WO2013105392A1 - 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
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- WO2013105392A1 WO2013105392A1 PCT/JP2012/082514 JP2012082514W WO2013105392A1 WO 2013105392 A1 WO2013105392 A1 WO 2013105392A1 JP 2012082514 W JP2012082514 W JP 2012082514W WO 2013105392 A1 WO2013105392 A1 WO 2013105392A1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/365—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/368—Silicon nitride
-
- 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 can be bonded to ceramics, metal or synthetic resin without applying a primer treatment, etc., and has excellent flexibility, mechanical properties, molding processability, heat resistance, and storage stability, and
- the present invention also relates to a method for producing the molded article, and particularly a molded article formed by bonding the thermoplastic polymer composition with ceramics, metal or synthetic resin by insert molding.
- 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 excellent in flexibility, mechanical properties and 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 Document 7 discloses a thermoplastic polymer composition containing a styrenic thermoplastic elastomer, a modified polyolefin and a softening agent.
- 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.
- Patent Document 8 discloses a thermoplastic polymer composition containing a specific styrenic thermoplastic elastomer and a functionalized polyolefin, which can be overmolded into a polar support containing polyamide and has a low compression set at high temperatures. It is disclosed.
- thermoplastic polymer composition disclosed in Patent Document 7 when the thermoplastic polymer composition disclosed in Patent Document 7 is placed in a temperature environment of 60 ° C. or higher when a molded product bonded to a metal or a synthetic resin is placed in a temperature environment of 60 ° C. or higher, the adhesiveness is practically insufficient. It decreases as much. This phenomenon becomes a problem in automobile parts that have a temperature of 60 ° C. or higher in summer. Further, the thermoplastic polymer composition disclosed in Patent Document 7 is not necessarily bonded with sufficient strength by insert molding, and is used when bonded to a housing material such as an electric / electronic device, an OA device, and a home appliance. It becomes a problem.
- thermoplastic polymer composition disclosed in Patent Document 8 a large amount of plasticizer must be used substantially to ensure moldability, and the plasticizer bleeds when the molded product is stored for a long period of time. Occurs, the adhesive properties deteriorate, and the storage stability is impaired.
- the thermoplastic polymer compositions disclosed in Patent Documents 7 and 8 have room for further improvement. Therefore, the object of the present invention is to be able to adhere to ceramics, metal or synthetic resin without applying a primer treatment, etc., and has excellent flexibility, mechanical properties, molding processability, heat resistance and storage stability.
- An object of the present invention is to provide a polymer composition and a molded article thereof, and further to provide a method for producing a molded article obtained by bonding the thermoplastic polymer composition with ceramics, metal or synthetic resin by insert molding.
- the above object is [1] having a polymer block containing an aromatic vinyl compound unit and a polymer block comprising a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more
- thermoplastic elastomer (A) has a weight average molecular weight (Mw) of 70,000 to 200,000 and is a linear block copolymer.
- Mw weight average molecular weight
- thermoplastic polymer composition [5] The thermoplastic polymer composition according to any one of [1] to [4], further comprising 1 to 100 parts by mass of a tackifying resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A).
- thermoplastic polymer composition according to any one of [1] to [5], wherein the polar group-containing polypropylene resin (B) is a carboxylic acid-modified polypropylene resin; [7] A molded article using the thermoplastic polymer composition according to any one of [1] to [6] above; [8] The molded article according to [7], wherein the thermoplastic polymer composition is bonded to at least one selected from ceramics, metals, and synthetic resins; [9] The molded article according to the above [8], wherein the 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 can be bonded to ceramics, metals or synthetic resins without applying a primer treatment or the like, and is excellent in flexibility, mechanical properties, molding processability, storage stability and heat resistance. Yes. Needless to say, it can be bonded to ceramics, metals or synthetic resins subjected to primer treatment.
- a molded product obtained by bonding the thermoplastic polymer composition of the present invention to ceramics, metal, or synthetic resin has practically sufficient adhesiveness even when placed in an environment of 60 ° C. or higher, It can be used for a wide range of applications.
- thermoplastic polymer composition in which the thermoplastic polymer composition is bonded with ceramics, metal or synthetic resin with higher adhesive strength can be produced by insert molding, and the molded product thus obtained has higher adhesive strength. It can also be used for applications that require.
- the molded article of the thermoplastic polymer composition of the present invention can maintain good adhesion without bleeding of the softener even after long-term storage.
- thermoplastic polymer composition comprises a polymer block containing an aromatic vinyl compound unit and a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more.
- thermoplastic elastomer (A) which is a block copolymer having a polymer block consisting of A thermoplastic polymer composition containing 10 to 120 parts by mass of the resin (B).
- thermoplastic polymer composition of the present invention may further contain a tackifier resin (C) and the like.
- 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 total amount of 1,2-bonds and 3,4-bonds is set to 40 mol% or more. It is presumed that the compatibility with the resin (B) is enhanced, and the resulting thermoplastic polymer composition is provided with high insert adhesiveness and high adhesiveness in a temperature environment of 60 ° C. or higher.
- the adhesiveness between the thermoplastic polymer composition and the insert part in a molded product obtained by insert molding may be referred to as “insert adhesiveness”.
- -Polymer blocks containing aromatic vinyl compound units Examples of the aromatic vinyl compound constituting the polymer block containing an aromatic vinyl compound unit 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% by mass or less, with respect to all constituent units of the polymer block containing the aromatic vinyl compound unit. More preferably, it is 5% by mass or less.
- the compound constituting the polymer block comprising conjugated diene compound units may be any conjugated diene of 4 to 8 carbon atoms or a mixture thereof, but is preferably a mixture of butadiene, isoprene, butadiene and isoprene. More preferably, it is isoprene.
- the polymer block containing the conjugated diene compound unit may have only the conjugated diene compound unit. However, as long as the effect of the present invention is not impaired, other copolymerizable monomer units together with the conjugated diene compound unit. You may have.
- Examples of other copolymerizable monomers include styrene, ⁇ -methylstyrene, 4-methylstyrene, and the like.
- the ratio is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to all the structural units of the polymer block composed of conjugated diene compound units.
- the total amount of 1,2-bond and 3,4-bond is 40 mol% or more. It needs to be. From the same viewpoint, it is preferably 45 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 50 to 80 mol%.
- the bond form other than 1,2-bond and 3,4-bond is 1,4-bond, and 1,2-bond is usually less than 5 mol%.
- the total amount of 1,2-bond and 3,4-bond can be calculated by 1 H-NMR measurement.
- the integrated value of the peak existing at 4.2 to 5.0 ppm derived from 1,2-bonds and 3,4-bond units and 5.0 to 5.5 derived from 1,4-bond units can be calculated from the ratio with the integrated value of the peak existing at 45 ppm.
- the bonding form of the polymer block containing the aromatic vinyl compound unit and the polymer block comprising the conjugated diene compound unit in the thermoplastic elastomer (A) is not particularly limited, and is linear, branched, radial, or these Any of the bonding forms in which two or more of these are combined may be used, but a linear bonding form is preferable.
- a linear bond form when a polymer block containing an aromatic vinyl compound unit is represented by a and a polymer block comprising a conjugated diene compound unit is represented by b, the diblock represented by ab.
- Block copolymer triblock copolymer represented by aba or b-a-b, tetrablock copolymer represented by abbab, abbab A pentablock copolymer represented by -a or ba-ba-ab, ( While-b) nX-type 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 a polymer block composed of a conjugated diene compound unit is hydrogenated (hereinafter sometimes abbreviated as “hydrogenated”). It is preferable that The hydrogenation rate of the polymer block comprising conjugated diene compound 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 thermoplastic elastomer (A) 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, and particularly preferably 15 to 25% by mass.
