性重合体組成物。
- 請求項1~7のいずれかに記載の熱可塑性重合体組成物を用いた成形品。
- 前記熱可塑性重合体組成物が、セラミックス、金属および合成樹脂から選択される少なくとも1種に接着してなる、請求項8に記載の成形品。
- 前記熱可塑性重合体組成物が、セラミックスおよび金属から選択される少なくとも1種に接着してなる、請求項9に記載の成形品。
- 前記熱可塑性重合体組成物が、セラミックス同士、金属同士もしくは合成樹脂同士を、またはセラミックス、金属および合成樹脂から選択される少なくとも2種を接着してなる、請求項8に記載の成形品。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11819964.5A EP2610305B1 (en) | 2010-08-27 | 2011-08-24 | Thermoplastic polymer composition and molded article |
ES11819964.5T ES2664971T3 (es) | 2010-08-27 | 2011-08-24 | Composición del polímero termoplástico y artículo moldeado |
KR1020137004799A KR101823715B1 (ko) | 2010-08-27 | 2011-08-24 | 열가소성 중합체 조성물 및 성형품 |
US13/818,695 US9670354B2 (en) | 2010-08-27 | 2011-08-24 | Thermoplastic polymer composition and molded article |
CN201180041696.7A CN103068915B (zh) | 2010-08-27 | 2011-08-24 | 热塑性聚合物组合物和成型品 |
JP2012530695A JP5809150B2 (ja) | 2010-08-27 | 2011-08-24 | 熱可塑性重合体組成物および成形品 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010191134 | 2010-08-27 | ||
JP2010-191134 | 2010-08-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012026501A1 true WO2012026501A1 (ja) | 2012-03-01 |
Family
ID=45723494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/069092 WO2012026501A1 (ja) | 2010-08-27 | 2011-08-24 | 熱可塑性重合体組成物および成形品 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9670354B2 (ja) |
EP (1) | EP2610305B1 (ja) |
JP (1) | JP5809150B2 (ja) |
KR (1) | KR101823715B1 (ja) |
CN (1) | CN103068915B (ja) |
ES (1) | ES2664971T3 (ja) |
WO (1) | WO2012026501A1 (ja) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013094997A (ja) * | 2011-10-28 | 2013-05-20 | Kuraray Co Ltd | 接着体の製造方法 |
WO2013105392A1 (ja) * | 2012-01-11 | 2013-07-18 | 株式会社クラレ | 熱可塑性重合体組成物および成形品 |
JP2013141794A (ja) * | 2012-01-11 | 2013-07-22 | Kuraray Co Ltd | 接着体の製造方法 |
WO2014129561A1 (ja) | 2013-02-22 | 2014-08-28 | 株式会社クラレ | 繊維、布及び不織布 |
JP2014168940A (ja) * | 2013-03-05 | 2014-09-18 | Kuraray Co Ltd | 接着体の製造方法 |
JP2015105345A (ja) * | 2013-11-29 | 2015-06-08 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
JPWO2013145594A1 (ja) * | 2012-03-29 | 2015-12-10 | 三井化学株式会社 | フェノール樹脂成形材料、摩擦材、およびフェノール樹脂成形品 |
WO2016031550A1 (ja) * | 2014-08-26 | 2016-03-03 | 株式会社クラレ | 熱可塑性重合体組成物、及び成形品 |
JP2017095617A (ja) * | 2015-11-25 | 2017-06-01 | 株式会社クラレ | 活性エネルギー線硬化性樹脂組成物、積層体および成形体、並びにそれらの製造方法 |
KR20170082599A (ko) * | 2014-11-10 | 2017-07-14 | 주식회사 쿠라레 | 합판 유리용 중간막 및 합판 유리 |
JPWO2016121868A1 (ja) * | 2015-01-28 | 2017-11-02 | 株式会社クラレ | 多層フィルム |
WO2017200052A1 (ja) | 2016-05-18 | 2017-11-23 | 株式会社クラレ | 樹脂組成物、フィルム及び合わせガラス用中間膜 |
WO2017199983A1 (ja) | 2016-05-18 | 2017-11-23 | 株式会社クラレ | 水添ブロック共重合体、制振材、遮音材、合わせガラス用中間膜、ダムラバー、靴底材料、床材、積層体および合わせガラス |
WO2018169014A1 (ja) * | 2017-03-17 | 2018-09-20 | Mcppイノベーション合同会社 | 炭素繊維強化プラスチック接着積層用熱可塑性エラストマー |
WO2019103047A1 (ja) | 2017-11-22 | 2019-05-31 | 株式会社クラレ | ブロック共重合体の水素添加物、樹脂組成物、及びこれらの各種用途 |
WO2019230872A1 (ja) | 2018-05-31 | 2019-12-05 | 株式会社クラレ | ブロック共重合体の水素添加物、樹脂組成物、及びこれらの各種用途 |
