WO2014077258A1 - プロピレン系重合体及びホットメルト接着剤 - Google Patents
プロピレン系重合体及びホットメルト接着剤 Download PDFInfo
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- WO2014077258A1 WO2014077258A1 PCT/JP2013/080611 JP2013080611W WO2014077258A1 WO 2014077258 A1 WO2014077258 A1 WO 2014077258A1 JP 2013080611 W JP2013080611 W JP 2013080611W WO 2014077258 A1 WO2014077258 A1 WO 2014077258A1
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- hot melt
- melt adhesive
- propylene
- polymer
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- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Definitions
- the present invention relates to a propylene polymer, and more particularly to a propylene polymer that can be used as a modifier of a hot melt adhesive.
- Hot-melt adhesives are solventless adhesives. After being applied to the adherend by heating and melting, it is solidified by cooling and expresses adhesiveness, allowing instant bonding and high-speed bonding. It is used in a wide range of fields. Adhesive materials to be bonded with hot melt adhesives and their use conditions vary, and various hot melt adhesives have been developed and supplied to the market for various applications. Regarding use conditions, various use temperatures from low temperature to high temperature are assumed, and in recent years, hot melt adhesives excellent in heat resistance have been demanded. In consideration of wetness of the base material and application to a base material having a complicated shape, the hot melt adhesive is required to have an appropriate open time.
- the open time refers to the adhesive holding time from when the coating is applied to the adherend until the temperature drops and the adhesiveness is lost, and from the viewpoint of workability, the open time is preferably longer. If the open time is too short, it is difficult to attach the adherend to the substrate. Thus, it is desired to develop a hot melt adhesive suitable for coating, which has a good balance between heat resistance and appropriate open time.
- Patent Document 1 discloses a hot melt adhesive containing an ethylene copolymer as a base polymer and containing a tackifying resin and a wax.
- Patent Document 3 discloses that a specific polymer (functionalized metallocene polymer) is used as a base polymer in order to improve the heat resistance of a hot melt adhesive.
- the hot melt adhesive described in Patent Document 3 does not have sufficient open time and does not sufficiently satisfy the heat resistance required by the user.
- An object of the present invention is to provide a hot melt adhesive having an appropriate open time, and further to provide a hot melt adhesive having a good balance between heat-resistant creep resistance and an appropriate open time.
- the following propylene polymer, hot melt adhesive and bonding method are provided.
- (A1) [mmmm] 60-80 mol%
- (B1) Weight average molecular weight (Mw) 10,000-55,000
- the hot melt adhesive according to any one of the above [3] to [6].
- the hot melt adhesive according to any one of the above.
- a step of melting the hot melt adhesive according to any one of the above [3] to [8] and applying it to at least one substrate, and bonding another substrate to the applied hot melt adhesive A method for bonding a base material to another base material, comprising a step of:
- the propylene polymer described in the above [1] is referred to as “the propylene polymer of the present invention”.
- the hot melt adhesive described in [3] above is referred to as “the hot melt adhesive of the first embodiment of the present invention”, and the hot melt adhesive described in [4] above is referred to as “the second melt of the present invention”.
- the hot-melt adhesive of the embodiment ".
- the hot melt adhesive having the propylene polymer described in [1] as a base polymer is referred to as “the hot melt adhesive according to the third embodiment of the present invention”.
- the hot melt adhesive containing the propylene polymer of the present invention as a modifier has an excellent balance between good heat resistance creep resistance and appropriate open time. Moreover, the hot melt adhesive of the present invention has an appropriate open time, and further has an excellent balance between good heat-resistant creep resistance and an appropriate open time.
- the propylene polymer of the present invention satisfies the following (a1) to (d1). Further, preferably, the following (e1) is satisfied.
- (A1) [mmmm] 60-80 mol%
- Weight average molecular weight (Mw) 10,000-55,000
- (E1) Melting point (Tm ⁇ D) 0 to 140 ° C.
- [mmmm] represents the mesopentad fraction
- [rmrm] represents the racemic mesoracemi mesopentad fraction.
- the propylene polymer of the present invention is a propylene polymer whose main component is a propylene unit, and a propylene homopolymer or a copolymerization ratio of propylene units is 50 mol% or more, preferably 70 mol% or more, more preferably It is a 90 mol% or more copolymer. Moreover, only 1 type of propylene homopolymer may be sufficient, and the mixture of 2 or more types of propylene homopolymers from which molecular weight, stereoregularity, etc. differ may be sufficient.
- Examples of the comonomer other than propylene in the propylene-based copolymer include ethylene and ⁇ -olefins having 4 or more carbon atoms (preferably ⁇ -olefins having 4 to 20 carbon atoms).
- Specific examples of the ⁇ -olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -Octadecene, 1-eicosene and the like. In this invention, 1 type, or 2 or more types can be used among these.
- the mesopentad fraction [mmmm] and the racemic meso-racemic mesopentad fraction [rmrm] are the same as those proposed by A. Zambelli in “Macromolecules, 6, 925 (1973)”.
- the meso fraction and the racemic meso racemic meso fraction in the pentad unit in the polypropylene molecular chain measured by the methyl group signal in the 13 C-NMR spectrum.
- a weight average molecular weight (Mw) and a number average molecular weight (Mn) are things of polystyrene conversion measured with the following apparatus and conditions, and molecular weight distribution (Mw / Mn) is these weight average molecular weights. It is a value calculated from (Mw) and number average molecular weight (Mn).
- ⁇ GPC measurement device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver.1.0)
- the propylene polymer of the present invention has a mesopentad fraction [mmmm] of 60 to 80 mol%. If [mmmm] is 60 mol% or more, it is excellent in cohesion force and heat-resistant creep property. Moreover, if [mmmm] is 80 mol% or less, favorable wettability is shown with respect to a to-be-adhered body. From this point of view, the mesopentad fraction [mmmm] is preferably more than 60 mol% and 80 mol% or less, more preferably more than 60 mol% and 75 mol% or less, still more preferably more than 60 mol% and 72 mol%. It is as follows. It is possible to control the mesopentad fraction by adjusting the monomer concentration and the reaction pressure.
- the propylene polymer of the present invention has a weight average molecular weight of 10,000 to 55,000.
- the weight average molecular weight is 10,000 or more, the cohesive force and heat-resistant creep resistance are strong.
- a weight average molecular weight is 55,000 or less, it is an appropriate viscosity and coatability is good.
- the weight average molecular weight is preferably 10,000 to 51,000, more preferably 15,000 to 40,000, and more preferably 15,000 to 37,000.
- the weight average molecular weight can be controlled by appropriately adjusting the polymerization conditions (propylene pressure, polymerization time, etc.).
- the propylene-based polymer of the present invention has a molecular weight distribution (Mw / Mn) of 2.5 or less.
- Mw / Mn molecular weight distribution
- the molecular weight distribution is preferably 2.4 or less, more preferably 2.2 or less.
- the molecular weight distribution (Mw / Mn) can be 2.5 or less.
- Racemic meso racemic meso fraction [rmrm] The propylene polymer of the present invention has a racemic meso racemic meso fraction [rmrm] of less than 2.5 mol%. When [rmrm] is less than 2.5 mol%, good cohesive force is exhibited. From such a viewpoint, the racemic meso racemic meso fraction [rmrm] is preferably less than 2.4 mol%, more preferably less than 2.2 mol%. [Rmrm] can be controlled by appropriately changing the catalyst using a metallocene catalyst as shown in the present specification.
- the melting point (Tm-D) of the propylene-based polymer of the present invention is preferably 0 to 140 ° C., more preferably 20 to 120 ° C., and still more preferably 90 to 120 ° C. from the viewpoint of improving open time and heat-resistant creep resistance. It is.
- a differential scanning calorimeter DSC-7, manufactured by Perkin Elmer
- 10 mg of a sample is held at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min.
- the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by the above is defined as the melting point (Tm-D). It is possible to control the melting point by adjusting the monomer concentration and the reaction pressure.
- Examples of the method for producing the propylene polymer of the present invention include a method of producing a propylene homopolymer by homopolymerizing propylene using a metallocene catalyst, propylene and ethylene, and / or an ⁇ -olefin having 4 or more carbon atoms. And a method for producing a propylene copolymer by copolymerization of Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables.
- Transition metal compounds having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group as described in JP-A-1-503636 Examples thereof include a catalyst obtained by combining a transition metal compound having a geometrically controlled ligand and a promoter.
- the ligand is preferably composed of a transition metal compound that forms a crosslinked structure via a crosslinking group, and in particular, the crosslinked structure is formed via two crosslinking groups.
- a method using a metallocene catalyst obtained by combining the formed transition metal compound and the cocatalyst is further preferred.
- M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series.
- E 1 and E 2 are substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group, phosphide group, hydrocarbon group and silicon-containing group, respectively.
- a ligand selected from the above, which forms a crosslinked structure via A 1 and A 2 and they may be the same or different from each other.
- X represents a ⁇ -bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E 1 , E 2 or Y.
- Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked with other Y, E 1 , E 2 or X.
- a 1 and A 2 are divalent bridging groups for linking two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium -Containing group, tin-containing group, -O-, -CO-, -S-, -SO 2- , -Se-, -NR 1- , -PR 1- , -P (O) R 1- , -BR 1 — Or —AlR 1 —, wherein R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which are the same or different from each other. Also good. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. ]
- M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. And lanthanoid metals.
- a metal element belonging to Group 4 of the periodic table is preferable, and titanium, zirconium and hafnium are particularly preferable.
- E 1 and E 2 are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N ⁇ ), phosphine group (—P ⁇ ), Hydrocarbon group [>CR-,> C ⁇ ] and silicon-containing group [>SiR-,> Si ⁇ ] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group)
- a ligand selected from among (A) A ligand selected from among (A), and a crosslinked structure is formed via A 1 and A 2 .
- E 1 and E 2 may be the same as or different from each other.
- a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.
- the substituent include a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing group.
- X represents a ⁇ -bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E 1 , E 2 or Y.
- Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include silicon-containing groups having 1 to 20 carbon atoms, phosphide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and acyl groups having 1 to 20 carbon atoms.
- halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
- hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group; vinyl group, propenyl group, cyclohexenyl group, etc.
- An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like.
- alkyl groups such as methyl group, ethyl group, and propyl group
- aryl groups such as phenyl group are preferable.
- alkoxy group having 1 to 20 carbon atoms examples include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group.
- aryloxy group having 6 to 20 carbon atoms examples include phenoxy group, methylphenoxy group, and dimethylphenoxy group.
- amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, methylethylamide group, and other alkylamide groups, divinylamide group, and dipropenylamide group.
- Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
- Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a tri
- Examples of the phosphide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, E
- Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, E
- acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
- Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E 1 , E 2 or X.
- Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
- Examples of the amine include amines having 1 to 20 carbon atoms, and specifically include methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine.
- Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; An arylamine such as naphthylamine can be mentioned.
- ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethy
- phosphines include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tribu
- a 1 and A 2 are divalent bridging groups for linking two ligands, including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and silicon-containing groups.
- R 2 and R 3 are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure.
- E represents an integer of 1 to 4)
- examples thereof include a silylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, and a diphenyldisilylene group.
- an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.
- Q represents an integer of 1 to 5 [(M valence) -2], and r represents an integer of 0 to 3.
- transition metal compound represented by the general formula (I) specific examples described in WO02 / 16450 are also preferable examples in the present invention. More preferable specific examples include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene). (Indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, and the like.
- the component (B-1) in the component (B) is any compound that can react with the transition metal compound of the component (A) to form an ionic complex.
- the transition metal compound of the component (A) can be used, what is represented by the following general formula (III), (IV) can be used conveniently.
- ([L 1 ⁇ R 10 ] k + ) a ([Z] ⁇ ) b (III) ([L 2 ] k + ) a ([Z] ⁇ ) b (IV) (However, L 2 is M 2, R 11 R 12 M 3, R 13 3 C or R 14 M 3.)
- L 1 represents a Lewis base
- [Z] ⁇ represents a non-coordinating anion [Z 1 ] ⁇ and [Z 2 ] ⁇
- [Z 1 ] ⁇ represents an anion having a plurality of groups bonded to the element, that is, [M 1 G 1 G 2 ... G f ] ⁇ .
- M 1 represents a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table.
- G 1 to G f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms , An organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms.
- G 1 to G f may form a ring.
- f represents an integer of [(valence of central metal M 1 ) +1].
- [Z 2 ] ⁇ is a Bronsted acid alone having a logarithm (pKa) of the reciprocal of the acid dissociation constant or a conjugate base of a combination of Bronsted acid and Lewis acid, or an acid generally defined as a super strong acid.
- a Lewis base may be coordinated.
- R 10 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group.
- R 11 and R 12 each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group.
- R 13 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
- R 14 represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine.
- M 2 includes elements in groups 1 to 3, 11 to 13, and 17 of the periodic table, and M 3 represents elements in groups 7 to 12 of the periodic table.
- L 1 examples include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
- R 10 include hydrogen, methyl group, ethyl group, benzyl group, and trityl group.
- R 11 and R 12 include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
- R 13 include a phenyl group, p-tolyl group, p-methoxyphenyl group, and the like.
- R 14 include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like.
- M 2 include Li, Na, K, Ag, Cu, Br, I, I 3 and the like.
- M 3 include Mn, Fe, Co, Ni, Zn. Etc.
- M 1 include B, Al, Si, P, As, Sb, etc., preferably B and Al are Can be mentioned.
- G 1 and G 2 to G f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like.
- Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group,
- the non-coordinating anion i.e. pKa of -10 or less Bronsted acid alone or Bronsted acid and the conjugate base of a combination of a Lewis acid [Z 2] - trifluoromethanesulfonic acid anion (CF 3 SO Specific examples of 3 ) - , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO 4 ) - , trifluoroacetate anion (CF 3 CO 2 ) - , Hexafluoroantimony anion (SbF 6 ) - , fluorosulfonate anion (FSO 3 ) - , chlorosulfonate anion (ClSO 3 ) - , fluorosulfonate anion / 5-antimony fluoride (FSO 3
- an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex that is, the (B-1) component compound
- an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex include triethylammonium tetraphenylborate, tetraphenylboric acid.
- Tri-n-butylammonium trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-
- the general formula (V) (Wherein R 15 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R 15 may be the same or different.
- a chain aluminoxane represented by the general formula (VI) (In the formula, R 15 and w are the same as those in the general formula (V).) The cyclic aluminoxane shown by these can be mentioned.
- Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method.
- a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water (ii) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (iii) a metal
- a method of reacting water adsorbed on a salt or the like with water adsorbed on an inorganic or organic substance with an organoaluminum compound and (iv) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water.
- the aluminoxane may be insoluble in toluene.
- the use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in terms of molar ratio when (B-1) compound is used as (B) catalyst component.
- the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high, which is not practical.
- the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.
- the catalyst component (B) (B-1) and (B-2) may be used alone or in combination of two or more.
- the catalyst for polymerization in the above production method can use an organoaluminum compound as the component (C) in addition to the components (A) and (B).
- the organoaluminum compound of the component (C) the general formula (VII) R 16 v AlJ 3-v (VII) [Wherein R 16 represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer) The compound shown by these is used.
- the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used alone or in combination of two or more.
- a preliminary contact can also be performed using (A) component, (B) component, and (C) component mentioned above.
- the preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but the method is not particularly limited, and a known method can be used.
- These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the (B) component that is the promoter.
- an effect of improving the molecular weight is also seen in addition to the above effect.
- the preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C.
- an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.
- the use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable.
- the catalyst component (C) the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer.
- the catalyst components can be supported on a suitable carrier and used.
- the type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used.
- inorganic oxide carriers or other inorganic carriers are preferable.
- Specific examples of the inorganic oxide carrier include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , Fe 2 O 3 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO 2 and Al 2 O 3 are particularly preferable.
- the inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
- a magnesium compound represented by the general formula MgR 17 X X 1 y typified by MgCl 2 , Mg (OC 2 H 5 ) 2 or the like, or a complex salt thereof can be used.
- R 17 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
- X 1 represents a halogen atom or an alkyl group having 1 to 20 carbon atoms
- x is 0 to 2
- y is 0 to 2
- x + y 2.
- the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, polyarylate, starch, and carbon.
- MgCl 2 , MgCl (OC 2 H 5 ), Mg (OC 2 H 5 ) 2 , SiO 2 , Al 2 O 3 and the like are preferable.
- the properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 ⁇ m, preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m.
- the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
- the specific surface area of the carrier is usually 1 to 1000 m 2 / g, preferably 50 to 500 m 2 / g, and the pore volume is usually 0.1 to 5 cm 3 / g, preferably 0.3 to 3 cm 3 / g. is there. When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease.
- the specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.
- the carrier is an inorganic oxide carrier, it is usually desirable to use it after firing at 150 to 1000 ° C., preferably 200 to 800 ° C.
- At least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component.
- the method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (i) at least one of the components (A) and (B) is mixed with the carrier.
- a method (ii) a method in which the support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent; (iii) the support and (A) A method of reacting the component and / or the component (B) with the organoaluminum compound or the halogen-containing silicon compound, (iv) after the component (A) or the component (B) is supported on the carrier, the component (B) or (A ) A method of mixing with the component, (v) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (vi) a carrier during the contact reaction of the component (A) with the component (B). Coexist Or the like can be used that way.
- an organoaluminum compound (C) can also be added.
- the catalyst when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves.
- the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave.
- an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
- the catalyst thus obtained may be used for polymerization after removing the solvent once and taking out as a solid, or may be used for polymerization as it is.
- a catalyst can be produced
- the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio.
- the use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio.
- the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio.
- the ratio of the component (A) to the carrier used in mass ratio is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500. If the proportion of the component (B) [component (B-1) or component (B-2)] and the carrier, or the proportion of component (A) and the carrier used deviates from the above ranges, the activity may decrease. is there.
- the average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 ⁇ m, preferably 10 to 150 ⁇ m, particularly preferably 20 to 100 ⁇ m, and the specific surface area is usually 20 to 1000 m 2 / g. It is preferably 50 to 500 m 2 / g. If the average particle size is less than 2 ⁇ m, fine powder in the polymer may increase, and if it exceeds 200 ⁇ m, coarse particles in the polymer may increase. When the specific surface area is less than 20 m 2 / g, the activity may decrease, and when it exceeds 1000 m 2 / g, the bulk density of the polymer may decrease.
- the amount of transition metal in 100 g of the support is usually 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of transition metal is outside the above range, the activity may be lowered. In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.
- propylene-based polymer of the present invention using the above-mentioned polymerization catalyst, propylene is homopolymerized to produce a propylene homopolymer, or propylene and ethylene and / or an ⁇ -olefin having 4 or more carbon atoms are produced.
- a propylene copolymer can be produced by copolymerization.
- the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a suspension polymerization method may be used.
- a polymerization method is particularly preferred.
- the solution polymerization method is particularly preferable from the viewpoint of easy control of the reaction.
- the polymerization temperature is usually ⁇ 100 to 250 ° C., preferably ⁇ 50 to 200 ° C., more preferably 0 to 130 ° C.
- the ratio of the catalyst to the reaction raw material is preferably 10 5 to 10 8 , particularly 10 6 to 10 7 , preferably from raw material monomer / component (A) (molar ratio).
- the polymerization time is usually from 5 minutes to 10 hours
- the reaction pressure is preferably from atmospheric pressure to 3 MPa (gauge), more preferably from atmospheric pressure to 2.5 MPa (gauge), more preferably from atmospheric pressure to 2 MPa (gauge). . It is possible to control the mesopentad fraction by adjusting the reaction pressure.
- Examples of the method for adjusting the molecular weight of the polymer include selection of the type, amount used, and polymerization temperature of each catalyst component, and further polymerization in the presence of hydrogen.
- a polymerization solvent for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. A monomer such as ⁇ -olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without solvent.
- aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene
- alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane
- prepolymerization can be performed using the polymerization catalyst.
- the prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used.
- the olefin used in the prepolymerization is not particularly limited, and examples thereof include ethylene, ⁇ -olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used in the polymerization. It is.
- the prepolymerization temperature is usually ⁇ 20 to 200 ° C., preferably ⁇ 10 to 130 ° C., more preferably 0 to 80 ° C.
- an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.
- the intrinsic viscosity [ ⁇ ] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.
- the propylene polymer of the present invention can be applied to the field of adhesives and the like.
- a hot melt adhesive having an excellent balance between good heat-resistant creep resistance and appropriate open time is provided. Can do.
- the hot melt adhesive of the first embodiment of the present invention contains an ethylene polymer (A) and the above-mentioned propylene polymer (B1) of the present invention.
- the propylene of the present invention described above is used with respect to 100 parts by mass of the ethylene-based polymer (A) from the balance between good heat-resistant creep resistance and appropriate open time. 1 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass of the polymer (B1).
- the hot melt adhesive of the first embodiment of the present invention is good. Excellent balance between heat resistance creep resistance and moderate open time.
- the ethylene-based polymer (A) used in the present invention is a base polymer of the hot melt adhesive of the present invention, and specific examples include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. It is done. From the viewpoint of adhesiveness, an ethylene- ⁇ -olefin copolymer is preferable. Specific examples of ⁇ -olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene.
- the ethylene polymer (A) used in the present invention is more preferably an ethylene-1-octene copolymer from the viewpoint of adhesion, and more preferably 63 to 65% by mass of a structural unit derived from ethylene, An ethylene-1-octene copolymer containing 35 to 37% by mass of structural units derived from 1-octene.
- the melting point of the ethylene polymer (A) used in the present invention is preferably 60 to 100 ° C., more preferably 60 to 75 ° C., from the viewpoint of heat resistance creep resistance.
- the melting point of the ethylene polymer (A) can be measured by differential scanning calorimetry.
- Examples of commercially available ethylene polymer (A) used in the present invention include Exact series (manufactured by Exxon Mobil), Affinity polymer series (manufactured by Dow Chemical Co.), and more preferably Affinity GA1950 (Dow). (Made by Chemical)) (all are trade names).
- the hot melt adhesive of the present invention may contain a tackifier resin (C).
- a tackifier resin examples include solids, semisolids, or liquids at room temperature composed of rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, and the like. You may use these individually or in combination of 2 or more types.
- tackifying resins include Imabe P-125, P-100, P-90 (above, manufactured by Idemitsu Kosan Co., Ltd.), Umex 1001 (manufactured by Sanyo Chemical Industries, Ltd.), Hi-Lets T1115 ( Mitsui Chemical Co., Ltd.), Clearon K100 (Yasuhara Chemical Co., Ltd.), ECR227, Escorez 2101 (above, Tonex Co., Ltd.), Alcon P100 (Arakawa Chemical Co., Ltd.), Regalrez 1078 (Hercules) And Eastotac H-130R (manufactured by Eastman Chemical Co., Ltd.).
- the content of the tackifier resin (C) in the hot melt adhesive of the present invention is based on 100 parts by mass of the ethylene polymer (A) from the viewpoint of improving the tackiness and improving the wettability to the adherend due to the decrease in viscosity.
- the amount is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and still more preferably 80 to 120 parts by mass.
- the hot melt adhesive of the present invention may contain a wax (D).
- the wax (D) include animal wax, plant wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, polyethylene oxide wax, polypropylene. Examples thereof include wax, oxidized polypropylene wax, higher fatty acid wax, higher fatty acid ester wax, and Fischer-Tropsch wax.
- the content of the wax (D) in the hot melt adhesive of the present invention is preferably 50 to 100 parts by mass with respect to 100 parts by mass of the ethylene-based polymer (A) from the viewpoint of improving flexibility and improving wettability due to viscosity reduction. It is 200 parts by mass, more preferably 60 to 150 parts by mass, still more preferably 70 to 120 parts by mass. As the amount of wax added increases, the viscosity of the hot melt adhesive decreases.
- the hot melt adhesive of the present invention may contain various additives such as a plasticizer, an inorganic filler, and an antioxidant as necessary.
- a plasticizer include paraffinic process oil, naphthenic process oil, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, and epoxy polymer plasticizers.
- the inorganic filler include clay, talc, calcium carbonate, barium carbonate and the like.
- Antioxidants include trisnoniphenyl phosphite, distearyl pentaerythritol diphosphite, ADEKA STAB 1178 (manufactured by ADEKA), Sumilizer TNP (manufactured by Sumitomo Chemical Co., Ltd.), Irgaphos 168 (manufactured by BASF), Sandstab P -Phosphoric antioxidants such as EPQ (manufactured by Sand), 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ', 5'-di-t-butyl- 4'-hydroxyphenyl) propionate, Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010 (manufactured by BASF), phenolic antioxidants, dilauryl-3,3'-thiodipropionate, pentaerythritol
- the hot melt adhesive of the second embodiment of the present invention contains an ethylene polymer (A) and a propylene polymer (B2) that satisfies the following (a2) and (b2).
- (A2) [mmmm] 20-80 mol%
- Weight average molecular weight (Mw) 1,000-150,000
- the propylene of the present invention described above is used with respect to 100 parts by mass of the ethylene-based polymer (A) from the balance between good heat-resistant creep resistance and appropriate open time. 1 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass of the polymer (B2).
- the propylene polymer (B2) of the present invention is good. Excellent balance between heat resistance creep resistance and moderate open time.
- the hot of the first embodiment of the present invention is used. This is the same as described for the melt adhesive.
- the propylene polymer (B2) used for the hot melt adhesive according to the second embodiment of the present invention satisfies the following (a2) and (b2). Further, preferably, the following (c2) to (e2) are satisfied.
- (A2) [mmmm] 20-80 mol%
- Weight average molecular weight (Mw) 1,000-150,000 (C2) Mw / Mn ⁇ 2.5 (D2) [rmrm] ⁇ 2.5 mol%
- Melting point (Tm ⁇ D) 0 to 140 ° C.
- the propylene polymer (B2) used in the hot melt adhesive according to the second embodiment of the present invention has a mesopentad fraction [mmmm] of 20 to 80 mol%.
- [mmmm] is less than 20 mol%, it is not preferable from the viewpoint of heat resistant creep resistance.
- [mmmm] exceeds 80 mol% it is unpreferable from a viewpoint of open time fall.
- the mesopentad fraction [mmmm] is preferably 20 to 70 mol%, more preferably 47 to 70 mol%, still more preferably 48 to 60 mol%.
- the mesopentad fraction [mmmm] is preferably more than 60 mol% and 80 mol% or less, more preferably more than 60 mol% and 75 mol from the viewpoint of a balance between good heat-resistant creep resistance and appropriate open time. % Or less, more preferably more than 60 mol% and 72 mol% or less.
- the propylene polymer (B2) used for the hot melt adhesive according to the second embodiment of the present invention has a weight average molecular weight of 1,000 to 150,000. If the weight average molecular weight is less than 1,000, it is not preferable from the viewpoints of heat resistance creep resistance and cohesive strength reduction. Moreover, when a weight average molecular weight exceeds 150,000, it is unpreferable from a viewpoint of the coating property fall by a melt viscosity raise.
- the weight average molecular weight is preferably 10,000 to 100,000, more preferably 15,000 to 80,000 from the viewpoint of open time and the balance between good heat-resistant creep resistance and appropriate open time.
- the propylene polymer (B2) used for the hot melt adhesive according to the second embodiment of the present invention has a molecular weight distribution (Mw / Mn) of 2.5 or less. If the molecular weight distribution is 2.5 or less, good coatability is exhibited. From such a viewpoint, the molecular weight distribution is preferably 2.4 or less, more preferably 2.2 or less.
- the propylene polymer (B2) used in the hot melt adhesive according to the second embodiment of the present invention has a racemic meso racemic meso fraction [rmrm] of 2.5 mol% or more. If [rmrm] is 2.5 mol% or more, it is preferable from the viewpoint of improving the open time. From such a viewpoint, the racemic meso racemic meso fraction [rmrm] is preferably 2.6 to 5.0 mol%, more preferably 2.7 to 5.0 mol%.
- the melting point (Tm-D) of the propylene-based polymer (B2) used for the hot melt adhesive of the second embodiment of the present invention is preferably 0 to 140 ° C. from the viewpoint of improving open time and heat-resistant creep resistance. More preferably, the temperature is 20 to 120 ° C, and still more preferably 40 to 100 ° C.
- the kind of monomer in a propylene polymer (B2) is the same as that of the monomer in the propylene polymer of this invention.
- the method for measuring the mesopentad fraction [mmmm], the racemic meso-racemic mesopentad fraction [rmrm], the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn) and the melting point (Tm-D) is as follows. This is the same as described above for the propylene-based polymer.
- the crystallinity of the polyolefin obtained can be controlled, and a propylene polymer (B2) can be obtained.
- the metallocene catalyst that can be used for the production of the propylene polymer (B2) include those described in JP-A No. 2000-256411.
- the hot melt adhesive of the third embodiment of the present invention contains the propylene polymer (B1) of the present invention as a base polymer.
- the propylene polymer (B1) of the present invention is preferably contained in an amount of 55% by mass or more, more preferably 60% by mass or more, and further preferably 65% by mass or more.
- the hot melt adhesive according to the third embodiment of the present invention is a packaging adhesive with a small coating amount when used because the propylene polymer (B1) of the present invention contained as a base polymer is relatively hard. However, it is suitable as an adhesive for woodworking with a large amount of coating when used.
- the hot melt adhesive according to the third embodiment of the present invention has a good heat-resistant creep property, and further has an excellent balance between the good heat-resistant creep property and an appropriate open time.
- the hot melt adhesive of the first or second embodiment of the present invention comprises an ethylene polymer (A), a propylene polymer (B1) or (B2), and a tackifying resin (C) as necessary.
- the wax (D) and various additives can be dry blended using a Henschel mixer or the like and melt-kneaded with a single-screw or twin-screw extruder, a plast mill, a Banbury mixer, or the like.
- the hot melt adhesive according to the third embodiment of the present invention includes a propylene polymer (B1) as a base polymer, and an ethylene polymer (A), a tackifier resin (C), and a wax as necessary.
- the hot melt adhesive of the present invention can be suitably used as an adhesive for packaging such as cardboard and an adhesive for woodworking.
- adhesives include reactive adhesives such as epoxy resins and acrylic resins, and solvent-based adhesives such as vinyl acetate and rubber.
- Adhesives water-based adhesives such as vinyl acetate emulsion, EVA emulsion, synthetic rubber latex, hot melt adhesives, phenolic adhesives, silicone adhesives, and adhesives.
- the material obtained by the present invention is excellent in applicability to hot melt adhesives and can be used for controlling the solidification rate and melt viscosity. Further, it is possible to obtain improved handling properties by preventing oil bleeding and suppressing stickiness.
- the addition of a base polymer having a low tensile elastic modulus can extend the open time, and the addition of a base polymer having a high tensile elastic modulus can reduce the set time.
- the melt viscosity is useful as an index for checking whether or not a hot melt adhesive can be sprayed from a nozzle. If the melt viscosity becomes too high, stringing occurs, which is not preferable for practical use. In the case of a hot melt adhesive for woodworking, since it is applied without using a nozzle, there is no practical problem even if the melt viscosity is high.
- the bonding method of the present invention is a method of bonding a substrate to another substrate, the step of melting the hot melt adhesive of the present invention and applying it to at least one substrate, and the applied hot melt adhesive A step of adhering another substrate to the substrate.
- Production Example 1 (Production of polypropylene 1) A stainless steel reactor with a stirrer and an internal volume of 0.2 m 3 , n-heptane at 25 L / h, triisobutylaluminum at 25 mmol / h, dimethylanilinium tetrakispentafluorophenylborate, complex A and triisobutylaluminum
- the catalyst component obtained by previously contacting propylene with propylene was continuously fed at 1.2 ⁇ mol / h per zirconium.
- Propylene and hydrogen were continuously supplied at a polymerization temperature of 65 ° C. so that the gas phase hydrogen concentration was 2.5 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
- Production Example 2 (Production of polypropylene 2) A stainless steel reactor with a stirrer and an internal volume of 0.2 m 3 , n-heptane at 25 L / h, triisobutylaluminum at 25 mmol / h, dimethylanilinium tetrakispentafluorophenylborate, complex A and triisobutylaluminum
- the catalyst component obtained by previously contacting propylene with propylene was continuously supplied at 1.8 ⁇ mol / h per zirconium.
- Propylene and hydrogen were continuously supplied at a polymerization temperature of 65 ° C. so that the gas phase hydrogen concentration was 1.5 mol% and the total pressure in the reactor was maintained at 1.0 MPa ⁇ G.
- Production Example 3 Manufacture of polypropylene 3
- the catalyst component obtained by previously contacting triisobutylaluminum and propylene was continuously fed at 0.7 mmol / h per zirconium.
- Propylene and hydrogen were continuously supplied at a polymerization temperature of 85 ° C. so that the gas phase hydrogen concentration was 5.0 mol% and the total pressure in the reactor was maintained at 1.7 MPa ⁇ G.
- Production Example 4 (Production of polypropylene 4) A stainless steel reactor with a stirrer and an internal volume of 0.2 m 3 , n-heptane at 25 L / h, triisobutylaluminum at 25 mmol / h, dimethylanilinium tetrakispentafluorophenylborate, complex C and triisobutylaluminum
- the catalyst component obtained by previously contacting propylene with propylene was continuously fed at 1.2 ⁇ mol / h per zirconium.
- Propylene and hydrogen were continuously supplied at a polymerization temperature of 70 ° C. so that the gas phase hydrogen concentration was 0.66 mol% and the total pressure in the reactor was kept at 0.66 MPa ⁇ G.
- Production Example 5 Production of polypropylene 5) Propylene and hydrogen were continuously fed at a polymerization temperature of 60 ° C. to maintain a gas phase hydrogen concentration of 3.5 mol% and the total pressure in the reactor at 0.7 MPa ⁇ G. A homopolymer (polypropylene 5) was obtained.
- Production Example 6 (Production of polypropylene 6) In the same manner as in Production Example 4 except that propylene and hydrogen were continuously fed so as to keep the gas phase hydrogen concentration at 0.66 mol% at a polymerization temperature of 60 ° C. and the total pressure in the reactor at 0.66 MPa ⁇ G. A homopolymer (polypropylene 6) was obtained.
- the mesopentad fraction [mmmm] and the racemic mesoracemi mesopentad fraction [rmrm] are determined according to the method proposed by A. Zambelli et al. In “Macromolecules, 6, 925 (1973)”.
- the meso fraction and the racemic meso racemic meso fraction in pentad units in the polypropylene molecular chain measured by the methyl group signal in the 13 C-NMR spectrum.
- the mesopentad fraction [mmmm] increases, the stereoregularity increases.
- Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement For the polypropylenes 1 to 6 obtained in Production Examples 1 to 6, the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained. The results are shown in Table 1.
- ⁇ GPC measurement device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 ⁇ l Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver.1.0)
- the open time refers to the adhesion holding time from when the coating is applied to the adherend until the temperature is lowered and the adhesiveness is lost.
- a hot melt adhesive heated to 180 ° C. and melted is applied to a K liner cardboard at a coating amount of 2.8 to 3.2 g / m, and after a predetermined time, an adhesive pressure of 2 kg / 25 cm 2 and a set time of 2 seconds. Bonded under the conditions of The adhesion test piece was left to stand in an environment of 23 ° C. and 50% humidity for 24 hours and peeled off by hand. Of the five measurements, the longest elapsed time in which four or more test pieces having a material destruction rate of 80% or more were taken as the open time (seconds).
- Open time evaluation The obtained open time value was evaluated according to the following criteria.
- the set time means the time until the hot melt adhesive bonded to the adherend is cooled and solidified to show the initial adhesive force.
- a hot melt adhesive heated to 180 ° C. and melted is applied to a K liner cardboard at a coating amount of 2.8 to 3.2 g / m, and after taking an open time of 2 seconds, an adhesive pressure of 2 kg / 25 cm 2 I stuck together.
- the adhesive test piece is peeled off after a predetermined pressing time has passed in an environment of 23 ° C. and humidity of 50%, and the shortest pressing in which the number of test pieces having a material destruction rate of 80% or more becomes four or more is measured five times.
- the elapsed time was set as the set time (seconds).
- Constant temperature creep is an index indicating the heat resistant creep property of the adhesive, and the longer the peeling time, the heat resistant creep property, and it is more difficult to peel off during transportation.
- a hot melt adhesive heated to 180 ° C. and melted is applied to a K liner cardboard at a coating amount of 2.8 to 3.2 g / m, and after taking an open time of 2 seconds, an adhesive pressure of 2 kg / 25 cm 2 Bonding was performed under the condition of a set time of 2 seconds.
- the adhesion test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity.
- a load of 200 g / g / 25 cm 2 was applied in the stress direction to the prepared test piece in an environment of 60 ° C. and 30% humidity, and the time until the bonded sample was peeled was measured. The measurement was made 5 times, and the average value of 3 points excluding the longest and shortest peeling time was taken as the value of the constant temperature creep test.
- the obtained constant temperature creep value was evaluated according to the following criteria. AA (6 points): constant temperature creep value is longer than 100 minutes. A (5 points): Constant creep value is 80 minutes or more and 100 minutes or less. B (4 points): Constant creep value is 70 minutes or more and less than 80 minutes. C (3 points): Constant creep value is 60 minutes or more and less than 70 minutes. D (2 points): Constant creep value is 50 minutes or more and less than 60 minutes. E (1 point): Constant creep value is less than 50 minutes.
- ⁇ Melt viscosity> The hot melt adhesive was melted at 180 ° C., and the viscosity was measured with a M2 rotor using a TVB-15 Brookfield viscometer. When the melt viscosity is high, stringing increases, but when the melt viscosity at 180 ° C. is 1,500 mPa ⁇ s or less, there is little stringing and excellent coatability.
- the hot melt adhesives of Examples 1 to 14 using the propylene-based polymer of the present invention have an excellent balance between heat resistance creep resistance and appropriate open time.
- Examples 1, 3, 4, and 8 to 14 are particularly preferable because both the open time and the heat resistant creep resistance are improved.
- Examples 2 and 5 to 7 compared with Comparative Example 1 in which no propylene-based polymer is used, one of open time and heat-resistant creep resistance is equivalent and the other is improved.
- the hot melt adhesives of the second embodiment of the present invention of Reference Examples 1 to 5 have a long open time while having appropriate heat-resistant creep resistance.
- Open time> A hot melt adhesive heated to 170 ° C. and melted was applied to a paper surface (general paper: 65 g / m 2 ) so as to have a thickness of 200 ⁇ m. Thereafter, the paper piece coated with the hot melt adhesive was adhered to the wood at regular intervals at room temperature, and a 5 kg weight was placed on the wood for 5 minutes to cool.
- the open time (seconds) was defined as the longest elapsed time that could be peeled off by hand after 30 minutes and peeled off from the adhesive surface without tearing paper or wood fibers.
- ⁇ Constant temperature creep> A hot melt adhesive heated to 170 ° C. and melted was applied to the paper surface (Kent paper: 210 g / m 2 ) so as to have a thickness of 200 ⁇ m. Thereafter, the piece of paper to which the hot melt adhesive was applied was adhered to the wood at room temperature, and a 5 kg weight was placed for 5 minutes to cool. The weight was removed, and the adhesion test piece was allowed to stand for 24 hours in an environment of 23 ° C. and 50% humidity. The prepared specimen was subjected to a load of 200 g in the stress direction in an environment of 70 ° C. or 90 ° C. and a relative humidity of 30%, and the time until the bonded sample was peeled was measured. Three measurements were taken, and the average value was taken as the value of the constant temperature creep test.
- the hot melt adhesive of the third embodiment of the present invention since the propylene-based polymer (B1) of the present invention contained as a base polymer is relatively hard, the coating amount during use Although it is not suitable as an adhesive for packaging with a small amount, it is suitable as an adhesive for woodworking with a large amount of coating at the time of use. In particular, since the adhesive for woodworking used in kitchens and the like requires durability at higher temperatures, the hot melt adhesives of Examples 15 and 16 that are excellent in constant temperature creep at 90 ° C. are useful as adhesives for woodworking. It is.
- Comparative Example 5 which uses the ethylene copolymer (A) as a base polymer and does not contain the propylene polymer of the present invention, the ethylene copolymer (A) itself is a material having adhesiveness. Time is a very good result. However, it is inferior in heat-resistant creep resistance, and particularly inferior in constant temperature creep at 90 ° C. As the temperature increases, the fluidity of the low molecular weight component increases and oozes out, making it impossible to maintain adhesion. In Comparative Example 6 using a propylene-based copolymer (BZ) whose molecular weight distribution is outside the scope of the present invention as a base polymer, the open time is slow.
- BZ propylene-based copolymer
- Comparative Examples 7 and 8 in which a wax is added to adjust the viscosity the open time is fast, but the adhesiveness is low, so the heat-resistant creep resistance is poor.
- the constant temperature creep at 70 ° C. is good, but the constant temperature creep at 90 ° C. is inferior.
- Reference Example 7 in which a wax is added to adjust the viscosity the open time is fast, but the adhesiveness is low, so that the heat resistance creep resistance is poor.
- the propylene polymer of the present invention can be suitably used in the field of hot melt adhesives.
- the hot melt adhesive of the present invention is an adhesive for packaging such as corrugated cardboard, sanitary goods, woodworking, bookbinding, textiles, electrical materials, cans, buildings and bags. It can be suitably used as an adhesive.
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Abstract
Description
このように、耐熱性と適度なオープンタイムとのバランスのとれた、塗工に好適なホットメルト接着剤の開発が望まれている。
また、特許文献2には、エチレン系共重合体をベースポリマーとし、これに粘着付与樹脂及びワックスを含有するホットメルト接着剤が開示されている。このものは低温において高い接着力を有するものの、オープンタイムが十分でなく、接着剤としての耐熱性、特に耐熱クリープ特性が悪い。
特許文献3には、ホットメルト接着剤の耐熱性を向上させるために、特定のポリマー(官能化メタロセン重合体)をベースポリマーとして使用することが開示されている。しかし、特許文献3に記載のホットメルト接着剤は、オープンタイムが十分でなく、ユーザーが要求する耐熱性を十分に満足するものではなかった。
[1]下記(a1)~(d1)を満たすプロピレン系重合体。
(a1)[mmmm]=60~80モル%
(b1)重量平均分子量(Mw)=10,000~55,000
(c1)Mw/Mn≦2.5
(d1)[rmrm]<2.5モル%
[2]下記(b1’)を満たす、上記[1]に記載のプロピレン系重合体。
(b1’)重量平均分子量(Mw)=10,000~51,000
[3]エチレン系重合体(A)100質量部に対して、上記[1]又は[2]に記載のプロピレン系重合体(B1)1~30質量部を含むホットメルト接着剤。
[4]エチレン系重合体(A)100質量部に対して、下記(a2)及び(b2)を満たすプロピレン系重合体(B2)1~30質量部を含むホットメルト接着剤。
(a2)[mmmm]=20~80モル%
(b2)重量平均分子量(Mw)=1,000~150,000
[5]前記エチレン系重合体(A)がエチレン-α-オレフィン共重合体である、上記[3]又は[4]に記載のホットメルト接着剤。
[6]前記エチレン系重合体(A)がエチレン-1-オクテン共重合体である、上記[3]~[5]のいずれかに記載のホットメルト接着剤。
[7]前記エチレン系重合体(A)が、エチレンから導かれる構成単位を63~65質量%、1-オクテンから導かれる構成単位を35~37質量%含有するエチレン-1-オクテン共重合体である、上記[3]~[6]のいずれかに記載のホットメルト接着剤。
[8]エチレン系重合体(A)100質量部に対して、粘着付与樹脂(C)50~200質量部及びワックス(D)50~200質量部を更に含む、上記[3]~[7]のいずれかに記載のホットメルト接着剤。
[9]上記[3]~[8]のいずれかに記載のホットメルト接着剤を溶融し、少なくとも1つの基材に塗布する工程、及び塗布されたホットメルト接着剤に他の基材を接着する工程を含む、基材と他の基材との接着方法。
以下、上記[1]に記載のプロピレン系重合体を「本発明のプロピレン系重合体」という。また、上記[3]に記載のホットメルト接着剤を「本発明の第1の実施態様のホットメルト接着剤」といい、上記[4]に記載のホットメルト接着剤を「本発明の第2の実施態様のホットメルト接着剤」という。また、上記[1]に記載のプロピレン系重合体をベースポリマーとするホットメルト接着剤を「本発明の第3の実施態様のホットメルト接着剤」という。
本発明のプロピレン系重合体は、下記(a1)~(d1)を満たす。また、好ましくは更に下記(e1)を満たす。
(a1)[mmmm]=60~80モル%
(b1)重量平均分子量(Mw)=10,000~55,000
(c1)Mw/Mn≦2.5
(d1)[rmrm]<2.5モル%
(e1)融点(Tm-D)=0~140℃
上記において、[mmmm]はメソペンタッド分率、[rmrm]はラセミメソラセミメソペンタッド分率を表す。
プロピレン系共重合体におけるプロピレン以外のコモノマーとしては、エチレン及び炭素数4以上のα-オレフィン(好ましくは炭素数4~20のα-オレフィン)が挙げられる。α-オレフィンの具体例としては、1-ブテン,1-ペンテン,4-メチル-1-ペンテン,1-ヘキセン,1-オクテン,1-デセン,1-ドデセン,1-テトラデセン,1-ヘキサデセン,1-オクタデセン,1-エイコセン等が挙げられる。本発明においては、これらのうち一種又は二種以上を用いることができる。
装置:日本電子(株)製、JNM-EX400型13C-NMR装置
方法:プロトン完全デカップリング法
濃度:220mg/ml
溶媒:1,2,4-トリクロロベンゼンと重ベンゼンの90:10(容量比)混合溶媒
温度:130℃
パルス幅:45°
パルス繰り返し時間:4秒
積算:10,000回
M=m/S×100
R=γ/S×100
S=Pββ+Pαβ+Pαγ
S:全プロピレン単位の側鎖メチル炭素原子のシグナル強度
Pββ:19.8~22.5ppm
Pαβ:18.0~17.5ppm
Pαγ:17.5~17.1ppm
γ:ラセミペンタッド連鎖:20.7~20.3ppm
m:メソペンタッド連鎖:21.7~22.5ppm
<GPC測定装置>
カラム :TOSO GMHHR-H(S)HT
検出器 :液体クロマトグラム用RI検出器 WATERS 150C
<測定条件>
溶媒 :1,2,4-トリクロロベンゼン
測定温度 :145℃
流速 :1.0ミリリットル/分
試料濃度 :2.2mg/ミリリットル
注入量 :160マイクロリットル
検量線 :Universal Calibration
解析プログラム:HT-GPC(Ver.1.0)
本発明のプロピレン系重合体は、メソペンタッド分率[mmmm]が60~80モル%である。[mmmm]が60モル%以上であれば、凝集力及び耐熱クリープ性に優れる。また、[mmmm]が80モル%以下であれば、被着体に対して良好な濡れ性を示す。このような観点から、メソペンタッド分率[mmmm]は、好ましくは60モル%を超え80モル%以下、より好ましくは60モル%を超え75モル%以下、更に好ましくは60モル%を超え72モル%以下である。モノマー濃度や反応圧力を調整することで、メソペンタッド分率を制御することが可能である。
本発明のプロピレン系重合体は、重量平均分子量が10,000~55,000である。重量平均分子量が10,000以上であれば、凝集力、耐熱クリープ性が強い。また、重量平均分子量が55,000以下であれば、適切な粘度で、塗工性が良い。このような観点から、重量平均分子量は、好ましくは10,000~51,000、より好ましくは15,000~40,000、より好ましくは15,000~37,000である。重量平均分子量は、重合条件(プロピレン圧、重合時間等)を適宜調整することで制御可能である。
本発明のプロピレン系重合体は、分子量分布(Mw/Mn)が2.5以下である。分子量分布が2.5以下であれば、塗工性に優れる。このような観点から、分子量分布は、好ましくは2.4以下、より好ましくは2.2以下である。メタロセン系触媒を用いることにより、分子量分布(Mw/Mn)を2.5以下とすることができる。
本発明のプロピレン系重合体は、ラセミメソラセミメソ分率[rmrm]が2.5モル%未満である。[rmrm]が2.5モル%未満であれば、良好な凝集力を示す。このような観点から、ラセミメソラセミメソ分率[rmrm]は、好ましくは2.4モル%未満、より好ましくは2.2モル%未満である。本明細書に示すようなメタロセン触媒を用いて触媒を適宜変更することにより、[rmrm]を制御させることができる。
本発明のプロピレン系重合体の融点(Tm-D)は、オープンタイム向上及び耐熱クリープ性向上の観点から、好ましくは0~140℃、より好ましくは20~120℃、更に好ましくは90~120℃である。
なお、本発明では、示差走査型熱量計(パーキン・エルマー社製、DSC-7)を用い、試料10mgを窒素雰囲気下-10℃で5分間保持した後、10℃/分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップを融点(Tm-D)とする。モノマー濃度や反応圧力を調整することで、融点を制御することが可能である。
本発明のプロピレン系重合体の製造方法としては、メタロセン触媒を用いて、プロピレンを単独重合してプロピレン単独重合体を製造する方法や、プロピレンとエチレン及び/又は炭素数4以上のα-オレフィンとを共重合してプロピレン共重合体を製造する方法が挙げられる。
メタロセン系触媒としては、特開昭58-19309号公報、特開昭61-130314号公報、特開平3-163088号公報、特開平4-300887号公報、特開平4-211694号公報、特表平1-502036号公報等に記載されるようなシクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基等を1又は2個配位子とする遷移金属化合物、及び該配位子が幾何学的に制御された遷移金属化合物と助触媒を組み合わせて得られる触媒が挙げられる。
具体的に例示すれば、(A)一般式(I)で表される遷移金属化合物、及び(B)(B-1)該(A)成分の遷移金属化合物又はその派生物と反応してイオン性の錯体を形成しうる化合物及び(B-2)アルミノキサンから選ばれる成分を含有する重合用触媒の存在下、プロピレンを単独重合させる方法又はプロピレンとエチレン及び/又は炭素数4以上のα-オレフィンとを共重合させる方法が挙げられる。
炭素数1~20のケイ素含有基としては、メチルシリル基、フェニルシリル基等のモノ炭化水素置換シリル基;ジメチルシリル基、ジフェニルシリル基等のジ炭化水素置換シリル基;トリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、トリシクロヘキシルシリル基、トリフェニルシリル基、ジメチルフェニルシリル基、メチルジフェニルシリル基、トリトリルシリル基、トリナフチルシリル基等のトリ炭化水素置換シリル基;トリメチルシリルエーテル基等の炭化水素置換シリルエーテル基;トリメチルシリルメチル基等のケイ素置換アルキル基;トリメチルシリルフェニル基等のケイ素置換アリール基等が挙げられる。なかでもトリメチルシリルメチル基、フェニルジメチルシリルエチル基等が好ましい。
炭素数1~20のアシル基としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、バレリル基、パルミトイル基、テアロイル基、オレオイル基等のアルキルアシル基、ベンゾイル基、トルオイル基、サリチロイル基、シンナモイル基、ナフトイル基、フタロイル基等のアリールアシル基、シュウ酸、マロン酸、コハク酸等のジカルボン酸からそれぞれ誘導されるオキサリル基、マロニル基、スクシニル基等が挙げられる。
アミンとしては、炭素数1~20のアミンが挙げられ、具体的には、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、シクロヘキシルアミン、メチルエチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジシクロヘキシルアミン、メチルエチルアミン等のアルキルアミン;ビニルアミン、プロペニルアミン、シクロヘキセニルアミン、ジビニルアミン、ジプロペニルアミン、ジシクロヘキセニルアミン等のアルケニルアミン;フェニルアミン、フェニルエチルアミン、フェニルプロピルアミン等のアリールアルキルアミン;ジフェニルアミン、ジナフチルアミン等のアリールアミンが挙げられる。
より好ましい具体例としては、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)ビス(インデニル)ジルコニウムジクロライド、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)(インデニル)(3-トリメチルシリルメチルインデニル)ジルコニウムジクロライド、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)ビス(3-トリメチルシリルメチルインデニル)ジルコニウムジクロライド等が挙げられる。
(〔L1-R10〕k+)a (〔Z〕-)b ・・・(III)
(〔L2〕k+)a(〔Z〕-)b ・・・(IV)
(ただし、L2はM2、R11R12M3、R13 3C又はR14M3である。)
〔Z1〕-は複数の基が元素に結合したアニオンすなわち〔M1G1G2・・・Gf〕-を示す。ここで、M1は周期律表第5~15族元素、好ましくは周期律表第13~15族元素を示す。G1~Gfはそれぞれ水素原子,ハロゲン原子,炭素数1~20のアルキル基,炭素数2~40のジアルキルアミノ基,炭素数1~20のアルコキシ基,炭素数6~20のアリール基,炭素数6~20のアリールオキシ基,炭素数7~40のアルキルアリール基,炭素数7~40のアリールアルキル基,炭素数1~20のハロゲン置換炭化水素基,炭素数1~20のアシルオキシ基,有機メタロイド基、又は炭素数2~20のヘテロ原子含有炭化水素基を示す。G1~Gfのうち2つ以上が環を形成していてもよい。fは〔(中心金属M1の原子価)+1〕の整数を示す。
〔Z2〕-は、酸解離定数の逆数の対数(pKa)が-10以下のブレンステッド酸単独又はブレンステッド酸及びルイス酸の組合せの共役塩基、あるいは一般的に超強酸と定義される酸の共役塩基を示す。また、ルイス塩基が配位していてもよい。
また、R10は水素原子,炭素数1~20のアルキル基,炭素数6~20のアリール基,アルキルアリール基又はアリールアルキル基を示す。
R11及びR12はそれぞれシクロペンタジエニル基,置換シクロペンタジエニル基,インデニル基又はフルオレニル基を示す。
R13は炭素数1~20のアルキル基,アリール基,アルキルアリール基又はアリールアルキル基を示す。
R14はテトラフェニルポルフィリン,フタロシアニン等の大環状配位子を示す。kは〔L1-R10〕,〔L2〕のイオン価数で1~3の整数、aは1以上の整数、b=(k×a)である。M2は、周期律表第1~3、11~13、17族元素を含むものであり、M3は、周期律表第7~12族元素を示す。
(B-1)は一種用いてもよく、また二種以上を組み合わせて用いてもよい。
で示される鎖状アルミノキサン、及び一般式(VI)
で示される環状アルミノキサンを挙げることができる。
これらのアルミノキサンは一種用いてもよく、二種以上を組み合わせて用いてもよい。
ここで、(C)成分の有機アルミニウム化合物としては、一般式(VII)
R16 v AlJ3-v ・・・(VII)
〔式中、R16は炭素数1~10のアルキル基、Jは水素原子、炭素数1~20のアルコキシ基、炭素数6~20のアリール基又はハロゲン原子を示し、vは1~3の整数である〕
で示される化合物が用いられる。
前記一般式(VII)で示される化合物の具体例としては、トリメチルアルミニウム,トリエチルアルミニウム,トリイソプロピルアルミニウム,トリイソブチルアルミニウム,ジメチルアルミニウムクロリド,ジエチルアルミニウムクロリド,メチルアルミニウムジクロリド,エチルアルミニウムジクロリド,ジメチルアルミニウムフルオリド,ジイソブチルアルミニウムヒドリド,ジエチルアルミニウムヒドリド,エチルアルミニウムセスキクロリド等が挙げられる。
これらの有機アルミニウム化合物は一種用いてもよく、二種以上を組合せて用いてもよい。
前記(A)触媒成分と(C)触媒成分との使用割合は、モル比で好ましくは1:1~1:10000、より好ましくは1:5~1:2000、さらに好ましくは1:10ないし1:1000の範囲が望ましい。該(C)触媒成分を用いることにより、遷移金属当たりの重合活性を向上させることができるが、あまり多いと有機アルミニウム化合物が無駄になるとともに、重合体中に多量に残存し、好ましくない。
無機酸化物担体としては、具体的には、SiO2,Al2O3,MgO,ZrO2,TiO2,Fe2O3,B2O3,CaO,ZnO,BaO,ThO2やこれらの混合物、例えばシリカアルミナ,ゼオライト,フェライト,グラスファイバーなどが挙げられる。これらの中では、特にSiO2,Al2O3が好ましい。なお、上記無機酸化物担体は、少量の炭酸塩,硝酸塩,硫酸塩などを含有してもよい。
一方、上記以外の担体として、MgCl2,Mg(OC2H5)2などで代表される一般式MgR17 XX1 yで表されるマグネシウム化合物やその錯塩などを挙げることができる。ここで、R17は炭素数1~20のアルキル基、炭素数1~20のアルコキシ基又は炭素数6~20のアリール基、X1はハロゲン原子又は炭素数1~20のアルキル基を示し、xは0~2、yは0~2であり、かつx+y=2である。各R17及び各X1はそれぞれ同一でもよく、また異なってもいてもよい。
また、有機担体としては、ポリスチレン,スチレン-ジビニルベンゼン共重合体,ポリエチレン,ポリ1-ブテン,置換ポリスチレン,ポリアリレートなどの重合体やスターチ,カーボンなどを挙げることができる。
上記製造方法において用いられる担体としては、MgCl2,MgCl(OC2H5),Mg(OC2H5)2,SiO2,Al2O3などが好ましい。また担体の性状は、その種類及び製法により異なるが、平均粒径は通常1~300μm、好ましくは10~200μm、より好ましくは20~100μmである。
粒径が小さいと重合体中の微粉が増大し、粒径が大きいと重合体中の粗大粒子が増大し嵩密度の低下やホッパーの詰まりの原因になる。
また、担体の比表面積は、通常1~1000m2/g、好ましくは50~500m2/g、細孔容積は通常0.1~5cm3/g、好ましくは0.3~3cm3/gである。
比表面積又は細孔容積のいずれかが上記範囲を逸脱すると、触媒活性が低下することがある。なお、比表面積及び細孔容積は、例えばBET法に従って吸着された窒素ガスの体積から求めることができる。
さらに、上記担体が無機酸化物担体である場合には、通常150~1000℃、好ましくは200~800℃で焼成して用いることが望ましい。
該担体に、(A)成分及び(B)成分の少なくとも一方を担持させる方法については、特に制限されないが、例えば(i)(A)成分及び(B)成分の少なくとも一方と担体とを混合する方法、(ii)担体を有機アルミニウム化合物又はハロゲン含有ケイ素化合物で処理したのち、不活性溶媒中で(A)成分及び(B)成分の少なくとも一方と混合する方法、(iii)担体と(A)成分及び/又は(B)成分と有機アルミニウム化合物又はハロゲン含有ケイ素化合物とを反応させる方法、(iv)(A)成分又は(B)成分を担体に担持させたのち、(B)成分又は(A)成分と混合する方法、(v)(A)成分と(B)成分との接触反応物を担体と混合する方法、(vi)(A)成分と(B)成分との接触反応に際して、担体を共存させる方法などを用いることができる。
なお、上記(iv)、(v)及び(vi)の反応において、(C)成分の有機アルミニウム化合物を添加することもできる。
このようにして得られた触媒は、いったん溶媒留去を行って固体として取り出してから重合に用いてもよいし、そのまま重合に用いてもよい。
また、本発明においては、(A)成分及び(B)成分の少なくとも一方の担体への担持操作を重合系内で行うことにより触媒を生成させることができる。例えば(A)成分及び(B)成分の少なくとも一方と担体とさらに必要により前記(C)成分の有機アルミニウム化合物を加え、エチレンなどのオレフィンを常圧~2MPa(gauge)加えて、-20~200℃で1分~2時間程度予備重合を行い触媒粒子を生成させる方法を用いることができる。
本発明においては、(B-1)成分と担体との使用割合は、質量比で好ましくは1:5~1:10000、より好ましくは1:10~1:500とするのが望ましく、(B-2)成分と担体との使用割合は、質量比で好ましくは1:0.5~1:1000、より好ましくは1:1~1:50とするのが望ましい。(B)成分として二種以上を混合して用いる場合は、各(B)成分と担体との使用割合が質量比で上記範囲内にあることが望ましい。また、(A)成分と担体との使用割合は、質量比で、好ましくは1:5~1:10000、より好ましくは1:10~1:500とするのが望ましい。
(B)成分〔(B-1)成分又は(B-2)成分〕と担体との使用割合、又は(A)成分と担体との使用割合が上記範囲を逸脱すると、活性が低下することがある。このようにして調製された本発明の重合用触媒の平均粒径は、通常2~200μm、好ましくは10~150μm、特に好ましくは20~100μmであり、比表面積は、通常20~1000m2/g、好ましくは50~500m2/gである。平均粒径が2μm未満であると重合体中の微粉が増大することがあり、200μmを超えると重合体中の粗大粒子が増大することがある。比表面積が20m2/g未満であると活性が低下することがあり、1000m2/gを超えると重合体の嵩密度が低下することがある。また、本発明の触媒において、担体100g中の遷移金属量は、通常0.05~10g、特に0.1~2gであることが好ましい。遷移金属量が上記範囲外であると、活性が低くなることがある。
このように担体に担持することによって工業的に有利な高い嵩密度と優れた粒径分布を有する重合体を得ることができる。
この場合、重合方法は特に制限されず、スラリー重合法,気相重合法,塊状重合法,溶液重合法,懸濁重合法などのいずれの方法を用いてもよいが、スラリー重合法,気相重合法が特に好ましい。また、反応の制御が容易という観点から溶液重合法が特に好ましい。
重合条件については、重合温度は通常-100~250℃、好ましくは-50~200℃、より好ましくは0~130℃である。また、反応原料に対する触媒の使用割合は、原料モノマー/上記(A)成分(モル比)が好ましくは105~108、特に106~107となることが好ましい。さらに、重合時間は通常5分~10時間、反応圧力は好ましくは常圧~3MPa(gauge)、より好ましくは常圧~2.5MPa(gauge)、さらに好ましくは常圧~2MPa(gauge)である。反応圧力を調整することで、メソペンタッド分率を制御することが可能である。
重合体の分子量の調節方法としては、各触媒成分の種類,使用量,重合温度の選択、さらには水素存在下での重合などがある。
重合に際しては、前記重合用触媒を用いて予備重合を行うことができる。予備重合は、固体触媒成分に、例えば、少量のオレフィンを接触させることにより行うことができるが、その方法に特に制限はなく、公知の方法を用いることができる。予備重合に用いるオレフィンについては特に制限はなく、例えばエチレン、炭素数3~20のα-オレフィン、あるいはこれらの混合物などを挙げることができるが、該重合において用いるオレフィンと同じオレフィンを用いることが有利である。
また、予備重合温度は、通常-20~200℃、好ましくは-10~130℃、より好ましくは0~80℃である。予備重合においては、溶媒として、脂肪族炭化水素,芳香族炭化水素,モノマーなどを用いることができる。これらの中で特に好ましいのは脂肪族炭化水素である。また、予備重合は無溶媒で行ってもよい。
予備重合においては、予備重合生成物の極限粘度[η](135℃デカリン中で測定)が0.2デシリットル/g以上、特に0.5デシリットル/g以上、触媒中の遷移金属成分1ミリモル当たりに対する予備重合生成物の量が1~10000g、特に10~1000gとなるように条件を調整することが望ましい。
本発明の第1の実施態様のホットメルト接着剤は、エチレン系重合体(A)及び上記の本発明のプロピレン系重合体(B1)を含有する。
本発明の第1の実施態様のホットメルト接着剤では、良好な耐熱クリープ性と適度なオープンタイムとのバランスから、エチレン系重合体(A)100質量部に対して、上記の本発明のプロピレン系重合体(B1)1~30質量部、好ましくは5~25質量部、より好ましくは10~20質量部を含有する。ベースポリマーであるエチレン系重合体(A)に対して本発明のプロピレン系重合体(B1)を改質剤として配合することにより、本発明の第1の実施態様のホットメルト接着剤は、良好な耐熱クリープ性と適度なオープンタイムとのバランスに優れる。
本発明に用いられるエチレン系重合体(A)は本発明のホットメルト接着剤のベースポリマーであり、具体的には、ポリエチレンや、エチレンと炭素数3~10のオレフィンとの共重合体が挙げられる。接着性の観点からは、好ましくはエチレン-α-オレフィン共重合体である。α-オレフィンの具体例としては、プロピレン、1-ブテン,1-ペンテン,4-メチル-1-ペンテン,1-ヘキセン,1-オクテン,1-デセン,1-ドデセン,1-テトラデセン,1-ヘキサデセン,1-オクタデセン,1-エイコセン等が挙げられる。本発明においては、これらのうち一種又は二種以上を用いることができる。これらのα-オレフィンの中でも1-オクテンが好ましい。本発明に用いられるエチレン系重合体(A)は、接着性の観点から、より好ましくはエチレン-1-オクテン共重合体であり、更に好ましくはエチレンから導かれる構成単位を63~65質量%、1-オクテンから導かれる構成単位を35~37質量%含有するエチレン-1-オクテン共重合体である。
本発明のホットメルト接着剤は、粘着付与樹脂(C)を含有してもよい。
粘着付与樹脂(C)としては、例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂などからなる常温で固体、半固体あるいは液状のもの等を挙げることができる。これらは単独で又は二種以上を組み合わせて用いてもよい。本発明では、ベースポリマーとの相溶性を考慮して、水素添加物を用いることが好ましい。中でも、熱安定性に優れる石油樹脂の水素化物がより好ましい。
粘着付与樹脂(C)の市販品としては、アイマーブP-125、P-100、P-90(以上、出光興産(株)製)、ユーメックス1001(三洋化成工業(株)製)、ハイレッツT1115(三井化学(株)製)、クリアロンK100(ヤスハラケミカル(株)製)、ECR227、エスコレッツ2101(以上、トーネックス(株)製)、アルコンP100(荒川化学(株)製)、Regalrez 1078(ハーキュレス(Hercules)社製)、Eastotac H-130R(イーストマン・ケミカル社製)等を挙げることができる(いずれも商品名)。
本発明のホットメルト接着剤における粘着付与樹脂(C)の含有量は、粘着性向上及び粘度低下による被着体への濡れ性向上の観点から、エチレン系重合体(A)100質量部に対して、好ましくは50~200質量部、より好ましくは70~150質量部、更に好ましくは80~120質量部である。
本発明のホットメルト接着剤は、ワックス(D)を含有してもよい。
ワックス(D)としては、例えば、動物ワックス、植物ワックス、カルナウバワックス、キャンデリラワックス、木蝋、蜜蝋、鉱物ワックス、石油ワックス、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタム、ポリエチレンワックス、酸化ポリエチレンワックス、ポリプロピレンワックス、酸化ポリプロピレンワックス、高級脂肪酸ワックス、高級脂肪酸エステルワックス、フィッシャー・トロプシュワックス等が挙げられる。
本発明のホットメルト接着剤におけるワックス(D)の含有量は、柔軟性向上、粘度低下による濡れ性の向上の観点から、エチレン系重合体(A)100質量部に対して、好ましくは50~200質量部、より好ましくは60~150質量部、更に好ましくは70~120質量部である。ワックスの添加量が多くなると、ホットメルト接着剤の粘度が低くなる。
また、本発明のホットメルト接着剤は、必要に応じて可塑剤、無機フィラー、酸化防止剤等の各種添加剤を含有してもよい。
可塑剤としては、パラフィン系プロセスオイル、ナフテン系プロセスオイル、フタル酸エステル類、アジピン酸エステル類、脂肪酸エステル類、グリコール類、エポキシ系高分子可塑剤などを例示できる。
無機フィラーとしては、クレー、タルク、炭酸カルシウム、炭酸バリウムなどを例示できる。
酸化防止剤としては、トリスノニフェニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、アデカスタブ1178((株)ADEKA製)、スミライザーTNP(住友化学(株)製)、イルガフォス168(BASF社製)、SandstabP-EPQ(サンド社製)、等のリン系酸化防止剤、2,6-ジ-t-ブチル-4-メチルフェノール、n-オクタデシル-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート、スミライザーBHT(住友化学(株)製)、イルガノックス1010(BASF社製)等のフェノール系酸化防止剤、ジラウリル-3,3’-チオジプロピオネート、ペンタエリスリトールテトラキス(3-ラウリルチオプロピオネート)、スミライザーTPL(住友化学(株)製)、ヨシノックスDLTP(吉富製薬(製))アンチオックスL(日油(株)製)等のイオウ系酸化防止剤などを例示できる。
本発明の第2の実施態様のホットメルト接着剤は、エチレン系重合体(A)と下記(a2)及び(b2)を満たすプロピレン系重合体(B2)を含有する。
(a2)[mmmm]=20~80モル%
(b2)重量平均分子量(Mw)=1,000~150,000
本発明の第2の実施態様のホットメルト接着剤では、良好な耐熱クリープ性と適度なオープンタイムとのバランスから、エチレン系重合体(A)100質量部に対して、上記の本発明のプロピレン系重合体(B2)1~30質量部、好ましくは5~25質量部、より好ましくは10~20質量部を含有する。ベースポリマーであるエチレン系重合体(A)に対して本発明のプロピレン系重合体(B2)を改質剤として配合することにより、本発明の第2の実施態様のホットメルト接着剤は、良好な耐熱クリープ性と適度なオープンタイムとのバランスに優れる。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)は、下記(a2)及び(b2)を満たす。また、好ましくは更に下記(c2)~(e2)を満たす。
(a2)[mmmm]=20~80モル%
(b2)重量平均分子量(Mw)=1,000~150,000
(c2)Mw/Mn≦2.5
(d2)[rmrm]≧2.5モル%
(e2)融点(Tm-D)=0~140℃
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)は、メソペンタッド分率[mmmm]が20~80モル%である。[mmmm]が20モル%未満であると耐熱クリープ性低下の観点から好ましくない。また、[mmmm]が80モル%を超えるとオープンタイム低下の観点から好ましくない。
オープンタイムの観点からは、メソペンタッド分率[mmmm]は、好ましくは20~70モル%、より好ましくは47~70モル%、更に好ましくは48~60モル%である。一方、良好な耐熱クリープ性と適度なオープンタイムとのバランスの観点からは、メソペンタッド分率[mmmm]は、好ましくは60モル%を超え80モル%以下、より好ましくは60モル%を超え75モル%以下、更に好ましくは60モル%を超え72モル%以下である。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)は、重量平均分子量が1,000~150,000である。重量平均分子量が1,000未満であると耐熱クリープ性及び凝集力低下の観点から好ましくない。また、重量平均分子量が150,000を超えると溶融粘度上昇による塗工性低下の観点から好ましくない。
オープンタイムの観点及び良好な耐熱クリープ性と適度なオープンタイムとのバランスの観点から、重量平均分子量は、好ましくは10,000~100,000、より好ましくは15,000~80,000である。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)は、分子量分布(Mw/Mn)が2.5以下である。分子量分布が2.5以下であれば、良好な塗工性を示す。このような観点から、分子量分布は、好ましくは2.4以下、より好ましくは2.2以下である。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)は、ラセミメソラセミメソ分率[rmrm]が2.5モル%以上である。[rmrm]が2.5モル%以上であれば、オープンタイム向上の観点から好ましい。このような観点から、ラセミメソラセミメソ分率[rmrm]は、好ましくは2.6~5.0モル%、より好ましくは2.7~5.0モル%である。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)の融点(Tm-D)は、オープンタイム向上及び耐熱クリープ性向上の観点から、好ましくは0~140℃、より好ましくは20~120℃、更に好ましくは40~100℃である。
また、メソペンタッド分率[mmmm]、ラセミメソラセミメソペンタッド分率[rmrm]、重量平均分子量(Mw)、分子量分布(Mw/Mn)及び融点(Tm-D)の測定方法については、本発明のプロピレン系重合体に関して上述したのと同様である。
本発明の第2の実施態様のホットメルト接着剤に用いられるプロピレン系重合体(B2)の製造方法としては、上述した本発明のプロピレン系重合体(プロピレン系重合体(B1))の製造方法と同様に、メタロセン触媒を用いて、プロピレンを単独重合してプロピレン単独重合体を製造する方法や、プロピレンとエチレン及び/又は炭素数4以上のα-オレフィンとを共重合してプロピレン共重合体を製造する方法が挙げられる。触媒を適宜選択することにより得られるポリオレフィンの結晶性を制御することができ、プロピレン系重合体(B2)を得ることができる。
プロピレン系重合体(B2)の製造に使用できるメタロセン触媒としては、例えば特開2000-256411号公報に記載されたものが挙げられる。
本発明の第3の実施態様のホットメルト接着剤は、上記の本発明のプロピレン系重合体(B1)をベースポリマーとして含有する。ホットメルト接着剤中、本発明のプロピレン系重合体(B1)を、好ましくは55質量%以上、より好ましくは60質量%以上、更に好ましくは65質量%以上含有する。
本発明の第3の実施態様のホットメルト接着剤は、ベースポリマーとして含有される本発明のプロピレン系重合体(B1)が比較的に硬いため、使用時の塗布量が少ない包装用の接着剤としては適していないが、使用時の塗布量が多い木工用の接着剤としては好適である。一般に、キッチン等に用いられる木工用の接着剤では、より高温での耐久性が求められる。これに対し、本発明の第3の実施態様のホットメルト接着剤は、良好な耐熱クリープ性を有しており、さらには良好な耐熱クリープ性と適度なオープンタイムとのバランスに優れる。
本発明の第1又は第2の実施態様のホットメルト接着剤は、エチレン系重合体(A)と、プロピレン系重合体(B1)又は(B2)と、必要に応じて粘着付与樹脂(C)、ワックス(D)及び各種添加剤とをヘンシェルミキサー等を用いてドライブレンドし、単軸又は2軸押出機、プラストミルやバンバリーミキサー等により溶融混練することで製造することができる。また、本発明の第3の実施態様のホットメルト接着剤は、ベースポリマーとしてのプロピレン系重合体(B1)と、必要に応じてエチレン系重合体(A)、粘着付与樹脂(C)、ワックス(D)及び各種添加剤とをヘンシェルミキサー等を用いてドライブレンドし、単軸又は2軸押出機、プラストミルやバンバリーミキサー等により溶融混練することで製造することができる。
本発明のホットメルト接着剤は、ダンボール等の包装用の接着剤や、木工用の接着剤として好適に使用することができる。
特に、本発明で得られる材料は、ホットメルト接着剤への適用性に優れ、固化速度や溶融粘度のコントロールに用いることができる。さらに、オイルのブリード(滲み出し)防止や、べた付き感の抑制などによるハンドリング性の向上などが得られる。例えば引張弾性率の低いベースポリマーを添加するとオープンタイムの延長、引張弾性率の高いベースポリマーを添加するとセットタイムの短縮が可能と考えられる。
ここで、溶融粘度は、ホットメルト接着剤をノズルから噴射して塗布できるか否かを見る指標として有用である。溶融粘度が高くなりすぎると、糸引きが生じ、実用上好ましくない。なお、木工用ホットメルト接着剤の場合は、ノズルを使用せずに塗布するため溶融粘度が高くても実用上問題はない。
本発明の接着方法は、基材と他の基材との接着方法であり、本発明のホットメルト接着剤を溶融し、少なくとも1つの基材に塗布する工程、及び塗布されたホットメルト接着剤に他の基材を接着する工程を含む。
[錯体A((1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)(インデニル)(3-トリメチルシリルメチルインデニル)ジルコニウムジクロリド)]
特許第4053993号公報の実施例5の記載に従って、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)(インデニル)(3-トリメチルシリルメチルインデニル)ジルコニウムジクロリドを合成した。
[錯体B((1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)-ビス(3-トリメチルシリルメチルインデニル)ジルコニウムジクロリド)]
特許第4053993号公報の参考例1の記載に従って、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)-ビス(3-トリメチルシリルメチルインデニル)ジルコニウムジクロリドを合成した。
[錯体C((1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)-ビス(インデニル)ジルコニウムジクロリド)]
特開2000-256411号公報の実施例1の記載に従って、(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)-ビス(インデニル)ジルコニウムジクロリドを合成した。
(ポリプロピレン1の製造)
撹拌機付き、内容積0.2m3のステンレス製反応器に、n-ヘプタンを25L/h、トリイソブチルアルミニウムを25mmol/h、さらに、ジメチルアニリニウムテトラキスペンタフルオロフェニルボレートと錯体Aとトリイソブチルアルミニウムとプロピレンを事前に接触させ得られた触媒成分をジルコニウムあたり1.2μmol/hで連続供給した。
重合温度65℃で気相部水素濃度を2.5mol%、反応器内の全圧を1.0MPa・Gに保つようプロピレンと水素を連続供給した。
得られた重合溶液に、イルガノックス1010(商品名、BASF社製)を、重合溶液中の含有量が1000ppmになるように添加し、溶媒を除去することにより、プロピレン単独重合体(ポリプロピレン1)を得た。
(ポリプロピレン2の製造)
撹拌機付き、内容積0.2m3のステンレス製反応器に、n-ヘプタンを25L/h、トリイソブチルアルミニウムを25mmol/h、さらに、ジメチルアニリニウムテトラキスペンタフルオロフェニルボレートと錯体Aとトリイソブチルアルミニウムとプロピレンを事前に接触させ得られた触媒成分をジルコニウムあたり1.8μmol/hで連続供給した。
重合温度65℃で気相部水素濃度を1.5mol%、反応器内の全圧を1.0MPa・Gに保つようプロピレンと水素を連続供給した。
得られた重合溶液に、イルガノックス1010(商品名、BASF社製)を、重合溶液中の含有量が1000ppmになるように添加し、溶媒を除去することにより、プロピレン単独重合体(ポリプロピレン2)を得た。
(ポリプロピレン3の製造)
撹拌機付き、内容積68m3のステンレス製反応器に、n-ヘプタンを5.2m3/h、トリイソブチルアルミニウムを0.6mol/h、さらに、ジメチルアニリニウムテトラキスペンタフルオロフェニルボレートと錯体Bとトリイソブチルアルミニウムとプロピレンを事前に接触させ得られた触媒成分をジルコニウムあたり0.7mmol/hで連続供給した。
重合温度85℃で気相部水素濃度を5.0mol%、反応器内の全圧を1.7MPa・Gに保つようプロピレンと水素を連続供給した。
得られた重合溶液に、イルガノックス1010(商品名、BASF社製)を、重合溶液中の含有量が1000ppmになるように添加し、溶媒を除去することにより、プロピレン単独重合体(ポリプロピレン3)を得た。
(ポリプロピレン4の製造)
撹拌機付き、内容積0.2m3のステンレス製反応器に、n-ヘプタンを25L/h、トリイソブチルアルミニウムを25mmol/h、さらに、ジメチルアニリニウムテトラキスペンタフルオロフェニルボレートと錯体Cとトリイソブチルアルミニウムとプロピレンを事前に接触させ得られた触媒成分をジルコニウムあたり1.2μmol/hで連続供給した。
重合温度70℃で気相部水素濃度を0.66mol%、反応器内の全圧を0.66MPa・Gに保つようプロピレンと水素を連続供給した。
得られた重合溶液に、イルガノックス1010(商品名、BASF社製)を、重合溶液中の含有量が1000ppmになるように添加し、溶媒を除去することにより、プロピレン単独重合体(ポリプロピレン4)を得た。
(ポリプロピレン5の製造)
重合温度60℃で気相部水素濃度を3.5mol%、反応器内の全圧を0.7MPa・Gに保つようプロピレンと水素を連続供給したこと以外は製造例4と同様にして、プロピレン単独重合体(ポリプロピレン5)を得た。
(ポリプロピレン6の製造)
重合温度60℃で気相部水素濃度を0.66mol%、反応器内の全圧を0.66MPa・Gに保つようプロピレンと水素を連続供給したこと以外は製造例4と同様にして、プロピレン単独重合体(ポリプロピレン6)を得た。
製造例1~6で得られたポリプロピレン1~6について、以下に示す装置及び条件で、13C-NMRスペクトルの測定を行った。なお、ピークの帰属は、エイ・ザンベリ(A.Zambelli)等により「Macromolecules,8,687(1975)」で提案された方法に従った。結果を表1に示す。
装置:日本電子(株)製、JNM-EX400型13C-NMR装置
方法:プロトン完全デカップリング法
濃度:220mg/ml
溶媒:1,2,4-トリクロロベンゼンと重ベンゼンの90:10(容量比)混合溶媒
温度:130℃
パルス幅:45°
パルス繰り返し時間:4秒
積算:10,000回
M=m/S×100
R=γ/S×100
S=Pββ+Pαβ+Pαγ
S:全プロピレン単位の側鎖メチル炭素原子のシグナル強度
Pββ:19.8~22.5ppm
Pαβ:18.0~17.5ppm
Pαγ:17.5~17.1ppm
γ:ラセミペンタッド連鎖:20.7~20.3ppm
m:メソペンタッド連鎖:21.7~22.5ppm
製造例1~6で得られたポリプロピレン1~6について、ゲルパーミエイションクロマトグラフィ(GPC)法により、重量平均分子量(Mw)及び分子量分布(Mw/Mn)を求めた。測定には、下記の装置及び条件を使用し、ポリスチレン換算の重量平均分子量を得た。結果を表1に示す。
<GPC測定装置>
カラム :TOSO GMHHR-H(S)HT
検出器 :液体クロマトグラム用RI検出器 WATERS 150C
<測定条件>
溶媒 :1,2,4-トリクロロベンゼン
測定温度 :145℃
流速 :1.0ml/分
試料濃度 :2.2mg/ml
注入量 :160μl
検量線 :Universal Calibration
解析プログラム:HT-GPC(Ver.1.0)
製造例1~6で得られたポリプロピレン1~6について、粘度計((株)離合社製、商品名:「VMR-053U-PC・F01」)、ウベローデ型粘度管(測時球容積:2~3ml、毛細管直径:0.44~0.48mm)、溶媒としてテトラリンを用いて、0.02~0.16g/dLの溶液を135℃にて測定した。結果を表1に示す。
製造例1~6で得られたポリプロピレン1~6について、示差走査型熱量計(パーキン・エルマー社製、DSC-7)を用い、試料10mgを窒素雰囲気下-10℃で5分間保持した後、10℃/分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップから融点(Tm-D)を求めた。また、後述する実施例6及び8~10で用いた2種のポリプロピレンのブレンドについても、上記と同様にしてラセミメソラセミメソペンタッド分率[rmrm]及び融点(Tm-D)を求めた。結果を表1に示す。
<エチレン系重合体(A)(ベースポリマー)>
エチレン-1-オクテン共重合体(商品名:Affinity GA1950、ダウ・ケミカル社製、重量平均分子量:38000、1-オクテンの含有量:35~37重量%、メルトフローレート:500g/10min)
<プロピレン系重合体(B)>
(B-X)エチレン-プロピレン共重合体(商品名:Licocene PP 2602、クラリアント社製、エチレン:プロピレン=15mol%:85mol%)
(B-Y)ポリプロピレン(商品名:ビスコール 660-P、三洋化成工業(株)製)
(B-Z)エチレン-プロピレン-ブテン共重合体(商品名:VESTOPLAST 708、Evonik社製、重量平均分子量(Mw):75,000、分子量分布(Mw/Mn):6.5)
<粘着付与樹脂(C)>
(C-1)脂肪族系炭化水素石油樹脂の水素化誘導体(商品名:Eastotac H-130R、イーストマン・ケミカル社製、軟化点:130℃)
(C-2)水添石油樹脂(商品名:アイマーブ P-125、出光興産(株)製、軟化点:125℃)
<ワックス(D)>
(D-1)フィッシャー・トロプシュワックス(商品名:Paraflint H1、サゾール・ワックス社製)
(D-2)ポリプロピレンワックス(商品名:ビスコール 660-P、三洋化成工業(株)製)
(包装用ホットメルト接着剤の製造)
表2及び3に記載の材料を、表2及び3に記載の配合比でSUS缶に入れ、180℃で30分加熱して溶融させた後、撹拌翼で15分混合・撹拌し、ホットメルト接着剤を作製した。得られたホットメルト接着剤について以下の評価を行った。
オープンタイムとは、被着材に塗布したときから温度が下がって粘着性がなくなるまでの粘着保持時間をいう。
180℃に加熱して溶融させたホットメルト接着剤を、Kライナーダンボールに塗工量2.8~3.2g/mで塗布し、所定時間経過後に接着圧2kg/25cm2、セットタイム2秒の条件で貼り合わせた。接着試験片を23℃、湿度50%の環境下で24時間静置し、手で剥離させた。5回測定したうち、材料破壊率80%以上の試験片が4個以上となる最長の経過時間をオープンタイム(秒)とした。
得られたオープンタイムの値について、以下の基準に従って評価した。
A(4点):オープンタイムが15秒以上。
B(3点):オープンタイムが14秒以上15秒未満。
C(2点):オープンタイムが13秒以上14秒未満。
D(1点):オープンタイムが13秒未満。
セットタイムとは、被着材に貼り合わせたホットメルト接着剤が冷却固化して初期接着力を示すまでの時間をいう。
180℃に加熱して溶融させたホットメルト接着剤を、Kライナーダンボールに塗工量2.8~3.2g/mで塗布し、2秒のオープンタイムをとった後に接着圧2kg/25cm2で貼り合わせた。接着試験片を23℃、湿度50%の環境下で所定の圧締時間が経過した後に剥離し、5回測定したうち材料破壊率80%以上の試験片が4個以上となる最短の圧締経過時間をセットタイム(秒)とした。
恒温クリープは接着剤の耐熱クリープ性を示す指標であり、剥離時間が長いほど耐熱クリープ性があり、輸送等の際に剥離しにくく好ましい。
180℃に加熱して溶融させたホットメルト接着剤を、Kライナーダンボールに塗工量2.8~3.2g/mで塗布し、2秒のオープンタイムをとった後に接着圧2kg/25cm2、セットタイム2秒の条件で貼り合わせた。接着試験片を23℃、湿度50%の環境下で24時間静置した。作製した試験片を60℃、湿度30%の環境下、応力方向に200g/g/25cm2の荷重をかけ、貼り合わせたサンプルが剥離するまでの時間を測定した。5回測定し、最長及び最短の剥離時間を除いた3点の平均値を恒温クリープ試験の値とした。
得られた恒温クリープの値について、以下の基準に従って評価した。
AA(6点):恒温クリープの値が100分より長い。
A(5点):恒温クリープの値が80分以上100分以下。
B(4点):恒温クリープの値が70分以上80分未満。
C(3点):恒温クリープの値が60分以上70分未満。
D(2点):恒温クリープの値が50分以上60分未満。
E(1点):恒温クリープの値が50分未満。
180℃においてそれぞれホットメルト接着剤を溶融させ、TVB-15型ブルックフィールド粘度計を用い、M2のローターで粘度を測定した。
溶融粘度が高いと糸引きが多くなるが、180℃における溶融粘度が1,500mPa・s以下であると糸曳きが少なく、塗布性に優れる。
上記のオープンタイム評価及び耐熱クリープ性評価について、以下の基準に従って総合評価を行った。
○:オープンタイム評価及び耐熱クリープ性評価の合計点が6点以上。
△:オープンタイム評価及び耐熱クリープ性評価の合計点が4点以上6点未満。
×:オープンタイム評価及び耐熱クリープ性評価の合計点が4点未満。
(木工用ホットメルト接着剤の製造)
表4に記載の材料を、表4の配合比でSUS缶に入れ、180℃で30分撹拌混合し、ホットメルト接着剤を作製した。得られたホットメルト接着剤について以下の評価を行った。
170℃に加熱して溶融させたホットメルト接着剤を、200μmの厚さになるように紙面(一般紙:65g/m2)に塗布した。
その後、ホットメルト接着剤の塗布された紙片を、室温で一定時間の間隔で木材と接着させ、5kgの重りを5分間乗せ冷却させた。30分経過後に手で剥離し、紙や木材の繊維を引き破ることなく接着面から剥がすことができる最長の経過時間をオープンタイム(秒)とした。
170℃に加熱して溶融させたホットメルト接着剤を、200μmの厚さになるように紙面(ケント紙:210g/m2)に塗布した。その後、ホットメルト接着剤が塗布された紙片を室温で木材と接着させ、5kgの重りを5分間乗せ冷却させた。重りを外し、接着試験片を23℃、湿度50%の環境下で24時間静置した。作製した試験片を、70℃又は90℃、相対湿度30%の環境下、応力方向に200gの荷重をかけ、貼り合わせたサンプルが剥離するまでの時間を測定した。3回測定し、平均値を恒温クリープ試験の値とした。
一方、エチレン系共重合体(A)をベースポリマーとし、本発明のプロピレン系重合体を含有しない比較例5では、エチレン系共重合体(A)自体が粘着性を有する材料であるため、オープンタイムは非常に良好な結果となっている。しかし、耐熱クリープ性に劣り、特に90℃における恒温クリープに著しく劣る。高温になるにつれ、低分子量成分の流動性が大きくなって、滲み出してしまい、接着を維持することができなくなっている。また、分子量分布が本発明の規定外であるプロピレン系共重合体(B-Z)をベースポリマーとする比較例6では、オープンタイムが遅い。粘度を調整するためワックスを添加した比較例7及び8では、オープンタイムが速くなるものの、粘着性が低くなるために耐熱クリープ性に劣る。
なお、プロピレン系重合体(B2)をベースポリマーとする参考例6では、70℃における恒温クリープは良好であるものの、90℃における恒温クリープに劣る。また、粘度を調整するためワックスを添加した参考例7では、オープンタイムが速くなるものの、粘着性が低くなるために耐熱クリープ性に劣る。
Claims (9)
- 下記(a1)~(d1)を満たすプロピレン系重合体。
(a1)[mmmm]=60~80モル%
(b1)重量平均分子量(Mw)=10,000~55,000
(c1)Mw/Mn≦2.5
(d1)[rmrm]<2.5モル% - 下記(b1’)を満たす、請求項1に記載のプロピレン系重合体。
(b1’)重量平均分子量(Mw)=10,000~51,000 - エチレン系重合体(A)100質量部に対して、請求項1又は2に記載のプロピレン系重合体(B1)1~30質量部を含むホットメルト接着剤。
- エチレン系重合体(A)100質量部に対して、下記(a2)及び(b2)を満たすプロピレン系重合体(B2)1~30質量部を含むホットメルト接着剤。
(a2)[mmmm]=20~80モル%
(b2)重量平均分子量(Mw)=1,000~150,000 - 前記エチレン系重合体(A)がエチレン-α-オレフィン共重合体である、請求項3又は4に記載のホットメルト接着剤。
- 前記エチレン系重合体(A)がエチレン-1-オクテン共重合体である、請求項3~5のいずれかに記載のホットメルト接着剤。
- 前記エチレン系重合体(A)が、エチレンから導かれる構成単位を63~65質量%、1-オクテンから導かれる構成単位を35~37質量%含有するエチレン-1-オクテン共重合体である、請求項3~6のいずれかに記載のホットメルト接着剤。
- エチレン系重合体(A)100質量部に対して、粘着付与樹脂(C)50~200質量部及びワックス(D)50~200質量部を更に含む、請求項3~7のいずれかに記載のホットメルト接着剤。
- 請求項3~8のいずれかに記載のホットメルト接着剤を溶融し、少なくとも1つの基材に塗布する工程、及び塗布されたホットメルト接着剤に他の基材を接着する工程を含む、基材と他の基材との接着方法。
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US14/442,544 US9605185B2 (en) | 2012-11-15 | 2013-11-12 | Propylene-based polymer and hot melt adhesive |
CN201380059270.3A CN104781291B (zh) | 2012-11-15 | 2013-11-12 | 丙烯系聚合物和热熔粘接剂 |
EP13854723.7A EP2921508A4 (en) | 2012-11-15 | 2013-11-12 | POLYMER ON PROPYLENE BASE AND MELT ADHESIVE THEREOF |
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WO2022045165A1 (ja) * | 2020-08-26 | 2022-03-03 | 出光興産株式会社 | プロピレン系樹脂組成物 |
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JPWO2014077258A1 (ja) | 2017-01-05 |
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