- the weight average molecular weight of the linear 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. More preferably, it is 60,000 to 200,000, more preferably 70,000 to 200,000, particularly preferably 70,000 to 190,000, and most preferably 80,000 to 180,000.
- the weight average molecular weight is 30,000 or more, good mechanical properties are obtained, and if it is 500,000 or less, good moldability is obtained.
- 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 120 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A).
- thermoplastic elastomer (A) More preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, particularly preferably Properly substantially to 0 parts by weight.
- the content is 120 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A)
- the mechanical properties such as tensile strength at break and tensile elongation at break are improved, and further, it adheres to ceramics, metals or synthetic resins.
- the molded product thus obtained is excellent in 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 (B) 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.
- It may consist of structural units that In particular, it is preferably composed of a structural unit derived from butadiene or isoprene or a structural unit derived from butadiene and isoprene.
- the amount of 1,4-bond can be calculated by the 1 H-NMR measurement described above.
- thermoplastic elastomer (A) Although the manufacturing method of a thermoplastic elastomer (A) is not specifically limited, For example, it can manufacture by an anionic polymerization method.
- 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 Usually, 0.01 to 0.2 parts by mass of an initiator such as an alkyllithium compound or a dilithium compound is used per 100 parts by mass of isoprene.
- 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, for example, isoprene. It is done.
- 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 total amount of 1,2-bonds and 3,4-bonds of the thermoplastic elastomer (A) can be increased.
- the total amount of 1,2-bond and 3,4-bond of the thermoplastic elastomer (A) can be easily controlled by the amount.
- 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 amount of the organic Lewis base used is, for example, lithium contained in the initiator from the viewpoint of making the total amount of 1,2-bond and 3,4-bond of the thermoplastic elastomer (A) 40 mol% or more.
- the stoichiometric ratio with respect to ions is preferably 0.01 to 1000 times, more preferably 0.1 to 100 times, and still more preferably 0.1 to 50 times.
- the amount of organic Lewis base used within this range the total amount of 1,2-bonds and 3,4-bonds of the thermoplastic elastomer (A) can be arbitrarily controlled.
- 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 styrenic thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated thermoplastic 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 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).
- steam stripping By drying, the hydrogenated thermoplastic elastomer (A) can be isolated.
- Poly group-containing polypropylene resin (B) By including the polar group-containing polypropylene-based resin (B) in the thermoplastic polymer composition of the present invention, it becomes possible to satisfactorily adhere to a ceramic, metal, or synthetic resin, and to the ceramic, metal, or synthetic resin. Even when a molded product obtained by bonding the thermoplastic polymer composition of the present invention is exposed to a temperature environment of 60 ° C. or higher, high adhesiveness is maintained.
- the polar group that the polar group-containing polypropylene resin (B) has include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; acid anhydride group.
- Propylene and a polar group containing copolymerizable monomer are random copolymerization, block copolymerization, or graft copolymerization by a well-known method. Obtained by. Among these, random copolymerization and graft copolymerization are preferable, and a graft copolymer is more preferable. In addition, it can also be obtained by subjecting a polypropylene resin to a reaction such as oxidation or chlorination by a known method.
- the polar group-containing polypropylene resin (B) may be obtained by copolymerizing an ⁇ -olefin other than propylene with a polar group-containing copolymerizable monomer together with propylene.
- the ⁇ -olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like.
- the ⁇ -olefin can be copolymerized with a polar group-containing copolymerizable monomer by a known method, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.
- the ratio of the structural unit derived from ⁇ -olefin other than propylene to the total structural unit of the polar group-containing polypropylene resin (B) is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, More preferably, it is 0 to 25 mol%.
- the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid, ester or anhydride thereof. Among these, unsaturated carboxylic acid or its ester or anhydride is preferable.
- Examples of the 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 acid and maleic anhydride are more preferable. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
- polar group-containing polypropylene resin (B) from the viewpoint of adhesiveness, a polypropylene containing a carboxyl group as a polar group, that is, a carboxylic acid-modified polypropylene resin is preferable, and a maleic acid-modified polypropylene resin or a maleic anhydride-modified polypropylene. More preferred is a resin.
- (meth) acrylic acid ester exemplified as the polar group-containing copolymerizable monomer
- Alkyl acrylates such as isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate
- methyl methacrylate, ethyl methacrylate, n-propyl methacrylate Such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, etc.
- Acid alkyl esters These (meth) acrylic acid esters may be used alone or in combination of two or
- the polar group of the polar group-containing polypropylene resin (B) may be post-treated after polymerization. For example, 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. In addition, hydrolysis of vinyl acetate may be performed.
- the melt flow rate (MFR) of the polar group-containing polypropylene resin (B) under the conditions of 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 300 g / 10 min, more preferably 0.8. It is 1 to 100 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 (B) under the above conditions is 0.1 g / 10 min or more, good moldability can be obtained.
- the melting point of the polar group-containing polypropylene resin (B) is preferably 100 ° C. or higher, more preferably 110 to 170 ° C., and still more preferably 120 to 145 ° C. from the viewpoint of heat resistance.
- the melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min.
- the ratio of the polar group-containing structural unit of the polar group-containing polypropylene resin (B) to the total structural unit of the polar group-containing polypropylene resin (B) is preferably 0.01 to 10% by mass. If it is 0.01 mass% or more, the adhesiveness with respect to ceramics, a metal, and a synthetic resin will become high. When the ratio of the polar group-containing structural unit is 10% by mass or less, the affinity with the thermoplastic elastomer (A) is improved and the mechanical properties are improved. Moreover, the production
- the ratio is preferably 0.01 to 7% by mass, more preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.1 to 3% by mass. %, More preferably 0.2 to 1% by mass.
- the thermoplastic polymer composition of the present invention contains 10 to 120 parts by mass of the polar group-containing polypropylene resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A).
- the polar group-containing polypropylene resin (B) is less than 10 parts by mass, it is difficult to adhere to ceramics, metal or synthetic resin.
- the polar group-containing polypropylene resin (B) is more than 120 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 (B) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, preferably with respect to 100 parts by mass of the thermoplastic elastomer (A). Is 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less. Accordingly, the content of the polar group-containing polypropylene resin (B) is preferably 15 to 100 parts by mass, more preferably 15 to 80 parts by mass, and still more preferably 100 parts by mass of the thermoplastic elastomer (A). 20 to 70 parts by mass.
- thermoplastic polymer composition of the present invention may further contain a tackifier resin (C) as necessary.
- a tackifier resin (C) By containing the tackifier resin (C), the moldability is further improved while maintaining the adhesive properties.
- the tackifying resin (C) 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 (C) 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, and hydrogenated aromatic hydrocarbon resins and hydrogenated terpene resins are more preferable.
- the softening point of the tackifier resin (C) is preferably 50 to 200 ° C, more preferably 65 to 180 ° C, and further preferably 80 to 160 ° C.
- the softening point is 50 ° C. or higher, it is possible to maintain the adhesive properties with respect to the environmental temperature and the storage stability of the molded article of the thermoplastic polymer composition.
- 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.
- the content thereof is preferably 1 to 100 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).
- the amount is 5 to 70 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 45 parts by mass.
- the content of the tackifying resin (C) 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. . (Other optional ingredients)
- the thermoplastic polymer composition of the present invention may contain a softening agent as necessary within a range that does not significantly impair the effects of the present invention.
- a softener is not particularly limited, and examples thereof include softeners generally used for rubber and plastics.
- 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
- phosphoric acid plasticizers such as organic phosphate esters and organic phosphite esters can also be used.
- Examples of monobasic organic acid esters include triethylene glycol dicaproate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-octylate, triethylene glycol di-2- Glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol represented by ethylhexyl acid ester, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, Examples thereof include 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, such as 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 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 storage stability of the molded article of the obtained thermoplastic polymer composition is not impaired, and relative to 100 parts by mass of the thermoplastic elastomer (A).
- the amount is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 28 parts by mass or less, and particularly preferably 10 parts by mass or less.
- 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, a charge as long as the effects of the invention are not impaired. It may contain an inhibitor, 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 by 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 is usually melt-kneaded 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 is usually melt-kneaded 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 90 or less, more preferably 30 to 90, more preferably 35 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 50 g / 10 min, more preferably 1 to 40 g / 10 min, still more preferably 2 to 30 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 compression molding method, a blow molding method, a calendar molding method, or a casting molding method can be employed. In addition, a general T-die method, a calendar method, an inflation method, a belt method, etc. can be employed for forming a film or a sheet.
- the molded article using the thermoplastic polymer composition of the present invention preferably does not bleed in order to maintain stable adhesion even after long-term storage.
- a sheet formed from a thermoplastic polymer composition is cut into 29 mm ⁇ , sanded with cardboard, loaded with a 1 kg weight, and the state of the cardboard after standing at 70 ° C. for 360 hours. It is preferable that no bleed is observed when observed.
- the present invention further provides a molded article obtained by bonding the thermoplastic polymer composition to at least one selected from ceramics, metals and synthetic resins, and further, the thermoplastic polymer composition comprises ceramics,
- a molded article obtained by bonding metals or synthetic resins, or at least two kinds selected from ceramics, metals and synthetic resins are preferable.
- the adhesive strength of the thermoplastic polymer composition in the molded article is preferably 20 N / 25 mm or more, more preferably 30 N / 25 mm or more, and further preferably 60 N / 25 mm or more in the compression molding method.
- the adhesive strength of 20 N / 25 mm or more is comparable to the adhesive strength in the case of performing a surface treatment such as a primer, and is an adhesive strength that can withstand practical use.
- the adhesive strength is a value measured according to JIS K 6854-2 by the method described in the examples.
- 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.
- it may be a 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.
- plating such as copper plating, nickel plating, chrome plating, tin plating, galvanization, platinum plating, gold plating, or silver plating.
- light metals such as aluminum and a magnesium alloy, are used for housing materials, such as an electronic / electric equipment, OA equipment, household appliances, and a member for motor vehicles, and such a housing material can also be used.
- 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 synthetic resin containing the inorganic filler are not impaired, and is generally preferably 0.1% relative to 100 parts by mass of the synthetic resin. 1 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 product in which the thermoplastic polymer composition of the present invention is bonded to ceramics or metal is not particularly limited, and any method can be used as long as it is a method for producing a molded product by melt bonding.
- the molding method include an insert molding method, an extrusion lamination method, a compression molding method, and a melt casting method.
- a method for producing a molded product by the insert molding method will be described later.
- a molded article can also be produced by directly extruding the molten thermoplastic polymer composition of the present invention extruded from a die having a predetermined shape.
- a molded product made of the thermoplastic polymer composition of the present invention is previously molded by an injection molding method or an extrusion molding method, and the molded product is previously It can also be produced by heating and pressurizing an adherend that has been formed into a shape and size using a compression molding machine or the like.
- a protective layer of a nonpolar resin such as an olefin resin or a cyclic olefin resin may be provided on the outermost layer on the surface that is not bonded 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.
- the present invention also provides a method for producing a molded article obtained by bonding the thermoplastic polymer composition of the present invention with ceramics, metal or synthetic resin by insert molding.
- insert molding refers to inserting the thermoplastic polymer composition into the mold having a predetermined shape and then inserting the thermoplastic polymer composition into the thermoplastic polymer composition.
- This is a method for obtaining a molded product comprising a product, and a molded product in which the insert part and the thermoplastic polymer composition are integrated by the method (hereinafter, the insert part and the thermoplastic polymer composition are bonded to each other).
- the molded product obtained by integrating them may be referred to as an adhesive body).
- Insert parts There is no restriction
- the insert part used in the present invention at least one selected from the group consisting of glass, ceramics, metal, metal-plated, and synthetic resin is preferably used. Ceramic, metal, metal-plated More preferably.
- FIGS. 1 to 6 There is no particular limitation on the mold used at the time of insert molding, but it is preferable to use a mold as shown in FIGS. 1 to 6, for example.
- 1 to 3 are a front view, a transverse sectional view, and a longitudinal sectional view, respectively, of the movable mold
- FIGS. 4 to 6 are a front view, a transverse sectional view, and a longitudinal sectional view, respectively, of the fixed mold.
- two cavities CAV1 and CAV2 are shown in FIG. 1, the cavities are dug to different depths, and CAV1 and CAV2 can be selected by switching the flow paths.
- the insert part (4) installed in the cavity can be fixed by the vacuum line (2).
- FIGS. 1, 5, and 6 show a state in which the insert part (4) and the thermoplastic polymer composition (5) are installed in the cavity.
- FIG. 4 shows a mold temperature adjusting water channel (6), and the thick arrows in FIGS. 1, 5, and 6 indicate the route through which the thermoplastic polymer composition is filled from the cylinder.
- the temperature of the insert part at the time of insert molding is preferably 30 to 150 ° C. If the temperature of the insert part is within the temperature range, sufficient adhesive strength can be obtained between the insert part and the thermoplastic polymer composition. From the same viewpoint, the temperature of the insert part is preferably 50 to 150 ° C., more preferably 80 to 150 ° C., still more preferably 100 to 150 ° C., and particularly preferably 115 to 145 ° C. If it is 30 degreeC or more, it is not necessary to provide a cooling equipment separately, and sufficient insert adhesiveness between insert components and a thermoplastic polymer composition is obtained. On the other hand, when the temperature is 150 ° C. or lower, the thermoplastic resin composition is less contracted and deformed in the cooling process, the desired shape is easily obtained, less energy is required for heating and cooling, and the molding cycle time is reduced.
- Mechanism for selectively controlling the temperature of the insert part means that it is close to the insert part. This is a temperature control function dedicated to insert parts. By selectively controlling the temperature of the insert part, the temperature of the insert part can be easily raised, and the adhesive can be easily released from the mold.
- a heating element such as an electric heater, an electromagnetic induction heater, a heat medium, or a hot plate can be used. When an electric heater or an electromagnetic induction heater is used, it can be used by being embedded in a mold, or a heating plate embedded with a heater can be attached to the mold surface.
- a heat medium flow path is provided in a mold, a heat medium having a predetermined temperature is supplied from the outside, and discharged to the outside.
- a heat medium Fluids, such as oil, water, water vapor
- a metal when used for the insert part, it may be directly energized and heated, or may be induction heated by an induction coil.
- thermoplastic polymer composition As a procedure for setting the temperature of the insert part within the above range, (1) A method [preheating method] in which the insert part is brought to a predetermined temperature before the thermoplastic polymer composition is filled into a mold holding the insert part. (2) A method in which the temperature is not adjusted at the stage of filling the thermoplastic polymer composition, and the temperature is raised to a predetermined temperature in the mold after filling [post-heating method], (3) A method of raising the temperature to some extent at the stage of filling the thermoplastic polymer composition, and further raising the temperature to a predetermined temperature in the mold after filling. Among these, from the viewpoint of adhesiveness control, the methods (1) and (2) are preferable.
- the method (1) is more preferable, and from the viewpoint of the appearance of the bonded body Therefore, the method (2) is more preferable.
- the temperature control of the insert part may be stopped immediately after the operation of filling the thermoplastic polymer composition into the mold is started, or during the filling of the thermoplastic polymer composition. The temperature adjustment of the insert part may be continued.
- the adhesive body obtained is taken out (released) from the mold, and the adhesive body is cooled as necessary.
- the surface temperature of the bonded body is preferably 30 to 50 ° C. before the bonded body is removed from the mold.
- the cooling method For example, the method (here also including natural cooling) performed via the temperature control mechanism of a metal mold
- a hot runner can be used at the time of insert molding as a means by which the removal of the solidified resin in the mold channel (for example, sprue, runner and gate) can be omitted and the adhesive can be easily released.
- As the heating method of the hot runner either an internal heating method or an external heating method can be used.
- Examples of the hot runner gate seal system include a thermal balance system and a valve gate system. Examples of the seal by thermal balance include a hot tip, a sprue gate, and a hot edge.
- thermoplastic polymer composition of the present invention can be bonded to ceramics, metals, or synthetic resins without performing primer treatment, and is excellent in flexibility, mechanical properties, molding processability, and heat resistance.
- a molded product obtained by bonding the thermoplastic polymer composition of the present invention to ceramics, metal or synthetic resin has practically sufficient adhesiveness even in an environment of 60 ° C. or more, and is widely used. It can be used.
- an adhesive formed by bonding the thermoplastic polymer composition with ceramics, metal or synthetic resin by insert molding can be produced with excellent insert adhesion, and higher adhesive strength in an environment of 60 ° C. or higher. It can also be used for applications that require.
- thermoplastic polymer composition of the present invention can be widely applied as the above-mentioned 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 of these are included in the scope of the present invention.
- it is suitable for impact mitigating materials, anti-slip materials, covering materials, waterproofing materials, design materials, automotive window moldings, gaskets, and glass / metal frame connections in solar cell modules, etc. that are bonded to the housing of electrical products. Can be used.
- thermoplastic polymer composition of the present invention is also suitably used as an adhesive.
- the thermoplastic polymer composition of the present invention since it has good adhesion to any of ceramics, metals and synthetic resins, it is an adhesive that bonds not only the same kind of materials but also different kinds of materials to each other. It is also preferably used as an agent.
- it since it has flexibility, it also has a buffering action against a difference in thermal expansion coefficient between different materials.
- thermoplastic polymer composition of the present invention is also suitably used as an adhesive sheet.
- a sheet by an extrusion method or the like, and sandwiching it with a member composed of at least one of ceramic, metal and synthetic resin, and thermocompression bonding, not only the same kind of materials but also different kinds of materials can be joined. .
- it since it has a softness
- 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 in the initiator) as an organic Lewis base. (Equivalent to 15 times the stoichiometric ratio to 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-polyisoprene-polystyrene.
- thermoplastic elastomer a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer).
- 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, and 1,2-contained in the polyisoprene block. The total amount of bonds and 3,4-bonds was 60 mol%.
- Thermoplastic elastomer (A2) 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 mass% cyclohexane solution) as an initiator, and 0.02 L of ethylene glycol dimethyl ether as an organic Lewis base (in the initiator) The stoichiometric ratio was 0.7 times as large as that of 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 (hereinafter referred to as thermoplastic elastomer)).
- A2) was obtained.
- the resulting thermoplastic elastomer (A2) 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 1,2-bonds contained in the polybutadiene block. The amount was 78 mol%.
- Thermoplastic elastomer (A3) 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 (A3) 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 (A4) A pressure-resistant container purged with nitrogen and dried was charged with 80 L of cyclohexane as a solvent and 0.40 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.6 L of tetrahydrofuran as an organic Lewis base (lithium in the initiator) (Equivalent to 15 times the stoichiometric ratio to 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-polyisoprene-polystyrene.
- thermoplastic elastomer a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer).
- thermoplastic elastomer (A4) has a weight average molecular weight of 72,800, a styrene content of 30% by mass, a hydrogenation rate of 90%, a molecular weight distribution of 1.04, and 1,2-contained in the polyisoprene block.
- the total amount of bonds and 3,4-bonds was 60 mol%.
- Thermoplastic elastomer (A'5) A pressure-resistant container purged with nitrogen and dried was charged with 80 L of cyclohexane as a solvent and 0.047 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator. After the temperature was raised to 50 ° C., 2.3 L of styrene was added and polymerized for 3 hours. Subsequently, a mixture of 8.1 L of isoprene and 6.6 L of butadiene was added for polymerization for 4 hours, and 2.3 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 the triblock copolymer consisting of the polystyrene block-poly (isoprene / butadiene) block-polystyrene block obtained above was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5 mass%) as a hydrogenation catalyst.
- thermoplastic elastomer (A′5) was obtained.
- the resulting thermoplastic elastomer (A'5) has a weight average molecular weight of 380,000, a styrene content of 30% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.04, and is contained in a poly (isoprene / butadiene) block.
- the total amount of 1,2-bond and 3,4-bond was 5 mol%.
- Thermoplastic elastomer (A'6) A pressure-resistant container purged with nitrogen and dried was charged with 80 L of cyclohexane as a solvent and 0.32 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator. After the temperature was raised to 50 ° C., 2.5 L of styrene was added for polymerization for 3 hours, subsequently 30 L of isoprene was added for polymerization for 4 hours, and further 2.5 L of styrene was added for polymerization 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.
- thermoplastic elastomer (A′6) was obtained.
- the resulting thermoplastic elastomer (A′6) has a weight average molecular weight of 97,000, a styrene content of 18% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.04, and 1,2 contained in the polyisoprene block.
- the total amount of bonds and 3,4-bonds was 5 mol%.
- Poly group-containing polypropylene resin (B1) 42 g of polypropylene “Prime Polypro F327” (manufactured by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were added at 180 ° C. using a batch mixer. Melt kneading was performed under the condition of a screw rotation speed of 40 rpm. MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B1)) is 6 g / 10 min, and the maleic anhydride concentration is 0.3%.
- the melting point was 138 ° C.
- the maleic anhydride concentration is a value obtained by titrating the obtained kneaded product with a methanol solution of potassium hydroxide, and the same applies hereinafter.
- the melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min, and so on.
- Poly group-containing polypropylene resin (B2) 42 g of polypropylene “Novatech PP FG3DE (manufactured by Nippon Polypro Co., Ltd.)”, 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were mixed at 180 ° C. using a batch mixer. Melt kneading was performed under the condition of a screw rotation speed of 40 rpm.
- MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B2)) is 10 g / 10 minutes, and the maleic anhydride concentration is 0.3%.
- the melting point was 143 ° C.
- MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B3)) is 250 g / 10 minutes, and the maleic anhydride concentration is 3.0%.
- the melting point was 161 ° C.
- Polypropylene resin (B4) Using a batch mixer, 42 g of polypropylene “Novatech PP E111G (manufactured by Prime Polymer Co., Ltd.)”, 8.4 g of maleic anhydride and 126 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were mixed using a batch mixer. Melt kneading was performed at a temperature of 100 ° C. and a screw rotation speed of 100 rpm.
- MFR 230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B4)) is 80 g / 10 minutes, and the maleic anhydride concentration is 6.0%.
- the melting point was 135 ° C.
- thermoplastic polymer compositions 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.
- thermoplastic polymer compositions prepared according to the following examples and comparative examples were cut into 29 mm ⁇ , sanded with cardboard, placed with a 1 kg weight, and allowed to stand at 70 ° C. for 360 hours. The state of the cardboard after the test was observed, and the case where no bleed was observed was marked with ⁇ , and the case where it was seen was marked with ⁇ .
- ⁇ 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 sheet of the thermoplastic polymer composition 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, and the outer dimensions are 200 mm ⁇ 200 mm, the inner dimensions are 150 mm ⁇ 150 mm.
- the metal spacer having a thickness of 2 mm was disposed at the center.
- the overlapped sheet and the metal spacer are sandwiched between polytetrafluoroethylene sheets, further sandwiched between the metal plates from the outside, and a load of 20 kgf / cm 2 (under the temperature conditions shown in Table 1 or Table 2 using a compression molding machine. (2N / mm 2 ) for 3 minutes to obtain a laminate composed of PET / thermoplastic polymer composition / glass plate.
- ⁇ 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. The same operation as the production of the body was performed to obtain a laminate comprising PET / thermoplastic polymer composition / aluminum plate.
- Examples 1 to 17 and Comparative Examples 1 to 5> After melt-kneading the raw materials listed in Table 1 or Table 2 at the ratio shown in Table 1 or Table 2 using a twin screw extruder under the conditions of 230 ° C. and screw rotation 200 rpm, they are extruded into strands and cut. A pellet of a thermoplastic polymer composition was obtained. The resulting pellet, 230 ° C. using a compression molding machine, by 3 minutes compression molding under the conditions of a load 100kgf / cm 2 (9.8N / mm 2), the thickness of 1mm of the thermoplastic polymer composition Got the sheet.
- thermoplastic polymer composition sheets were measured according to the measurement method. Moreover, the adhesive force with a glass plate and the adhesive force with an aluminum plate were measured according to the said method. Furthermore, the bleeding property of the obtained thermoplastic polymer composition was measured according to the above method. The results are shown in Table 1.
- molded articles were produced by insert molding according to the following method, and insert adhesiveness was evaluated.
- the following adherend (insert part) shown in Table 1 or 2 was fixed in the mold by a vacuum line.
- the heater was energized, and the adherend was adjusted to the temperature shown in Table 1 or 2 by heat conduction.
- the adhesive body was obtained by cooling the surface temperature of the adhesive body to 30 ° C.
- Tables 1 and 2 show the insert adhesiveness (adhesive force) at 23 ° C. of the obtained adhesive.
- Adherent As the adherend, the surface of both surfaces of each of the following insert parts having a length of 100 mm, a width of 35 mm and a thickness of 1 mm was washed using an aqueous surfactant solution and distilled water in this order, and dried at 65 ° C. It was.
- thermoplastic polymer compositions obtained in Examples 1 to 14 have excellent adhesion to ceramics (glass) and metal without performing primer treatment, etc. Excellent properties and moldability. Further, the adhesive strength is good even in an environment of 60 ° C., and the heat resistance is excellent. Furthermore, an adhesive body with sufficient strength can be obtained even in insert molding, and the insert adhesiveness is excellent. Moreover, even if the molded article of the thermoplastic polymer composition is stored for a long period of time, no bleeding is observed, and the storage stability is excellent. From Examples 4 to 9, by containing the tackifier resin (C), the moldability can be further improved while maintaining good adhesion to the environmental temperature.
- thermoplastic polymer composition of the present invention is excellent in adhesion to insert parts such as aluminum and galvanized steel sheets (Examples 1 and 15). Further, if the insert temperature is kept for a certain time after filling with the thermoplastic polymer composition, the adhesive force can be further improved (Example 17).
- Comparative Example 1 having a small content of the polar group-containing polypropylene resin (B)
- Comparative Example 3 using the polar group-containing polyethylene resin (B′5)
- the thermoplastic elastomer (A) Comparative Example 4 using thermoplastic elastomers (A′5) and (A′6) having a polymer block having a conjugated diene compound unit in which the total amount of 2-bond and 3,4-bond is less than 40 mol% And 5 are all poor in adhesion.
- Comparative Example 2 in which the content of the polar group-containing polypropylene resin (B) exceeds 120 parts by mass, the adhesive strength at room temperature, the heat resistance and the insert adhesiveness are the same as those in Examples, but the flexibility is insufficient.
- 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.
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Abstract
Description
このような問題に対し、スチレン系熱可塑性エラストマー、変性ポリオレフィンおよび軟化剤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8では、ポリアミドを含む極性支持体へのオーバーモールディングが可能で高温下の圧縮永久歪の小さい、特定のスチレン系熱可塑性エラストマーおよび官能化ポリオレフィンを含有する熱可塑性重合体組成物が開示されている。
特許文献8に開示された熱可塑性重合体組成物では、実質的には成形加工性確保のために可塑剤を多量に使用しなければならず、成形品を長期保存した際に可塑剤のブリードが発生して接着特性が低下し、保存安定性が損なわれる。
以上より、特許文献7および8に開示された熱可塑性重合体組成物には、さらなる改良の余地があった。
しかして、本発明の目的は、プライマー処理などを施すことなくセラミックス、金属または合成樹脂と接着することができ、柔軟性、力学特性、成形加工性、耐熱性、保存安定性に優れた熱可塑性重合体組成物およびその成形品を提供すること、さらに、該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と接着してなる成形品をインサート成形によって製造する方法を提供することにある。
〔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-結合および3,4-結合量の合計量が40モル%以上である共役ジエン化合物単位からな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、極性基含有ポリプロピレン系樹脂(B)10~120質量部を含有する熱可塑性重合体組成物(但し、ポリビニルアセタール樹脂を1質量部以上含有する熱可塑性重合体組成物を除く);
〔2〕共役ジエン化合物単位がイソプレン単位である、上記〔1〕の熱可塑性重合体組成物;
〔3〕前記熱可塑性エラストマー(A)100質量部に対して、前記極性基含有ポリプロピレン系樹脂(B)10~100質量部を含有する、上記〔1〕または〔2〕の熱可塑性重合体組成物;
〔4〕前記熱可塑性エラストマー(A)の重量平均分子量(Mw)が70,000~200,000であり、かつ直鎖状のブロック共重合体である、上記〔1〕~〔3〕のいずれかの熱可塑性重合体組成物;
〔5〕さらに粘着付与樹脂(C)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〕~〔4〕のいずれかの熱可塑性重合体組成物;
〔6〕極性基含有ポリプロピレン系樹脂(B)が、カルボン酸変性ポリプロピレン系樹脂である、上記〔1〕~〔5〕のいずれかの熱可塑性重合体組成物;
〔7〕上記〔1〕~〔6〕のいずれかの熱可塑性重合体組成物を用いた成形品;
〔8〕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〔7〕の成形品;
〔9〕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;
〔10〕インサート部品を保持した金型へ上記〔1〕~〔6〕のいずれかの熱可塑性重合体組成物を充填して成形するインサート成形による成形品の製造方法であって、インサート成形時のインサート部品の温度を30~150℃にする、上記〔7〕の成形品の製造方法;
〔11〕インサート部品として、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種を用いる、上記〔7〕の成形品の製造方法;
を提供することにより達成される。
また、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は、60℃以上の環境下に置かれても、実用的に十分な接着性を有し、幅広い用途に使用可能である。さらに、インサート成形によって、該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とより高い接着強度で接着してなる成形品を製造することができ、こうして得られる成形品は、より高い接着強度が求められる用途にも使用可能である。
また、本発明の熱可塑性重合体組成物の成形品は長期保管しても軟化剤などがブリードすることなく、良好な接着性を維持できる。
[熱可塑性重合体組成物]
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-結合および3,4-結合量の合計量が40モル%以上である共役ジエン化合物単位からな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、極性基含有ポリプロピレン系樹脂(B)10~120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、粘着付与樹脂(C)などをさらに含んでいてもよい。以下、本発明の熱可塑性重合体組成物の構成成分について説明する。
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、共役ジエン化合物単位からなる重合体ブロックにおいて1,2-結合および3,4-結合量の合計量を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(B)との相容性が高まり、得られる熱可塑性重合体組成物に、高いインサート接着性と60℃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。なお、本明細書では、インサート成形により得られた成形品における熱可塑性重合体組成物とインサート部品との接着性を「インサート接着性」と称することがある。
-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を含有する重合体ブロックの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。
共役ジエン化合物単位からなる重合体ブロックを構成する化合物は、全ての4から8個の炭素原子の共役ジエンまたはこれらの混合物であってよいが、好ましくはブタジエン、イソプレン、ブタジエンおよびイソプレンの混合物であり、より好ましくはイソプレンである。共役ジエン化合物単位を含有する重合体ブロックは、共役ジエン化合物単位のみを有していてもよいが、本発明の効果を損なわない限り、共役ジエン化合物単位と共に、他の共重合性単量体単位を有していてもよい。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が挙げられる。その割合は、共役ジエン化合物単位からなる重合体ブロックの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。
なお、1,2-結合および3,4-結合量の合計量は、1H-NMR測定によって算出できる。具体的には、1,2-結合および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。
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、共役ジエン化合物単位からな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、直鎖状の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、より好ましくは60,000~200,000、さらに好ましくは70,000~200,000、特に好ましくは70,000~190,000、最も好ましくは80,000~180,000である。重量平均分子量が30,000以上であれば良好な力学特性が得られ、500,000以下であれば良好な成形加工性が得られる。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、共役ジエン化合物、例えばイソプレン、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、共役ジエン化合物、例えばイソプレンを逐次重合させ、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、共役ジエン化合物、例えばイソプレン、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-結合および3,4-結合量の合計量を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-結合および3,4-結合量の合計量を制御できる。
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、水添された熱可塑性エラストマー(A)を単離できる。
本発明の熱可塑性重合体組成物に極性基含有ポリプロピレン系樹脂(B)を含有させることにより、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(B)が有する極性基としては、例えば、(メタ)アクリロイルオキシ基;水酸基;アミド基;塩素原子などのハロゲン原子;カルボキシル基;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(B)の製造方法に特に制限はないが、プロピレンおよび極性基含有共重合性単量体を、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。これらの中でも、ランダム共重合、グラフト共重合が好ましく、グラフト共重合体がより好ましい。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の反応に付することによっても得られる。
極性基含有ポリプロピレン系樹脂(B)は、プロピレンと共に、プロピレン以外のα-オレフィンを極性基含有共重合性単量体と共重合させたものであってもよい。該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。該α-オレフィンは公知の方法で極性基含有共重合性単量体と共重合することができ、例えばランダム共重合、ブロック共重合またはグラフト共重合など方法が挙げられる。これらプロピレン以外のα-オレフィンを由来とする構造単位の、極性基含有ポリプロピレン系樹脂(B)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、マレイン酸、無水マレイン酸がより好ましい。これらの極性基含有共重合性単量体は、1種を単独で用いてもよいし、2種以上を組み合わせてもよい。
極性基含有ポリプロピレン系樹脂(B)としては、接着性の観点から、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、マレイン酸変性ポリプロピレン系樹脂、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。
極性基含有ポリプロピレン系樹脂(B)の融点は、耐熱性の観点から、好ましくは100℃以上、より好ましくは110~170℃、さらに好ましくは120~145℃である。ここで、融点とは、10℃/minで昇温した際の示差走査熱量測定曲線の吸熱ピークから読み取った値である。
これらより、極性基含有ポリプロピレン系樹脂(B)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15~100質量部、より好ましくは15~80質量部、さらに好ましくは20~70質量部である。
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(C)をさらに含有させることができる。粘着付与樹脂(C)を含有させることによって、接着特性を維持しつつ、成形加工性がさらに向上する。
かかる粘着付与樹脂(C)としては、例えば脂肪族不飽和炭化水素樹脂、脂肪族飽和炭化水素樹脂、脂環式不飽和炭化水素樹脂、脂環式飽和炭化水素樹脂、芳香族炭化水素樹脂、水添芳香族炭化水素樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂、テルペンフェノール樹脂、水添テルペンフェノール樹脂、テルペン樹脂、水添テルペン樹脂、芳香族炭化水素変性テルペン樹脂、クマロン・インデン樹脂、フェノール樹脂、キシレン樹脂などが挙げられる。粘着付与樹脂(C)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。これらの中でも、脂肪族飽和炭化水素樹脂、脂環式飽和炭化水素樹脂、水添芳香族炭化水素樹脂、水添テルペン樹脂が好ましく、水添芳香族炭化水素樹脂、水添テルペン樹脂がより好ましい。
(その他の任意成分)
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。
その他、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。
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。
軟化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の成形品の保存安定性が損なわれ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28質量部以下、特に好ましくは10質量部以下である。
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。
無機充填材は、本発明の熱可塑性重合体組成物の耐熱性、耐候性などの物性の改良、硬度調整、増量剤としての経済性の改善などに有用である。かかる無機充填材は特に制限されず、例えば、炭酸カルシウム、タルク、水酸化マグネシウム、水酸化アルミニウム、マイカ、クレー、天然ケイ酸、合成ケイ酸、酸化チタン、カーボンブラック、硫酸バリウム、ガラスバルーン、ガラス繊維などが挙げられる。無機充填材は、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、圧縮成形法、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。
また、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はアルミニウム、マグネシウム合金といった軽金属が用いられており、このようなハウジング材を用いることもできる。
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合成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。
インサート成形法により成形品を製造する方法については後述する。
押出しラミネーション法により成形品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、セラミックスまたは金属からなる被着体の表面、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本発明の熱可塑性重合体組成物を直接押出して成形品を製造することもできる。
圧縮成形法により成形品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、その成形品を、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、圧縮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保護層を設けてもよい。
本発明はまた、本発明の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と接着してなる成形品をインサート成形によって製造する方法を提供する。
ここで「インサート成形」とは、所定の形状をもつ金型内にセラミックス、金属または合成樹脂からなるインサート部品を挿入した後、熱可塑性重合体組成物を充填することで当該熱可塑性重合体組成物からなる成形品を得る方法のことをいい、当該方法により当該インサート部品と当該熱可塑性重合体組成物とが一体化した成形品(以下、インサート部品と熱可塑性重合体組成物とが接着して一体化して得られた成形品を、接着体と称することがある。)を得ることができる。
(インサート部品)
インサート部品を金型内に保持する方法に特に制限は無く、公知の方法を採用することができ、例えばピンなどを使用して固定する方法、真空ラインにより固定する方法が挙げられる。
本発明に用いられるインサート部品としては、ガラス、セラミックス、金属、金属メッキされたもの、合成樹脂からなる群から選択される少なくとも1種が用いられていることが好ましく、セラミックス、金属、金属メッキされたものであることがより好ましい。
インサート成形時に用いる金型に特に制限は無いが、例えば図1~図6に示されるような金型を用いることが好ましい。
図1~図3はそれぞれ可動側金型の正面図、横断面図、縦断面図であり、図4~図6はそれぞれ固定側金型の正面図、横断面図、縦断面図である。
図1において、CAV1とCAV2という2つのキャビティーが示されているが、それぞれ異なる深さに掘られたキャビティーとなっており、流路を切り替えることにより、CAV1とCAV2とを選択できる。また、キャビティー内に設置されたインサート部品(4)を真空ライン(2)で固定できるようになっている。図2および図3は、インサート部品(4)および熱可塑性重合体組成物(5)がキャビティー内に設置された状態を示している。図4は、金型温調用水路(6)を示しており、図1、図5および図6の太い矢印は、シリンダーから熱可塑性重合体組成物が充填される経路を示している。
本発明において、インサート成形時のインサート部品の温度は、好ましくは30~150℃である。インサート部品の温度が当該温度範囲でれば、インサート部品と熱可塑性重合体組成物との間に充分な接着強度が得られる。同様の観点から、インサート部品の温度は、好ましくは50~150℃、より好ましくは80~150℃、さらに好ましくは100~150℃、特に好ましくは115~145℃である。30℃以上であれば、冷却設備を別途設ける必要がなく、また、インサート部品と熱可塑性重合体組成物との間の充分なインサート接着性が得られる。一方、150℃以下であれば、冷却過程における当該熱可塑性樹脂組成物の収縮・変形が小さく、目的の形状を得易いと共に、加熱・冷却に必要なエネルギーが少なく、成形サイクル時間が低減する。
「金型の温度調節機構」とは、金型が有する、金型自体の温度を調節する機能のことであり、「インサート部品の温度を選択的に制御する機構」とは、インサート部品の近くに設けた、インサート部品専用の温度調節機能のことである。
インサート部品の温度を選択的に制御することで、インサート部品の昇温が容易となり、また、接着体の離型も容易になる。インサート部品の温度の選択的な制御には、電気ヒーター、電磁誘導加熱ヒーター、熱媒体、熱板などの発熱体を利用することができる。
電気ヒーターや電磁誘導加熱ヒーターを利用する場合、金型内に埋め込んで利用したり、ヒーターの埋め込まれた加熱板を金型表面に取り付けて利用したりすることができる。熱媒体を利用する場合、金型内に熱媒体流路を設け、所定温度の熱媒体を外部から供給し、外部へ排出する方法が挙げられる。熱媒体としては、特に制限は無いが、油、水、水蒸気、空気、窒素、燃焼ガスなどの流体が挙げられる。
なお、インサート部品に金属が用いられている場合は、直接通電させて加熱してもよいし、誘導コイルによって誘導加熱してもよい。
また、インサート部品の温度を前記範囲に保持する時間に特に制限は無く、生産効率の観点から、好ましくは3分以内、より好ましくは2分以内であるが、接着性の観点からは、好ましくは5秒以上、より好ましくは15秒以上、さらに好ましくは30秒以上である。なお、実質的に保持時間を設けずに、すぐに後述する冷却操作に移行しても充分な接着力が得られる。
より効率よくインサート部品の温度を調節するには、インサート部品の周辺と金型の間に断熱構造を設けることも有効である。
(1)前記熱可塑性重合体組成物を、インサート部品を保持した金型へ充填する前に、インサート部品を所定温度にしておく方法[前加熱法]、
(2)熱可塑性重合体組成物を充填する段階では温度調節を行わず、充填した後に金型内で所定温度に昇温する方法[後加熱法]、
(3)熱可塑性重合体組成物を充填する段階である程度昇温し、充填した後にさらに金型内で所定温度まで昇温する方法、などが挙げられる。これらの中でも、接着性制御の観点から、(1)、(2)の方法が好ましく、インサート部品の温度制御の容易性の観点からは(1)の方法がより好ましく、接着体の外観の観点からは、(2)の方法がより好ましい。
なお、上記(1)の場合、熱可塑性重合体組成物を金型へ充填する作業を開始した直後にインサート部品の温度調節を停止してもよいし、熱可塑性重合体組成物の充填中にインサート部品の温度調節を継続していてもよい。
例えば、電気製品のハウジングに接着した衝撃緩和材、滑り止め、被覆材、防水材、意匠材、自動車ウィンドウのモール、ガスケット、太陽電池モジュールにおけるガラスと金属製枠体との接続部などに好適に使用できる。
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、有機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、上記で得られたポリスチレン-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(以下、熱可塑性エラストマー(A1)と称する)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、ポリイソプレンブロックに含まれる1,2-結合および3,4-結合量の合計量は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、有機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、上記で得られたポリスチレン-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(以下、熱可塑性エラストマー(A2)と称する)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、ポリブタジエンブロックに含まれる1,2-結合量は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、上記で得られたポリスチレン-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(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)0.40Lを仕込み、有機ルイス塩基としてテトラヒドロフラン0.6L(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4.2Lを加えて3時間重合させ、引き続いてイソプレン28Lを加えて4時間重合を行い、さらにスチレン4.2L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-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、上記で得られたポリスチレン-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-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(以下、熱可塑性エラストマー(A4)と称する)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72,800、スチレン含有量は30質量%、水素添加率は90%、分子量分布は1.04、ポリイソプレンブロックに含まれる1,2-結合および3,4-結合量の合計量は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)0.047L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8.1Lおよびブタジエン6.6Lの混合液を加えて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、上記で得られた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(以下、熱可塑性エラストマー(A’5)と称する)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380,000、スチレン含量は30質量%、水添率は97%、分子量分布は1.04、ポリ(イソプレン/ブタジエン)ブロックに含まれる1,2-結合および3,4-結合量の合計量は5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)0.32Lを仕込んだ。50℃に昇温した後、スチレン2.5Lを加えて3時間重合させ、引き続いてイソプレン30Lを加えて4時間重合を行い、さらにスチレン2.5L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、上記で得られたポリスチレンブロック-ポリイソプレンブロック-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(以下、熱可塑性エラストマー(A’6)と称する)を得た。得られた熱可塑性エラストマー(A’6)の重量平均分子量は97,000、スチレン含量は18質量%、水添率は97%、分子量分布は1.04、ポリイソプレンブロックに含まれる1,2-結合および3,4-結合量の合計量は5モル%であった。