WO2021181999A1 (ja) * | 2020-03-10 | 2021-09-16 | 株式会社ガラステクノシナジー | 樹脂組成物、およびポリビニルアセタール樹脂のリサイクル方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014007211A1 (de) | 2014-05-19 | 2015-11-19 | Kraiburg Tpe Gmbh & Co. Kg | Thermoplastische Elastomerenzusammensetzungen mit Haftung zu metallischen Oberflächen |
WO2016104740A1 (ja) * | 2014-12-25 | 2016-06-30 | 日本ゼオン株式会社 | ブロック共重合体水素化物および合わせガラス |
RU2689781C2 (ru) * | 2014-12-30 | 2019-05-29 | Публичное акционерное общество "СИБУР Холдинг" | Способ получения бутадиен-стирольных блок-сополимеров |
CN105534510A (zh) * | 2016-02-18 | 2016-05-04 | 夏放军 | 一种高精度血压计 |
KR102204482B1 (ko) * | 2016-07-27 | 2021-01-18 | 주식회사 쿠라레 | 필름, 피착체 표면에 그 필름이 접착된 가식 성형체, 그 가식 성형체의 제조 방법 |
EP3636431A4 (en) | 2017-06-06 | 2021-03-10 | Kuraray Co., Ltd. | MULTI-LAYER FILM AND ITS MANUFACTURING PROCESS |
CN107673764B (zh) * | 2017-09-27 | 2018-05-29 | 中国科学院长春光学精密机械与物理研究所 | 一种用于碳化硅素坯连接的粘结剂及其制备方法 |
WO2019134949A1 (en) * | 2018-01-08 | 2019-07-11 | Kuraray Europe Gmbh | Polyvinyl butyral as adhesion promoter in elastomeric adhesive formulations |
CN109504023A (zh) * | 2018-12-04 | 2019-03-22 | 南通大学 | 一种可粘附玻璃的热塑性弹性体及其制备方法 |
US11566129B2 (en) * | 2019-11-06 | 2023-01-31 | Kuraray Co., Ltd. | Thermoplastic elastomer composition |
CN116157467A (zh) * | 2020-12-14 | 2023-05-23 | 安隆化成株式会社 | 防滑垫用树脂组合物及其制造方法、以及防滑垫及其制造方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6325005A (ja) | 1986-07-17 | 1988-02-02 | Mitsubishi Petrochem Co Ltd | 積層体の製造方法 |
JPH09156035A (ja) | 1995-12-11 | 1997-06-17 | Dainippon Ink & Chem Inc | 金属部品のラミネート成形方法 |
JP2006206715A (ja) | 2005-01-27 | 2006-08-10 | Dow Corning Toray Co Ltd | 車両モールディング用熱可塑性エラストマー組成物および車両用モールディング付きガラス板 |
JP2006274158A (ja) * | 2005-03-30 | 2006-10-12 | Nippon Zeon Co Ltd | エラストマー組成物及び接着剤組成物 |
JP2006291019A (ja) | 2005-04-08 | 2006-10-26 | Dow Corning Toray Co Ltd | 熱可塑性エラストマー組成物および車両用モールディング付きガラス板 |
WO2007122995A1 (ja) * | 2006-04-18 | 2007-11-01 | Kuraray Co., Ltd. | 熱可塑性樹脂組成物およびそれからなる床タイル |
JP2008120929A (ja) * | 2006-11-13 | 2008-05-29 | Kitagawa Ind Co Ltd | 強粘着エラストマー組成物、および固定具 |
WO2009081877A1 (ja) | 2007-12-20 | 2009-07-02 | Kuraray Co., Ltd. | 熱可塑性重合体組成物及びそれからなる成形品 |
JP2009227844A (ja) | 2008-03-24 | 2009-10-08 | Unitika Ltd | 強化ポリアミド樹脂組成物 |
JP2010001364A (ja) | 2008-06-19 | 2010-01-07 | Unitika Ltd | ガラス繊維強化ポリアミド樹脂組成物 |
JP2010512426A (ja) * | 2006-12-07 | 2010-04-22 | スリーエム イノベイティブ プロパティズ カンパニー | ブロックコポリマーとアクリル接着剤とのブレンド |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4556690A (en) * | 1983-05-10 | 1985-12-03 | Mitsui Petrochemical Industries, Ltd | Acetal resin composition |
JPH0621209B2 (ja) * | 1983-08-11 | 1994-03-23 | 三菱化成株式会社 | 接着剤用又はフィルム用樹脂組成物 |
FI79124C (fi) * | 1986-05-28 | 1989-11-10 | Neste Oy | Modifierad polyolefin. |
JPH06325005A (ja) | 1993-05-14 | 1994-11-25 | Fujitsu Ltd | 再構成可能なトーラス・ネットワーク方式 |
DE69629806T2 (de) * | 1995-04-24 | 2004-07-01 | Polyplastics Co. Ltd. | Polyacetalharzzusammensetzung |
JP3285501B2 (ja) * | 1996-10-25 | 2002-05-27 | ポリプラスチックス株式会社 | ポリアセタール樹脂組成物 |
US6663975B1 (en) * | 1999-11-16 | 2003-12-16 | Bridgestone Corporation | Resin composition and gasket material |
US20050027072A1 (en) * | 2003-01-24 | 2005-02-03 | Hofmann George Henry | Process for conversion of polyvinyl butyral (PVB) scrap into processable pellets |
US20050159548A1 (en) * | 2004-01-16 | 2005-07-21 | Jean-Pierre Ibar | Miscible blends of normally immiscible polymers |
CN102822270B (zh) | 2010-03-31 | 2015-05-13 | 可乐丽股份有限公司 | 热塑性聚合物组合物以及由其形成的成型体 |
-
2011
- 2011-08-24 KR KR1020137004799A patent/KR101823715B1/ko active IP Right Grant
- 2011-08-24 WO PCT/JP2011/069092 patent/WO2012026501A1/ja active Application Filing
- 2011-08-24 CN CN201180041696.7A patent/CN103068915B/zh active Active
- 2011-08-24 EP EP11819964.5A patent/EP2610305B1/en active Active
- 2011-08-24 JP JP2012530695A patent/JP5809150B2/ja not_active Expired - Fee Related
- 2011-08-24 US US13/818,695 patent/US9670354B2/en active Active
- 2011-08-24 ES ES11819964.5T patent/ES2664971T3/es active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6325005A (ja) | 1986-07-17 | 1988-02-02 | Mitsubishi Petrochem Co Ltd | 積層体の製造方法 |
JPH09156035A (ja) | 1995-12-11 | 1997-06-17 | Dainippon Ink & Chem Inc | 金属部品のラミネート成形方法 |
JP2006206715A (ja) | 2005-01-27 | 2006-08-10 | Dow Corning Toray Co Ltd | 車両モールディング用熱可塑性エラストマー組成物および車両用モールディング付きガラス板 |
JP2006274158A (ja) * | 2005-03-30 | 2006-10-12 | Nippon Zeon Co Ltd | エラストマー組成物及び接着剤組成物 |
JP2006291019A (ja) | 2005-04-08 | 2006-10-26 | Dow Corning Toray Co Ltd | 熱可塑性エラストマー組成物および車両用モールディング付きガラス板 |
WO2007122995A1 (ja) * | 2006-04-18 | 2007-11-01 | Kuraray Co., Ltd. | 熱可塑性樹脂組成物およびそれからなる床タイル |
JP2008120929A (ja) * | 2006-11-13 | 2008-05-29 | Kitagawa Ind Co Ltd | 強粘着エラストマー組成物、および固定具 |
JP2010512426A (ja) * | 2006-12-07 | 2010-04-22 | スリーエム イノベイティブ プロパティズ カンパニー | ブロックコポリマーとアクリル接着剤とのブレンド |
WO2009081877A1 (ja) | 2007-12-20 | 2009-07-02 | Kuraray Co., Ltd. | 熱可塑性重合体組成物及びそれからなる成形品 |
JP2009227844A (ja) | 2008-03-24 | 2009-10-08 | Unitika Ltd | 強化ポリアミド樹脂組成物 |
JP2010001364A (ja) | 2008-06-19 | 2010-01-07 | Unitika Ltd | ガラス繊維強化ポリアミド樹脂組成物 |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013094997A (ja) * | 2011-10-28 | 2013-05-20 | Kuraray Co Ltd | 接着体の製造方法 |
EP3168024A1 (en) * | 2012-01-11 | 2017-05-17 | Kuraray Co., Ltd. | Thermoplastic polymer composition and molded article |
WO2013105392A1 (ja) * | 2012-01-11 | 2013-07-18 | 株式会社クラレ | 熱可塑性重合体組成物および成形品 |
JP2013141794A (ja) * | 2012-01-11 | 2013-07-22 | Kuraray Co Ltd | 接着体の製造方法 |
US10745598B2 (en) | 2012-01-11 | 2020-08-18 | Kuraray Co., Ltd. | Thermoplastic polymer composition and molded article |
US10767089B2 (en) | 2012-01-11 | 2020-09-08 | Kuraray Co., Ltd. | Thermoplastic polymer composition and molded article |
JPWO2013145594A1 (ja) * | 2012-03-29 | 2015-12-10 | 三井化学株式会社 | フェノール樹脂成形材料、摩擦材、およびフェノール樹脂成形品 |
WO2014129561A1 (ja) | 2013-02-22 | 2014-08-28 | 株式会社クラレ | 繊維、布及び不織布 |