ポリプロピレン「プライムポリプロF327」(株式会社プライムポリマー製)42g、無水マレイン酸160mgおよび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(極性基含有ポリプロピレン系樹脂(B1))のMFR[230℃、荷重2.16kg(21.18N)]は6g/10分、無水マレイン酸濃度は0.3%であり、融点は138℃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。また、融点は10℃/minで昇温した際の示差走査熱量測定曲線の吸熱ピークから読み取った値であり、以下同様である。
ポリプロピレン「ノバテックPP FG3DE (日本ポリプロ株式会社製)」42g、無水マレイン酸160mgおよび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(極性基含有ポリプロピレン系樹脂(B2))のMFR[230℃、荷重2.16kg(21.18N)]は10g/10分、無水マレイン酸濃度は0.3%であり、融点は143℃であった。
ポリプロピレン「ノバテックPP F113G(株式会社プライムポリマー製)」42g、無水マレイン酸5gおよび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1.3gを、バッチミキサーを用いて200℃およびスクリュー回転数100rpmの条件下で溶融混練した。得られた混練物(極性基含有ポリプロピレン系樹脂(B3))のMFR[230℃、荷重2.16kg(21.18N)]は250g/10分、無水マレイン酸濃度は3.0%であり、融点は161℃であった。
ポリプロピレン「ノバテックPP E111G(株式会社プライムポリマー製)」42g、無水マレイン酸8.4gおよび2,5-ジメチル-2,5-ジ(ターシャルブチルパーオキシ)ヘキサン126mgを、バッチミキサーを用いて200℃およびスクリュー回転数100rpmの条件下で溶融混練した。得られた混練物(極性基含有ポリプロピレン系樹脂(B4))のMFR[230℃、荷重2.16kg(21.18N)]は80g/10分、無水マレイン酸濃度は6.0%であり、融点は135℃であった。
ポリエチレン「ネオゼックス0434N」(株式会社プライムポリマー製)42g、無水マレイン酸160mgおよび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(極性基含有ポリエチレン系樹脂(B’3))のMFR[190℃、荷重2.16kg(21.18N)]は2g/10分、無水マレイン酸濃度は0.3%であり、融点は117℃であった。
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(C2)〕
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(C3)〕
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(C4)〕
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℃
〔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-380」(出光興産株式会社製)
(1)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。
下記方法で作製した、PET/熱可塑性重合体組成物/ガラス板の積層体、および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、環境温度23℃または60℃の条件で測定し、接着力を測定した。なお、60℃における接着力は耐熱性の指標となる。
(5)ブリード性の測定
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29mmφにカットし、ボール紙でサンドし、1kgの重りを乗せ、70℃で360時間静置した後のボール紙の状態を観察し、ブリードが見られない場合を○、見られる場合を×とした。
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、表1または表2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。
表1または表2に記載の原料を表1または表2に示す割合にて、二軸押出機を用いて230℃、スクリュー回転200rpmの条件で溶融混練した後、ストランド状に押し出し、切断して熱可塑性重合体組成物のペレットを得た。得られたペレットを、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。
なお、実施例1~14および比較例1~5においては、前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MFR、硬度、引張破断強度および引張破断伸度を測定した。また、ガラス板との接着力およびアルミニウム板との接着力を、前記方法に従って測定した。さらに、得られた熱可塑性重合体組成物のブリード性を前記方法に従って測定した。結果を表1に示す。
まず、図1~図6に示す金型を使用し、表1または表2に示す下記被着体(インサート部品)を真空ラインによって金型内に固定した。ヒーターを通電させ、熱伝導によって被着体を表1または表2に示す温度に調節した。金型温度30℃、シリンダー温度230℃の条件にて、表1または表2に示す配合からなる熱可塑性重合体組成物をCAV2へ充填し、充填を開始した直後に、ヒーターの通電を停止し、接着体の表面温度を30℃まで冷却することによって接着体を得た。得られた接着体の23℃におけるインサート接着性(接着力)を表1および表2に示す。
(被着体)
被着体として、長さ100mm×幅35mm×厚さ1mmの下記各インサート部品の両面の表面を、界面活性剤水溶液、蒸留水をこの順に用いて洗浄し、65℃で乾燥させたものを用いた。
インサート部品(a):アルミニウム板(A5052P)
インサート部品(b):電気亜鉛メッキ鋼板(SECC)
また、本発明の熱可塑性重合体組成物は、アルミニウム、亜鉛メッキ鋼板などのインサート部品に対する接着性に優れる(実施例1および15)。また、熱可塑性重合体組成物の充填後にインサート温度を一定時間保持しておくと、接着力をさらに向上できる(実施例17)。
一方、極性基含有ポリプロピレン系樹脂(B)の含有量が少ない比較例1、極性基含有ポリエチレン系樹脂(B’5)を用いた比較例3、熱可塑性エラストマー(A)の代わりに、1,2-結合および3,4-結合量の合計量が40モル%未満の共役ジエン化合物単位を有する重合体ブロックを有する熱可塑性エラストマー(A’5)および(A’6)を用いた比較例4および5は、全て接着力に劣る。極性基含有ポリプロピレン樹脂(B)の含有量が120質量部を上回る比較例2においては、室温での接着力、耐熱性およびインサート接着性ともに実施例と同等だが、柔軟性が不足している。
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-結合および3,4-結合量の合計量が40モル%以上である共役ジエン化合物単位からな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、極性基含有ポリプロピレン系樹脂(B)10~120質量部を含有する熱可塑性重合体組成物(但し、ポリビニルアセタール樹脂を1質量部以上含有する熱可塑性重合体組成物を除く)。
- 共役ジエン化合物単位がイソプレン単位である、請求項1に記載の熱可塑性重合体組成物。
- 前記熱可塑性エラストマー(A)100質量部に対して、前記極性基含有ポリプロピレン系樹脂(B)10~100質量部を含有する、請求項1または2に記載の熱可塑性重合体組成物。
- 前記熱可塑性エラストマー(A)の重量平均分子量(Mw)が70,000~200,000であり、かつ直鎖状のブロック共重合体である、請求項1~3のいずれかに記載の熱可塑性重合体組成物。
- さらに粘着付与樹脂(C)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1~4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(B)が、カルボン酸変性ポリプロピレン系樹脂である、請求項1~5のいずれかに記載の熱可塑性重合体組成物。
- 請求項1~6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7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。
- インサート部品を保持した金型へ請求項1~6のいずれかに記載の熱可塑性重合体組成物を充填して成形するインサート成形による成形品の製造方法であって、インサート成形時のインサート部品の温度を30~150℃にする、請求項7に記載の成形品の製造方法。
- インサート部品として、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種を用いる、請求項7に記載の成形品の製造方法。
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ES12865189.0T ES2626035T3 (es) | 2012-01-11 | 2012-12-14 | Composición de polímero termoplástico y artículo moldeado |
CN201280066704.8A CN104024330B (zh) | 2012-01-11 | 2012-12-14 | 热塑性聚合物组合物及成型品 |
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Also Published As
Publication number | Publication date |
---|---|
EP2803701A1 (en) | 2014-11-19 |
TWI586746B (zh) | 2017-06-11 |
JP5998154B2 (ja) | 2016-09-28 |
TW201741425A (zh) | 2017-12-01 |
KR102127961B1 (ko) | 2020-06-30 |
US10745598B2 (en) | 2020-08-18 |
EP2803701B1 (en) | 2017-02-22 |
US20200109323A1 (en) | 2020-04-09 |
US20140349127A1 (en) | 2014-11-27 |
EP2803701A4 (en) | 2015-07-29 |
EP3168024A1 (en) | 2017-05-17 |
CN104024330B (zh) | 2016-08-03 |
US10767089B2 (en) | 2020-09-08 |
CN104024330A (zh) | 2014-09-03 |
EP3168024B1 (en) | 2019-02-27 |
KR20190022887A (ko) | 2019-03-06 |
TW201339235A (zh) | 2013-10-01 |
ES2626035T3 (es) | 2017-07-21 |
US20170226390A1 (en) | 2017-08-10 |
KR20140109944A (ko) | 2014-09-16 |
TWI628252B (zh) | 2018-07-01 |
ES2725711T3 (es) | 2019-09-26 |
JPWO2013105392A1 (ja) | 2015-05-11 |
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