KR20150120378A (ko) | 2013-02-22 | 2015-10-27 | 가부시키가이샤 구라레 | 섬유, 천 및 부직포 |
JP2014168940A (ja) * | 2013-03-05 | 2014-09-18 | Kuraray Co Ltd | 接着体の製造方法 |
JP2015105345A (ja) * | 2013-11-29 | 2015-06-08 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
KR20170046137A (ko) | 2014-08-26 | 2017-04-28 | 주식회사 쿠라레 | 열가소성 중합체 조성물, 및 성형품 |
JP5942055B1 (ja) * | 2014-08-26 | 2016-06-29 | 株式会社クラレ | 熱可塑性重合体組成物、及び成形品 |
WO2016031550A1 (ja) * | 2014-08-26 | 2016-03-03 | 株式会社クラレ | 熱可塑性重合体組成物、及び成形品 |
KR20170082599A (ko) * | 2014-11-10 | 2017-07-14 | 주식회사 쿠라레 | 합판 유리용 중간막 및 합판 유리 |
KR102469393B1 (ko) * | 2014-11-10 | 2022-11-22 | 쿠라라이 유럽 게엠베하 | 합판 유리용 중간막 및 합판 유리 |
JPWO2016121868A1 (ja) * | 2015-01-28 | 2017-11-02 | 株式会社クラレ | 多層フィルム |
JP2017095617A (ja) * | 2015-11-25 | 2017-06-01 | 株式会社クラレ | 活性エネルギー線硬化性樹脂組成物、積層体および成形体、並びにそれらの製造方法 |
KR20190008570A (ko) | 2016-05-18 | 2019-01-24 | 주식회사 쿠라레 | 수지 조성물, 필름 및 접합 유리용 중간막 |
WO2017199983A1 (ja) | 2016-05-18 | 2017-11-23 | 株式会社クラレ | 水添ブロック共重合体、制振材、遮音材、合わせガラス用中間膜、ダムラバー、靴底材料、床材、積層体および合わせガラス |
WO2017200052A1 (ja) | 2016-05-18 | 2017-11-23 | 株式会社クラレ | 樹脂組成物、フィルム及び合わせガラス用中間膜 |
WO2018169014A1 (ja) * | 2017-03-17 | 2018-09-20 | Mcppイノベーション合同会社 | 炭素繊維強化プラスチック接着積層用熱可塑性エラストマー |
US11572460B2 (en) | 2017-03-17 | 2023-02-07 | Mcpp Innovation Llc | Thermoplastic elastomer for carbon fiber reinforced plastic bonding lamination |
WO2019103047A1 (ja) | 2017-11-22 | 2019-05-31 | 株式会社クラレ | ブロック共重合体の水素添加物、樹脂組成物、及びこれらの各種用途 |
WO2019230872A1 (ja) | 2018-05-31 | 2019-12-05 | 株式会社クラレ | ブロック共重合体の水素添加物、樹脂組成物、及びこれらの各種用途 |
WO2021181999A1 (ja) * | 2020-03-10 | 2021-09-16 | 株式会社ガラステクノシナジー | 樹脂組成物、およびポリビニルアセタール樹脂のリサイクル方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2610305A4 (en) | 2014-05-21 |
KR101823715B1 (ko) | 2018-01-30 |
KR20130097167A (ko) | 2013-09-02 |
CN103068915A (zh) | 2013-04-24 |
US9670354B2 (en) | 2017-06-06 |
JPWO2012026501A1 (ja) | 2013-10-28 |
EP2610305B1 (en) | 2018-02-07 |
CN103068915B (zh) | 2015-09-16 |
JP5809150B2 (ja) | 2015-11-10 |
EP2610305A1 (en) | 2013-07-03 |
ES2664971T3 (es) | 2018-04-24 |
US20130157069A1 (en) | 2013-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5809150B2 (ja) | 熱可塑性重合体組成物および成形品 | |
JP5809138B2 (ja) | 熱可塑性重合体組成物および成形品 | |
JP5998154B2 (ja) | 熱可塑性重合体組成物および成形品 | |
JP5802669B2 (ja) | 熱可塑性重合体組成物および成形品 | |
JP6504461B2 (ja) | 熱可塑性エラストマー組成物、成形体及び接着剤 | |
JP5942055B1 (ja) | 熱可塑性重合体組成物、及び成形品 | |
JPWO2009081877A1 (ja) | 熱可塑性重合体組成物及びそれからなる成形品 | |
WO2011125796A1 (ja) | 熱可塑性重合体組成物およびそれからなる成形体 | |
JP5785874B2 (ja) | 接着体の製造方法 | |
JP5830352B2 (ja) | 接着体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180041696.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11819964 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2012530695 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011819964 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13818695 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20137004799 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |