WO2014069604A1 - 粘接着剤組成物及びこれを用いた粘着テープ - Google Patents
粘接着剤組成物及びこれを用いた粘着テープ Download PDFInfo
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- WO2014069604A1 WO2014069604A1 PCT/JP2013/079638 JP2013079638W WO2014069604A1 WO 2014069604 A1 WO2014069604 A1 WO 2014069604A1 JP 2013079638 W JP2013079638 W JP 2013079638W WO 2014069604 A1 WO2014069604 A1 WO 2014069604A1
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- Prior art keywords
- group
- adhesive composition
- polyolefin
- adhesive
- mpa
- Prior art date
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- 238000005259 measurement Methods 0.000 claims abstract description 40
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- GVFLIEBOPZQLON-UHFFFAOYSA-M silver;fluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)CF GVFLIEBOPZQLON-UHFFFAOYSA-M 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical group C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 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
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
-
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
Definitions
- the present invention relates to an adhesive composition containing a polyolefin-based polymer and a pressure-sensitive adhesive tape using the same.
- Patent Document 1 discloses a protective film produced by mixing an ethylene-based polymer with liquid polybutene or polyisobutylene as a tackifier.
- Patent Document 2 discloses an adhesive tape made of an olefin polymer and an adhesive resin.
- the conventional adhesive tries to increase the adhesive strength, adhesive residue is generated when the substrate is peeled off, the adhesive tape is difficult to reuse, and the adhesive has a low holding power.
- the addition amount of the tackifier or the like is increased in order to increase the adhesive force, the holding force is insufficient, and the balance between the adhesive force and the holding force is not sufficient.
- the problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition having a high adhesive force and holding power and having no adhesive residue and a pressure-sensitive adhesive tape using the same, using a polyolefin polymer. .
- the following adhesive composition and pressure-sensitive adhesive tape are provided.
- [1] 5 to 95% by mass of a polyolefin in which a melting point by a differential scanning calorimeter (DSC) is not observed or a melting point is less than 20 ° C. and ⁇ H is less than 5 J / g;
- An adhesive composition comprising 95 to 5% by mass of a polyolefin having a melting point of 20 ° C. or more and 160 ° C. or less and ⁇ H of 5 J / g or more and 100 J / g or less,
- An adhesive composition having a storage elastic modulus at 25 ° C. of 1 MPa or higher and 200 MPa or lower and a storage elastic modulus at 50 ° C.
- the adhesive composition of the present invention and the pressure-sensitive adhesive tape using the same have high adhesive strength and holding power and no adhesive residue.
- the adhesive composition according to the first embodiment of the present invention includes a specific amorphous polyolefin (1) and a specific crystalline polyolefin (2).
- the adhesive composition of the second embodiment of the present invention includes a specific amorphous polyolefin (1) and a specific thermoplastic elastomer (3).
- the adhesive composition of the first embodiment is preferable from the viewpoint of high adhesive strength and holding power, no adhesive residue, and excellent applicability.
- maintenance force, and the balance of adhesive residue can be provided by mixing polymer materials with which crystallinity was controlled appropriately.
- the “holding force” refers to a force that can be withstand when a static load is applied to the adherend adhesive portion of the tape in the length direction of the tape.
- the adhesive strength is improved by containing the specific amorphous polyolefin (1), while the viscosity of the present invention is improved by containing the specific crystalline polyolefin (2) or the specific thermoplastic elastomer (3). It is considered that the adhesive composition can suppress the occurrence of adhesive residue.
- Polyolefin (1) used in the present invention has no melting point (Tm) observed by a differential scanning calorimeter (DSC) or a melting point of less than 20 ° C. and a melting endotherm ( ⁇ H) of less than 5 J / g. It is. In the present invention, it is hereinafter also referred to as “amorphous polyolefin (1)”.
- Tm melting point
- ⁇ H melting endotherm
- the fact that the melting point is not observed with a differential scanning calorimeter means that the crystal melting peak cannot be substantially observed because the crystallization rate is very slow or no crystallization occurs in the DSC measurement. .
- ⁇ H is often not substantially observable. Even when ⁇ H cannot be observed, ⁇ H is considered to be less than 5 J / g. That is, the ⁇ H is not observed or is less than 5 J / g.
- the content of the amorphous polyolefin (1) in the adhesive composition of the present invention is 5% by mass or more and 95% by mass from the viewpoint of the balance of adhesive strength, tackiness, holding power, and low adhesive residue.
- % Preferably 10% to 90% by mass, more preferably 20% to 85% by mass, still more preferably 30% to 80% by mass, and still more preferably 45% to 75% by mass. % Or less.
- the amorphous polyolefin (1) used in the present invention is not particularly limited, but is preferably an olefin polymer having 2 to 12 carbon atoms, more preferably an ⁇ -olefin polymer having 3 to 12 carbon atoms. More preferably, it is at least one selected from the group consisting of 1-butene homopolymer, propylene homopolymer, and 1-butene-propylene copolymer. From the viewpoint of improving the adhesive strength at a low temperature, it is preferable to use a 1-butene homopolymer having a glass transition temperature Tg lower than that of the propylene homopolymer.
- the amorphous polyolefin (1) used in the present invention preferably satisfies the following (a1) to (a5).
- A1 Mesopentad fraction (mmmm) is 3 to 40 mol%. Alternatively, the mesodiad fraction (m) is 30 to 95 mol%.
- A2) The sum of the 1,3-bond fraction and the 1,4-bond fraction is less than 0.3 mol%.
- A3) The 2,1-bond fraction is less than 0.3 mol%.
- the molecular weight distribution (Mw / Mn) measured by the gel permeation chromatograph (GPC) method is 4.0 or less.
- the weight average molecular weight (Mw) measured by GPC method is 5,000 to 1,000,000.
- the mesopentad fraction (mmmm), mesodyad fraction (m), 1,3-bond fraction, 1,4-bond fraction and 2,1-bond fraction were reported by Asakura et al. Polymer Journal, 16, 717 (1984) ", J. Am. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. This is determined in accordance with the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
- signals of methylene group and methine group were measured using 13 C nuclear magnetic resonance spectrum, and mesopentad fraction (mmmm), mesodyad fraction (m), 1,3-bond fraction, 1, Determine 4-bond fraction and 2,1-bond fraction.
- the 13 C-NMR spectrum is measured with the following apparatus and conditions. Apparatus: JNM-EX400 type 13 C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10,000 times
- 1,3-bond fraction and 2,1-bond fraction of the propylene homopolymer and the 1-butene-propylene copolymer can be calculated from the above-mentioned 13 C-NMR spectrum measurement results by the following formula.
- 1,3-bond fraction (D / 2) / (A + B + C + D) ⁇ 100 (mol%)
- 2,1-bond fraction [(A + B) / 2] / (A + B + C + D) ⁇ 100 (mol%)
- C Integrated value of 19.5 to 22.5 ppm
- D Integrated value of 27.6 to 27.8 ppm
- the 1,4-bond fraction of 1-butene-propylene copolymer and the 1,4-bond fraction and 2,1-bond fraction of 1-butene homopolymer are shown in the above 13 C-NMR spectrum. From the measurement result, it can be calculated by the following formula.
- 1,4-bond fraction E / (A + B + C + D + E) ⁇ 100 (mol%)
- 2,1-bond fraction ⁇ (A + B + D) / 3 ⁇ / (A + B + C + D) ⁇ 100 (mol%)
- E 31.1 ppm integrated value
- the mesopentad fraction (mmmm) is preferably 3 from the viewpoint that the adhesive composition of the present invention repeatedly adheres. It is ⁇ 40 mol%, more preferably 3 to 25 mol%, still more preferably 3 to 10 mol%.
- the mesodyad fraction (m) is preferably 30 from the viewpoint of a balance between heat resistance and adhesiveness. It is ⁇ 95 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 85 mol%.
- the 1-butene-propylene copolymer in the present invention means that the total of the copolymerization ratio of propylene units and the copolymerization ratio of 1-butene units is 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. % Or more.
- ethylene or an ⁇ -olefin having 5 or more carbon atoms may be contained as a comonomer.
- ⁇ -olefin used as a comonomer examples include pentene-1, heptene-1, hexene-1, heptene-1, octene-1, decene-1, 4-methylpentene-1, 3-methylbutene-1, Examples thereof include dienes such as 1,3-butadiene, hexadiene, pentadiene, heptadiene and octadiene.
- the 1-butene-propylene copolymer is preferably a random copolymer.
- the structural unit obtained from 1-butene is preferably 15 mol% or more, more preferably 50 mol% or more, and particularly preferably 75 mol% or more.
- the 1-butene unit is 15 mol% or more, the low temperature characteristics of the pressure-sensitive adhesive containing the same polymer are improved. From the viewpoint of low temperature characteristics, it is better that the number of structural units obtained from 1-butene is larger.
- Each structural unit in the 1-butene-propylene copolymer can be calculated as follows from the measurement result of the 13 C-NMR spectrum described above.
- the mesodyad fraction (m) can be calculated from the following formula.
- Mesodyad fraction (m) (integrated value of 40.4 to 39.9 ppm) / (integrated value of 40.4 to 39.9 ppm + integrated value of 40.7 to 40.4 ppm)
- the amorphous polyolefin (1) used in the present invention has a total of 1,3-bond fraction and 1,4-bond fraction. Preferably it is less than 0.3 mol%, More preferably, it is less than 0.1 mol%, More preferably, it is 0 mol%. When it is within the above range, the fluidity at a low temperature is good, the low-temperature adhesiveness is improved, and the compatibility with the tackifier is good.
- the above “total of 1,3-bond fraction and 1,4-bond fraction” refers to 1,3-bond when the amorphous polyolefin (1) used in the present invention is a propylene homopolymer.
- This means a bond fraction which means a 1,4-bond fraction when it is a 1-butene homopolymer, and a 1,3-bond fraction when it is a propylene-1-butene copolymer. It means the sum of 1,4-bond fractions.
- the control of the 1,3-bond fraction and the 1,4-bond fraction is performed according to the structure of the main catalyst and the polymerization conditions in the same manner as the control of the 2,1-bond fraction described later.
- the amorphous polyolefin (1) used in the present invention preferably has a 2,1-bond fraction of less than 0.3 mol%, more preferably 0.1 mol. %, More preferably 0 mol%. When it is within the above range, the fluidity at a low temperature is good, the low-temperature adhesiveness is improved, and the compatibility with the tackifier is good.
- the 2,1-bond fraction is controlled by the structure of the main catalyst and the polymerization conditions. Specifically, the structure of the main catalyst has a great influence, and the 2,1-bond can be controlled by narrowing the insertion field of the monomer around the central metal of the main catalyst, and conversely, the insertion field should be widened.
- the number of 2,1-bonds can be increased.
- a catalyst called a half metallocene type has a wide insertion field around the central metal, so that structures such as 2,1-bonds and long-chain branches are easily generated.
- suppression can be expected, in the case of the racemic type, the stereoregularity becomes high, and it is difficult to obtain an amorphous polymer as shown in the present invention.
- a racemic type as will be described later introduces a substituent at the 3-position with a double-bridged metallocene catalyst and controls the center metal insertion field to obtain an amorphous polymer with very few 2,1-bonds. be able to.
- the amorphous polyolefin (1) used in the present invention has a molecular weight distribution (Mw / Mn) measured by GPC method of preferably 4 or less, more preferably 3.5 or less, and still more preferably 3.0 or less.
- Mw / Mn molecular weight distribution measured by GPC method of preferably 4 or less, more preferably 3.5 or less, and still more preferably 3.0 or less.
- the amorphous polyolefin (1) used in the present invention has a weight average molecular weight (Mw) measured by GPC method of preferably 5,000 to 1,000,000, more preferably 9,000 to 200,000, The preferred range is 20,000 to 100,000. If Mw is 5,000 or more, stickiness is reduced. When Mw is 1,000,000 or less, the fluidity is improved and the moldability (coating property) is improved.
- the said weight average molecular weight (Mw) and number average molecular weight (Mn) are the polystyrene conversion measured with the following apparatus and conditions,
- the said molecular weight distribution (Mw / Mn) is these weight average molecular weights (Mw).
- the number average molecular weight (Mn) is the weight average molecular weight (Mw).
- ⁇ 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 method for producing the amorphous polyolefin (1) used in the present invention includes a method for producing a propylene homopolymer or a 1-butene homopolymer by homopolymerizing propylene or 1-butene using a metallocene catalyst. And 1-butene-propylene copolymer by copolymerization of 1-butene and propylene (further used, ⁇ -olefin having 5 to 20 carbon atoms).
- metallocene catalyst examples 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 or different.
- 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 40 carbon atoms include dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups.
- Dialkenyl phosphide group such as divinyl phosphide group, dipropenyl phosphide group, dicyclohexenyl phosphide group; dibenzyl phosphide group, bis (phenylethyl) phosphide group, bis (phenylpropyl) phosphide group, etc.
- Bis (arylalkyl) phosphide group diphenyl phosphide group, ditolyl phosphide group, bis (dimethylphenyl) phosphide group, bis (trimethylphenyl) phosphide group, bis (ethylphenyl) phosphide group, bis (propylphenyl) phosphate Fido group, bis (biphenyl) phosphide group, bis (naphthyl) phosphide group, bis (methylnaphthyl) phosphide group, bis (anthracenyl) phosphide group, and a diarylamino phosphide group such as bis (Fenantoniru) phosphido group.
- 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 30 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 or different, 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 compounds represented by the general formula (I) a transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following general formula (II) as a ligand is preferable. .
- X 1 represents a ⁇ -bonding ligand, and when plural X 1, a plurality of X 1 may be the same or different, may be crosslinked with other X 1 or Y 1. Specific examples of X 1 include the same examples as those exemplified in the description of X in formula (I).
- Y 1 represents a Lewis base, if Y 1 is plural, Y 1 may be the same or different, may be crosslinked with other Y 1 or X 1. Specific examples of Y 1 are the same as those exemplified in the description of Y in the general formula (I).
- R 4 to R 9 each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
- R 4 to R 9 may be the same or different from each other, and adjacent groups may be bonded to each other to form a ring. Among these, it is preferable that R 6 and R 7 form a ring and R 8 and R 9 form a ring.
- R 4 and R 5 a group containing a heteroatom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.
- R 4 and R 6 or R 6 and R 7 preferably form a ring
- R 5 and R 8 or R 8 and R 9 preferably form a ring
- a group containing a heteroatom such as oxygen, halogen, or silicon is preferable from the viewpoint of increasing the polymerization activity.
- the transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
- 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 (3-n-butylindenyl) zirconium dichloride, (1,2′-methylphenylsilylene) (2 , 1′-methylphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride (Sym.), (1,1′-ethylene) (2,2′-tetramethyldisylylene) bisindenylzirconium dichloride, etc. Can be mentioned.
- 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 defined as a Bronsted acid alone having a logarithm (pKa) of the reciprocal of the acid dissociation constant of ⁇ 10 or less, or a conjugate base of a combination of Bronsted acid and Lewis acid, or generally a super strong acid. Indicates a conjugate base of an 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 bringing the component (A) into contact with, for example, the component (B).
- 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 it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
- 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. If the particle size is small, fine powder in the polymer increases, and if 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 component (A) and the component (B) is mixed with the carrier.
- a method (ii) a method in which a 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 a normal sound wave, particularly preferably an ultrasonic wave is used.
- 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.
- a propylene homopolymer or a 1-butene homopolymer is produced by homopolymerizing propylene or 1-butene using the polymerization catalyst described above, 1-butene and propylene can be copolymerized to produce a 1-butene-propylene copolymer.
- 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 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, and the reaction pressure is preferably from atmospheric pressure to 3 MPa (gauge), more preferably from atmospheric pressure to 2 MPa (gauge). Examples of the method for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and 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 carried out, 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 polyolefin (2) used in the adhesive composition of the first embodiment of the present invention has a melting point (Tm) of 20 ° C. or higher and 160 ° C. or lower and a melting endotherm ( ⁇ H) of 5 J / g. It is 100 J / g or less. In the present invention, it is hereinafter also referred to as “crystalline polyolefin (2)”.
- Tm melting point
- ⁇ H melting endotherm
- the melting point of the crystalline polyolefin (2) is 20 ° C. or higher and 160 ° C. or lower, preferably 20 ° C.
- the melting endotherm ⁇ H of the crystalline polyolefin (2) is 5 J / g or more and 100 J / g or less, preferably 10 J / g or more and 100 J / g or less, more preferably 10 J / g or more. 90 J / g or less.
- the content of the crystalline polyolefin (2) in the adhesive composition of the first embodiment of the present invention is 5% by mass or more and 95% by mass or less, preferably from the viewpoint of adhesive strength and tackiness. It is 10 mass% or more and 90 mass% or less, More preferably, it is 15 mass% or more and 80 mass% or less, More preferably, it is 20 mass% or more and 70 mass% or less, More preferably, it is 25 mass% or more and 55 mass% or less.
- the crystalline polyolefin (2) used in the adhesive composition of the first embodiment of the present invention is not particularly limited, but is preferably a polymer of olefins having 2 to 12 carbon atoms, more preferably carbon.
- the crystalline polyolefin (2) may be a copolymer.
- the crystalline polyolefin (2) used in the adhesive composition of the first embodiment of the present invention preferably satisfies the following (b1) to (b2), and satisfies the following (b1) to (b4) It is more preferable.
- (B1) Mesopentad fraction (mmmm) is 20 to 60 mol%.
- (B2) The intrinsic viscosity [ ⁇ ] measured in tetralin at 135 ° C. is 0.01 to 2.0 deciliter / g.
- Racemic pentad fraction (rrrr) and (1-mmmm) satisfy the following relationship. [Rrrr / (1-mmmm)] ⁇ 0.1
- the amount of component (W25) eluted at 25 ° C. or lower in the temperature programmed chromatography is 20 to 100% by mass.
- the mesopentad fraction (mmmm) is the adhesive composition of the present invention.
- the amount is preferably 20 to 60 mol%, more preferably 40 to 58 mol%, and still more preferably 48 to 56 mol%.
- the method for measuring the mesopentad fraction (mmmm) is as described above.
- the intrinsic viscosity [ ⁇ ] of the crystalline polyolefin (2) used in the adhesive composition of the first embodiment of the present invention is from the viewpoint of reducing the adhesive residue of the adhesive composition of the present invention. It is preferably 0.01 to 2.0 deciliter / g, more preferably 0.1 to 1.0 deciliter / g, still more preferably 0.2 to 0.5 deciliter / g.
- the intrinsic viscosity is measured at 135 ° C. in tetralin using an Ubbelohde type viscosity tube.
- the relationship between (rrrr) and (1-mmmm) is such that rrrr / (1-mmmm) is preferably 0.1 or less, more preferably 0.06 or less, and still more preferably 0.04 from the viewpoint of adhesive residue. It is as follows.
- (rrrr) and (mmmm) here are calculated not as numerical values in mol% units but as normal ratios.
- the crystalline polyolefin (2) used in the adhesive composition according to the first embodiment of the present invention has a component amount (W25) eluting at 25 ° C. or lower in the temperature rising chromatography of 20 to 100% by mass. Some are preferable, 30 to 100% by mass is more preferable, 50 to 100% by mass is further preferable, and 60 to 100% by mass is particularly preferable.
- W25 is the amount (% by mass) of the component that is not adsorbed by the packing material at a TREF column temperature of 25 ° C. in the elution curve determined by temperature-programmed chromatography.
- W25 is an index indicating whether or not the polyolefin is soft. When this value is increased, it means that there are many components having a low elastic modulus and / or the non-uniformity of stereoregularity distribution is widened.
- Method for producing crystalline polyolefin (2) As the method for producing the polyolefin (2) used in the present invention, as in the method for producing the amorphous polyolefin (1), propylene or 1-butene is homopolymerized using a metallocene catalyst, and a propylene homopolymer or A method for producing a 1-butene homopolymer or a 1-butene-propylene copolymer obtained by copolymerizing 1-butene and propylene (further used, an ⁇ -olefin having 5 to 20 carbon atoms). The method of manufacturing is mentioned.
- the crystallinity of the polyolefin obtained can be controlled, and the crystalline polyolefin (2) can be obtained.
- the metallocene catalyst that can be used for the production of the crystalline polyolefin (2) include those described in JP-A No. 2000-256411.
- thermoplastic elastomer (3) having a glass transition temperature of 50 ° C. or higher and 150 ° C. or lower is used from the viewpoint of improving the holding power.
- the glass transition temperature of the thermoplastic elastomer (3) is preferably 80 ° C. or higher and 150 ° C. or lower.
- thermoplastic elastomer examples include ethylene-vinyl acetate copolymer, acrylic rubber, natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), Ethylene propylene rubber (EPM, EPDM), polyisobutylene, styrene-ethylene-butylene-styrene copolymer (SEBS), acrylonitrile-butadiene copolymer (NBR), styrene-butadiene-styrene block copolymer (SBS), styrene -Isoprene-styrene block copolymer (SIS), polyvinyl alkyl ether (for example, polyvinyl isobutyl ether) and the like. You may use a thermoplastic elastomer individually or in combination of 2 or more types.
- the content of the thermoplastic elastomer (3) in the adhesive composition of the second embodiment of the present invention is 5% by mass or more and 95% by mass or less, preferably from the viewpoint of adhesion and tackiness. It is 10 mass% or more and 90 mass% or less, More preferably, it is 15 mass% or more and 80 mass% or less, More preferably, it is 20 mass% or more and 70 mass% or less, More preferably, it is 25 mass% or more and 55 mass% or less.
- the adhesive composition of the first embodiment of the present invention may contain a thermoplastic elastomer.
- the content of the thermoplastic elastomer in the adhesive composition of the first embodiment of the present invention is preferably 0% by mass or more and 50% by mass from the viewpoint of coating properties because many thermoplastic elastomers have high viscosity. It is 0 mass% or less, More preferably, it is 0 mass% or more and 45 mass% or less, More preferably, it is 0 mass% or more and 40 mass% or less.
- the adhesive composition of the present invention may contain a tackifier.
- the tackifier include solid, semi-solid or liquid materials at room temperature made of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin and the like. You may use these individually or in combination of 2 or more types.
- tackifiers include Imabe P-125, P-100, P-90 (above, manufactured by Idemitsu Kosan Co., Ltd.), Umex 1001 (manufactured by Sanyo Chemical Industries, Ltd.), Hi-Rets T1115 (Mitsui Chemicals). Co., Ltd.), Clearon K100 (manufactured by Yasuhara Chemical Co., Ltd.), ECR227, Escorez 2101 (manufactured by Tonex Co., Ltd.), Alcon P100 (manufactured by Arakawa Chemical Co., Ltd.), Regalrez 1078 (manufactured by Hercules) ) (All are trade names).
- the content of the tackifier in the adhesive composition of the present invention is preferably 0% by mass or more and 50% by mass or less, more preferably 5% by mass or more, from the viewpoint of the balance between improvement in tackiness and adhesive residue. It is 50 mass% or less, More preferably, it is 10 mass% or more and 30 mass% or less.
- the adhesive composition of the present invention may contain a solvent.
- a solvent include ethyl acetate, acetone, tert-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether acetate, ethyl cellosolve, Ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, etc., and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, methoxybenzene, 1,2-dimethoxybenzene, hexane, cyclohexane, heptane, pentane
- organic solvents such as
- the adhesive composition of the present invention may contain an additive.
- additive conventionally known additives can be blended within a range that does not impair the effects of the present invention.
- foaming agents for example, foaming agents, anti-fogging stabilizers, ultraviolet absorbers, light stabilizers, heat stabilizers, antistatic agents. , Flame retardants, synthetic oils, waxes, electrical property improvers, oils (process oils), viscosity modifiers, anti-coloring agents, anti-fogging agents, pigments, dyes, plasticizers, softeners, anti-aging agents, hydrochloric acid absorbers , Chlorine scavengers, antioxidants and the like.
- the storage elastic modulus (E ′) at 25 ° C. obtained from the solid viscoelasticity measurement of the composition is 1 MPa or more and 200 MPa or less. A higher elastic modulus indicates a harder material.
- the storage elastic modulus E ′ at 25 ° C. near room temperature
- the holding power is insufficient and adhesive residue is generated.
- the adhesive strength and tack are insufficient.
- the present invention requires that the material be a moderately soft material having a storage elastic modulus E ′ of 1 MPa or more.
- the storage elastic modulus at 25 ° C. is preferably 3 MPa or more and 100 MPa or less, more preferably 5 MPa or more and 80 MPa or less.
- the storage elastic modulus (E ′) at 50 ° C. obtained from the solid viscoelasticity measurement of the composition is 1 MPa or more and 100 MPa or less. If the storage elastic modulus E ′ at 50 ° C. (high temperature) is too low, the holding power at high temperature is insufficient and adhesive residue is generated.
- 50 degreeC is a temperature which should be endured as an adhesive tape, and is required to be moderately soft at this temperature. From such a viewpoint, the storage elastic modulus at 50 ° C. is preferably 1 MPa or more and 80 MPa or less, more preferably 3 MPa or more and 60 MPa or less.
- the storage elastic modulus at 25 ° C. and the storage elastic modulus at 50 ° C. are approximately the same, and it is preferable that the storage elastic modulus does not vary in any temperature range.
- the solid viscoelasticity measurement in the present invention is performed by the following method. Using a viscoelasticity measuring device (product name: DMS 6100 (EXSTAR6000) manufactured by SII Nano Technology Co., Ltd.), measurement is performed under the following conditions in a nitrogen atmosphere. (Measurement condition) Measurement mode: Tensile mode Measurement temperature: Two points of -150 ° C to 230 ° C, 25 ° C and 50 ° C, are observed. Temperature increase rate: 5 ° C / min Measurement frequency: 1Hz Sample size: length 10mm, width 4mm, thickness 1mm (press molded product)
- the adhesive composition of this invention can be used conveniently for an adhesive tape or a protective film.
- the pressure-sensitive adhesive tape of the present invention uses the above-mentioned adhesive composition for an adhesive layer, and the adhesive composition may be applied directly on a support or on an auxiliary support. And then transferred onto the final support.
- the material of the support is not particularly limited, and for example, woven fabric, knit, scrim, non-woven fabric, laminate, net, film, paper, tissue, foam, foam film and the like can be used.
- Examples of the film include polypropylene, polyethylene, polybutene, oriented polyester, hard PVC and soft PVC, polyolefin foam, polyurethane foam, EPDM, and chloroprene foam.
- the support can be prepared chemically by priming or by a physical pretreatment such as corona prior to abutting the adhesive composition.
- the back side of the support can be provided with an anti-adhesive physical treatment or coating.
- 1,2-dichlorotetramethyldisilane (9.4 ml, 5.1 mmol) was added dropwise at 0 ° C.
- the solvent was distilled off, the residue was extracted with hexane (150 ml ⁇ 2 times), and 1,2-di (1H-inden-2-yl) -1,1, 2,2-Tetramethyldisilane was obtained as a white solid (15.4 grams, 44.4 mmol, 86% yield).
- the reaction mixture was stirred at room temperature for 1 hour and then evaporated to dryness, and the residue was extracted with hexane (150 milliliters) to give the bibridged ligand as a colorless oily liquid (14.2 grams, 37.9 millimoles). ). This was dissolved in diethyl ether (120 ml), n-butyllithium (2.6 mol / liter, 32 ml, 84 mmol) was added dropwise at 0 ° C., and the mixture was stirred for 1 hour at room temperature to precipitate a white powder.
- Synthesis example 4 [Complex D ((1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (3-neopentylindenyl) zirconium dichloride)]
- a Schlenk bottle was charged with 5.0 g (14.5 mmol) of (1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (indene) and 40 mL of ether, and n-BuLi (hexane solution, 2 .69M) 12.0 mL was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 8 hours.
- the mesodyad fraction (m) was calculated by the following formula.
- Mesodyad fraction (m) (integrated value of 40.4 to 39.9 ppm) / (integrated value of 40.4-39.9 ppm + integrated value of 40.7 to 40.4 ppm)
- ⁇ 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)
- Production Example 2 (Production of crystalline 1-butene homopolymer)
- Complex B (10 ⁇ mol / mL, 0.30 mL, 0.6 ⁇ mol) was used instead of Complex A, and N, N-dimethylanilinium tetrakis (pentafluoro) was used instead of MAO (2000 ⁇ mol) manufactured by Tosoh Finechem.
- 68 g of crystalline 1-butene homopolymer was obtained in the same manner as in Production Example 1 except that 1.8 ⁇ mol (10 ⁇ mol / mL, 0.18 mL) of a heptane slurry of phenyl) borate was used (polymer b).
- the physical properties of the polymer b were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- Production Example 3 (Production of crystalline 1-butene homopolymer)
- Complex C (10 ⁇ mol / mL, 0.04 mL, 0.4 ⁇ mol) was used instead of Complex A, and N, N-dimethylanilinium tetrakis (pentafluoro) was used instead of MAO (2000 ⁇ mol) manufactured by Tosoh Finechem.
- Phenyl) borate heptane slurry (10 ⁇ mol / mL, 0.12 mL, 1.2 ⁇ mol) was used in the same manner as in Production Example 1 except that the polymerization temperature was 52 ° C. Obtained (polymer c).
- the physical properties of the polymer c were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- the total pressure was set to 0.8 MPa by bringing propylene into the temperature at 60 ° C. while stirring. Then, after polymerization for 20 minutes, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 57 g of an amorphous 1-butene-propylene copolymer (Polymer d).
- the physical properties of the polymer d were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- Production Example 7 (1) Preparation of solid catalyst component A three-necked flask with a stirrer with an internal volume of 0.5 liter was replaced with nitrogen gas, and then 20 ml of dehydrated heptane, 4 g of diethoxymagnesium, and 1.6 g of dibutyl phthalate were added. In addition, the inside of the system was kept at 90 ° C., and 4 ml of titanium tetrachloride was added dropwise with stirring. Further, 111 ml of titanium tetrachloride was added dropwise, and the temperature was raised to 110 ° C. To the obtained solid phase part, 115 ml of titanium tetrachloride was added and reacted at 110 ° C. for another 2 hours.
- Production Example 8 In Production Example 5, 85 g of crystalline propylene homopolymer was obtained in the same manner as in Production Example 5 except that the polymerization temperature was changed to 65 ° C. (Polymer h). The physical properties of the polymer h were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- Production Example 9 In Production Example 5, 84 g of crystalline propylene homopolymer was obtained in the same manner as in Production Example 5 except that Complex E was used in place of Complex D (Polymer i). The physical properties of the polymer i were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- Production Example 10 In Production Example 9, 80 g of a crystalline propylene homopolymer was obtained in the same manner as in Production Example 9 except that the polymerization temperature was changed to 65 ° C. (Polymer j). The physical properties of the polymer j were measured in the same manner as in Production Example 1. The results are shown in Table 1.
- Example 1 (Preparation of adhesive composition and adhesive tape) 7.0 g of polymer a produced in Production Example 1 and 3.0 g of polymer e produced in Production Example 5 were placed in a 50 mL sample bottle, heated at 180 ° C. for 30 minutes and melted, and then with a metal spoon. Thorough mixing and stirring were performed to prepare an adhesive composition. The obtained adhesive composition was sandwiched between a PET film for a substrate (trade name: Lumirror S10, thickness 50 ⁇ m, manufactured by Toray Industries, Inc.) and a release PET film, and heated at 110 ° C. After coating so that the thickness of the pressure-sensitive adhesive layer was about 30 ⁇ m, the release PET film was peeled off and stabilized at room temperature for one day to obtain a test piece of pressure-sensitive adhesive tape.
- a PET film for a substrate trade name: Lumirror S10, thickness 50 ⁇ m, manufactured by Toray Industries, Inc.
- Measurement of solid viscoelasticity Using a viscoelasticity measuring device (trade name: DMS 6100 (EXSTAR6000) manufactured by SII Nano Technology Co., Ltd.), measurement was performed under the following conditions under a nitrogen atmosphere. ⁇ Measurement conditions> Measurement mode: Tensile mode Measurement temperature: Two points of -150 ° C to 230 ° C, 25 ° C and 50 ° C, were observed. Temperature increase rate: 5 ° C / min Measurement frequency: 1Hz Sample size: length 10mm, width 4mm, thickness 1mm (press molded product)
- the holding force was measured according to JIS Z 0237.
- the pressure-sensitive adhesive tape on which the pressure-sensitive adhesive layer is formed is bonded to and bonded to a PET film for adherend (trade name: Lumirror S10, thickness 50 ⁇ m) so that the adhesion area is 25 mm ⁇ 25 mm.
- the part was applied with a rubber roller twice with a force of 2.0 kg / 25 mm and adhered.
- the obtained test piece was applied with a weight of 1 kg in an environment of a temperature of 50 ° C. and a humidity of 30%, and the time for the weight to fall from the adherend was measured. The results are shown in Table 2.
- Example 2 In Example 1, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 1 except that the polymer c produced in Production Example 3 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- Example 3 In Example 1, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 1 except that the polymer b produced in Production Example 2 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- Example 4 6.0 g of polymer a produced in Production Example 1, 2.0 g of polymer b produced in Production Example 2, and 2.0 g of tackifier (made by Idemitsu Kosan Co., Ltd., trade name: Imabe P-100) The mixture was placed in a 50 mL sample bottle, heated at 180 ° C. for 30 minutes to melt, and then sufficiently mixed and stirred with a metal spoon to prepare an adhesive composition.
- Table 2 shows the evaluation results of the test pieces. Except having used the obtained adhesive composition, it carried out similarly to Example 1, and obtained the adhesive tape test piece. Table 2 shows the evaluation results of the test pieces.
- Example 5 In Example 1, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 1 except that the polymer d produced in Production Example 4 was used instead of the polymer a. Table 2 shows the evaluation results of the test pieces.
- Example 6 1.5 g of polymer a produced in Production Example 1, 7.0 g of polymer e produced in Production Example 5, and 1.5 g of process oil (trade name: Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.) The mixture was placed in a 50 mL sample bottle, heated at 180 ° C. for 30 minutes to melt, and then sufficiently mixed and stirred with a metal spoon to prepare an adhesive composition.
- Table 2 shows the evaluation results of the test pieces. Except having used the obtained adhesive composition, it carried out similarly to Example 1, and obtained the adhesive tape test piece. Table 2 shows the evaluation results of the test pieces.
- Example 7 In Example 5, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 5 except that the polymer f produced in Production Example 6 was used instead of the polymer d. Table 2 shows the evaluation results of the test pieces.
- Example 8 In Example 7, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 7 except that the polymer h produced in Production Example 8 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- Example 9 In Example 7, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 7 except that the polymer i produced in Production Example 9 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- Example 10 In Example 7, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 7 except that the polymer j produced in Production Example 10 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- Example 1 an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 1 except that the blending amount of the polymer a was 10.0 g and the polymer e was not used. Table 2 shows the evaluation results of the test pieces.
- Example 2 an adhesive composition was used in the same manner as in Example 1 except that a tackifier (trade name: Imabe P-100, manufactured by Idemitsu Kosan Co., Ltd.) was used instead of the polymer e. And an adhesive tape test piece were obtained. Table 2 shows the evaluation results of the test pieces.
- a tackifier trade name: Imabe P-100, manufactured by Idemitsu Kosan Co., Ltd.
- Comparative Example 3 In Comparative Example 1, an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Comparative Example 1 except that the polymer f produced in Production Example 6 was used instead of the polymer a. Table 2 shows the evaluation results of the test pieces.
- Example 7 an adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 7 except that the polymer g produced in Production Example 7 was used instead of the polymer e. Table 2 shows the evaluation results of the test pieces.
- the adhesive composition of the present invention can be used in the field of pressure-sensitive adhesive tapes.
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Abstract
Description
[1](1)示差走査型熱量計(DSC)による融点が観測されないか又は融点が20℃未満であり、かつ、ΔHが5J/g未満であるポリオレフィン5~95質量%と、
(2)融点が20℃以上160℃以下であり、かつ、ΔHが5J/g以上100J/g以下であるポリオレフィン95~5質量%と
を含む粘接着剤組成物であって、
該組成物の固体粘弾性測定から得られる25℃における貯蔵弾性率が1MPa以上200MPa以下であり、50℃における貯蔵弾性率が1MPa以上100MPa以下である、粘接着剤組成物。
[2](1)示差走査型熱量計(DSC)による融点が観測されないか又は融点が20℃未満であり、かつ、ΔHが5J/g未満であるポリオレフィン5~95質量%と、
(3)ガラス転移温度が50℃以上150℃以下である熱可塑性エラストマー95~5質量%と
を含む粘接着剤組成物であって、
該組成物の固体粘弾性測定から得られる25℃における貯蔵弾性率が1MPa以上200MPa以下であり、50℃における貯蔵弾性率が1MPa以上100MPa以下である、粘接着剤組成物。
[3]前記ポリオレフィン(1)が、炭素数2~12のオレフィンの重合体である、上記[1]又は[2]に記載の粘接着剤組成物。
[4]前記ポリオレフィン(1)が、炭素数3~12のα-オレフィンの重合体である、上記[1]~[3]のいずれかに記載の粘接着剤組成物。
[5]前記ポリオレフィン(1)が、1-ブテン単独重合体、プロピレン単独重合体及び1-ブテン-プロピレン共重合体からなる群から選ばれる少なくとも1種である、上記[1]~[4]のいずれかに記載の粘接着剤組成物。
[6]前記ポリオレフィン(1)が、GPC法により測定した重量平均分子量(Mw)が5,000~1,000,000である、上記[1]~[5]のいずれかに記載の粘接着剤組成物。
[7]粘着性付与材を更に含む、上記[1]~[6]のいずれかに記載の粘接着剤組成物。
[8]上記[1]~[7]のいずれかに記載の粘接着剤組成物を粘接着層に用いた粘着テープ。
以下、上記[1]に記載の粘接着剤組成物を「第1の実施形態の粘接着剤組成物」といい、上記[2]に記載の粘接着剤組成物を「第2の実施形態の粘接着剤組成物」という。
本発明の第1の実施形態の粘接着剤組成物は、特定の非晶質ポリオレフィン(1)と、特定の結晶性ポリオレフィン(2)とを含むことを特徴とする。
また、本発明の第2の実施形態の粘接着剤組成物は、特定の非晶質ポリオレフィン(1)と、特定の熱可塑性エラストマー(3)とを含むことを特徴とする。
これらのうち、粘着力及び保持力が高く、かつ糊残りがなく、塗布性に優れるという観点からは、第1の実施形態の粘着材組成物が好ましい。
その効果の作用機序については定かではないが以下のように推定される。結晶性が制御されたポリマー材料同士を適正に混合することにより、組成物中に結晶点が生じて組成物全体の保持力が向上すると考えられる。
また、特定の非晶質ポリオレフィン(1)を含有することで粘着力が向上する一方、特定の結晶性ポリオレフィン(2)又は特定の熱可塑性エラストマー(3)を含有することで、本発明の粘接着剤組成物は、糊残りの発生を抑制することができると考えられる。
本発明に用いられるポリオレフィン(1)は、示差走査型熱量計(DSC)による融点(Tm)が観測されないか又は融点が20℃未満であり、かつ、融解吸熱量(ΔH)が5J/g未満である。本発明では、以下「非晶質ポリオレフィン(1)」ともいう。融点Tm及び融解吸熱量ΔHは、実施例に記載の方法で測定される。
本発明において、融点が示差走査熱量計(DSC)で観測されないとは、DSC測定において結晶化速度が極めて遅い、又は結晶化が全く起こらないため、結晶融解ピークを実質的に観測できないことをいう。なお、融点が観測されない場合、ΔHも実質的に観測できないときが多い。ΔHが観測できないときもΔHは5J/g未満とみなす。すなわち、当該ΔHは、観測されないか又は5J/g未満である。
低温での粘着力を向上させる観点からは、プロピレン単独重合体よりもガラス転移温度Tgの低い1-ブテン単独重合体を用いる方が好ましい。
(a1)メソペンタッド分率(mmmm)が3~40モル%である。またはメソダイアッド分率(m)が30~95モル%である。
(a2)1,3-結合分率及び1,4-結合分率の合計が0.3モル%未満である。
(a3)2,1-結合分率が0.3モル%未満である。
(a4)ゲルパーミエイションクロマトグラフ(GPC)法により測定した分子量分布(Mw/Mn)が4.0以下である。
(a5)GPC法により測定した重量平均分子量(Mw)が5,000~1,000,000である。
13C-NMRスペクトルの測定は、下記の装置及び条件にて行う。
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:230mg/ミリリットル
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:10000回
1,3-結合分率=(D/2)/(A+B+C+D)×100(モル%)
2,1-結合分率=[(A+B)/2]/(A+B+C+D)×100(モル%)
A:15~15.5ppmの積分値
B:17~18ppmの積分値
C:19.5~22.5ppmの積分値
D:27.6~27.8ppmの積分値
1,4-結合分率=E/(A+B+C+D+E)×100(モル%)
2,1-結合分率={(A+B+D)/3}/(A+B+C+D)×100(モル%)
A:29.0~28.2ppmの積分値
B:35.4~34.6ppmの積分値
C:38.3~36.5ppmの積分値
D:43.6~42.8ppmの積分値
E:31.1ppmの積分値
本発明に用いられる非晶質ポリオレフィン(1)が単独重合体である場合、そのメソペンタッド分率(mmmm)は、本発明の粘接着剤組成物が繰り返し粘接着する観点から、好ましくは3~40モル%、より好ましくは3~25モル%、更に好ましくは3~10モル%である。
また、本発明に用いられる非晶質ポリオレフィン(1)が1-ブテン-プロピレン共重合体である場合、そのメソダイアッド分率(m)は、耐熱性及び粘着性のバランスの観点から、好ましくは30~95モル%、より好ましくは40~90モル%、更に好ましくは50~85モル%である。
上記1-ブテン-プロピレン共重合体は、ランダム共重合体であることが好ましい。
1-ブテン-プロピレン共重合体における、各構造単位は、上述の13C-NMRスペクトルの測定結果より、下記のように算出できる。
[ダイアッド連鎖強度]
a(プロピレン-プロピレン連鎖):48.0~46.2ppmの積分値
b(プロピレン-ブテン連鎖):44.4~43.0ppmの積分値
c(ブテン-ブテン連鎖):40.8~39.8ppmの積分値
[ダイアッド連鎖分率(モル%)]
d(プロピレン-プロピレン連鎖分率)=a/(a+b+c)×100(モル%)
e(プロピレン-ブテン連鎖分率)=b/(a+b+c)×100(モル%)
f(ブテン-ブテン連鎖分率)=c/(a+b+c)×100(モル%)
[共重合比(モル%)]
プロピレン単位共重合比=d+e/2
1-ブテン単位共重合比=f+e/2
メソダイアッド分率(m)=(40.4~39.9ppmの積分値)/(40.4~39.9ppmの積分値+40.7~40.4ppmの積分値)
本発明に用いられる非晶質ポリオレフィン(1)は、1,3-結合分率及び1,4-結合分率の合計が好ましくは0.3モル%未満であり、より好ましくは0.1モル%未満であり、更に好ましくは0モル%である。上記範囲内であると、低温での流動性が良好となり、低温接着性が改善し、また、粘着性付与材との相溶性が良好となる。
上記「1,3-結合分率及び1,4-結合分率の合計」とは、本発明に用いられる非晶質ポリオレフィン(1)が、プロピレン単独重合体である場合には1,3-結合分率を意味し、1-ブテン単独重合体である場合には1,4-結合分率を意味し、プロピレン-1-ブテン共重合体である場合には1,3-結合分率及び1,4-結合分率の合計を意味する。
1,3-結合分率及び1,4-結合分率の制御は、後述の2,1-結合分率の制御と同様にして、主触媒の構造や重合条件によって行われる。
本発明に用いられる非晶質ポリオレフィン(1)は、2,1-結合分率が好ましくは0.3モル%未満であり、より好ましくは0.1モル%未満であり、更に好ましくは0モル%である。上記範囲内であると、低温での流動性が良好となり、低温接着性が改善し、また、粘着性付与材との相溶性が良好となる。
2,1-結合分率の制御は、主触媒の構造や重合条件によって行われる。具体的には、主触媒の構造が大きく影響し、主触媒の中心金属周辺のモノマーの挿入場を狭くすることで2,1-結合を制御することができ、逆に挿入場を広くすることで2,1-結合を増やすことができる。例えばハーフメタロセン型と呼ばれる触媒は中心金属周辺の挿入場が広いため、2,1-結合や長鎖分岐などの構造が生成しやすく、ラセミ型のメタロセン触媒であれば、2,1-結合を抑制することが期待できるが、ラセミ型の場合は立体規則性が高くなり、本発明で示しているような非晶質ポリマーを得ることは困難である。例えば後述するようなラセミ型でも2重架橋したメタロセン触媒で3位に置換基を導入し、中心金属の挿入場を制御することで非晶かつ2,1-結合の非常に少ない重合体を得ることができる。
本発明に用いられる非晶質ポリオレフィン(1)は、GPC法により測定した分子量分布(Mw/Mn)が好ましくは4以下、より好ましくは3.5以下、更に好ましくは3.0以下である。分子量分布(Mw/Mn)が4以下であると、粘接着剤原料に用いた場合に糊残りが低減される。
本発明に用いられる非晶質ポリオレフィン(1)は、GPC法により測定した重量平均分子量(Mw)が好ましくは5,000~1,000,000、より好ましくは9,000~200,000、更に好ましくは20,000~100,000である。Mwが5,000以上であると、べたつきが低減される。またMwが1,000,000以下であると、流動性が向上し、成形性(塗工性)が良好となる。
<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)
本発明に用いられる非晶質ポリオレフィン(1)の製造方法としては、メタロセン触媒を用いて、プロピレン又は1-ブテンを単独重合してプロピレン単独重合体又は1-ブテン単独重合体を製造する方法や、1-ブテンとプロピレン(さらに必要に応じて用いられる炭素数5~20のα-オレフィン)とを共重合して1-ブテン-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、プロピレン又は1-ブテンを単独重合させる方法、又は1-ブテンとプロピレン(さらに必要に応じて用いられる炭素数5~20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。
X1はσ結合性の配位子を示し、X1が複数ある場合、複数のX1は同じでも異なっていてもよく、他のX1又はY1と架橋していてもよい。このX1の具体例としては、一般式(I)のXの説明で例示したものと同じものを挙げることができる。
Y1はルイス塩基を示し、Y1が複数ある場合、複数のY1は同じでも異なっていてもよく、他のY1又はX1と架橋していてもよい。このY1の具体例としては、一般式(I)のYの説明で例示したものと同じものを挙げることができる。R4~R9はそれぞれ水素原子,ハロゲン原子,炭素数1~20の炭化水素基,炭素数1~20のハロゲン含有炭化水素基,珪素含有基又はヘテロ原子含有基を示すが、その少なくとも一つは水素原子でないことが必要である。また、R4~R9はたがいに同一でも異なっていてもよく、隣接する基同士がたがいに結合して環を形成していてもよい。なかでも、R6とR7は環を形成していること及びR8とR9は環を形成していることが好ましい。R4及びR5としては、酸素、ハロゲン、珪素等のヘテロ原子を含有する基が重合活性が高くなり好ましい。別の好ましい形態として、R4とR6あるいはR6とR7は環を形成していること及びR5とR8あるいはR8とR9は環を形成していることが好ましい。R4及びR5、R7、R9が環を形成していない場合の置換基としては、重合活性が高くなる点で、酸素、ハロゲン、珪素等のヘテロ原子を含有する基が好ましい。
この二重架橋型ビスシクロペンタジエニル誘導体を配位子とする遷移金属化合物は、配位子間の架橋基にケイ素を含むものが好ましい。
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(3-n-ブチルインデニル)ジルコニウムジクロライド、(1,2’-メチルフェニルシリレン)(2,1’-メチルフェニルシリレン)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(Sym.)、(1,1’-エチレン)(2,2’-テトラメチルジシリレン)ビス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わせの共役塩基、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。
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)さらに好ましくは常圧~2MPa(gauge)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の実施態様の粘接着剤組成物に用いられるポリオレフィン(2)は、融点(Tm)が20℃以上160℃以下であり、かつ、融解吸熱量(ΔH)が5J/g以上100J/g以下である。本発明では、以下「結晶性ポリオレフィン(2)」ともいう。融点Tm及び融解吸熱量ΔHは、実施例に記載の方法で測定される。
(b1)メソペンタッド分率(mmmm)が20~60モル%である。
(b2)テトラリン中135℃にて測定した極限粘度[η]が0.01~2.0デシリットル/gである。
(b3)ラセミペンタッド分率(rrrr)と(1-mmmm)とが下記の関係を満たす。
[rrrr/(1-mmmm)]≦0.1
(b4)昇温クロマトグラフィーにおける25℃以下で溶出する成分量(W25)が20~100質量%である。
本発明の第1の実施態様の粘接着剤組成物に用いられる結晶性ポリオレフィン(2)が単独重合体である場合、そのメソペンタッド分率(mmmm)は、本発明の粘接着剤組成物の糊残りが少なくなる観点から、好ましくは20~60モル%、より好ましくは40~58モル%、更に好ましくは48~56モル%である。メソペンタッド分率(mmmm)の測定方法は、上述したとおりである。
本発明の第1の実施態様の粘接着剤組成物に用いられる結晶性ポリオレフィン(2)の極限粘度[η]は、本発明の粘接着剤組成物の糊残りが少なくなる観点から、好ましくは0.01~2.0デシリットル/g、より好ましくは0.1~1.0デシリットル/g、更に好ましくは0.2~0.5デシリットル/gである。ここで、極限粘度は、ウベローデ型粘度管を用いてテトラリン中135℃にて測定される。
本発明の第1の実施態様の粘接着剤組成物に用いられる結晶性ポリオレフィン(2)のラセミペンタッド分率(rrrr)と(1-mmmm)との関係は、糊残りの観点から、rrrr/(1-mmmm)が、好ましくは0.1以下、より好ましくは0.06以下、更に好ましくは0.04以下である。なお、ここでの(rrrr)及び(mmmm)は、モル%単位の数値ではなく、通常の比率として計算する。
本発明の第1の実施態様の粘接着剤組成物に用いられる結晶性ポリオレフィン(2)は、の昇温クロマトグラフィーにおける25℃以下で溶出する成分量(W25)が20~100質量%であるものが好ましく、30~100質量%がより好ましく、50~100質量%が更に好ましく、60~100質量%が特に好ましい。W25とは、昇温クロマトグラフィーにより測定して求めた溶出曲線におけるTREFのカラム温度25℃において充填剤に吸着されないで溶出する成分の量(質量%)である。W25は、ポリオレフィンが軟質であるか否かを表す指標である。この値が大きくなると弾性率の低い成分が多くなったり、及び/又は立体規則性分布の不均一さが広がっていることを意味する。
本発明に用いられるポリオレフィン(2)の製造方法としては、非晶質ポリオレフィン(1)の製造方法と同様に、メタロセン触媒を用いて、プロピレン又は1-ブテンを単独重合してプロピレン単独重合体又は1-ブテン単独重合体を製造する方法や、1-ブテンとプロピレン(さらに必要に応じて用いられる炭素数5~20のα-オレフィン)とを共重合して1-ブテン-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、結晶性ポリオレフィン(2)を得ることができる。
結晶性ポリオレフィン(2)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2の実施態様の粘接着剤組成物では、保持力向上の観点から、ガラス転移温度が50℃以上150℃以下である熱可塑性エラストマー(3)が用いられる。熱可塑性エラストマー(3)のガラス転移温度は、好ましくは80℃以上150℃以下である。
(粘着性付与材)
本発明の粘接着剤組成物は、粘着性付与材を含有してもよい。
粘着性付与材としては、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、ブテン系重合体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。
粘着性付与材の市販品としては、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)等を挙げることができる(いずれも商品名)。
本発明の粘接着剤組成物における粘着性付与材の含有量は、粘着性向上と糊残りとのバランスの観点から、好ましくは0質量%以上50質量%以下、より好ましくは5質量%以上50質量%以下、更に好ましくは10質量%以上30質量%以下である。
本発明の粘接着剤組成物は溶媒を含有していてもよい。その具体例としては、酢酸エチル、アセトン、tert-ブチルアルコール、グリセリン、エチレングリコール、トリエチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセタート、ジエチレングリコールジメチルエーテル、エチレングリコールジメチルエーテルアセタート、エチルセルソルブ、エチルセルソルブアセタート、ブチルセルソルブ、ブチルセルソルブアセタート等や、ベンゼン、トルエン、キシレン、エチルベンゼン、メトキシベンゼン、1,2-ジメトキシベンゼン、ヘキサン、シクロヘキサン、ヘプタン、ペンタンなどの芳香族炭化水素類などの有機溶媒を挙げることができる。
本発明の粘接着剤組成物は、添加剤を含有してもよい。
添加剤としては、従来公知の添加剤を本発明の効果を阻害しない範囲で配合することができ、例えば、発泡剤、耐侯安定剤、紫外線吸収剤、光安定剤、耐熱安定剤、帯電防止剤、難燃剤、合成油、ワックス、電気的性質改良剤、オイル(プロセスオイル)、粘度調製剤、着色防止剤、防曇剤、顔料、染料、可塑剤、軟化剤、老化防止剤、塩酸吸収剤、塩素捕捉剤、酸化防止剤等が挙げられる。
(25℃における貯蔵弾性率)
本発明の粘接着剤組成物は、該組成物の固体粘弾性測定から得られる25℃における貯蔵弾性率(E’)が1MPa以上200MPa以下である。弾性率が高いほど固い材料であることを示す。25℃(室温付近)での貯蔵弾性率E’が低すぎると、保持力が不足するとともに糊残りが発生する一方、高すぎると粘着力やタックが不足する。ここで、25℃は、粘着テープとして使用する際の温度であり、この温度において固すぎると接着しないので、本発明では貯蔵弾性率E’が200MPa以下の柔らかい材料であることが求められる。一方、柔らかすぎると糊残りが出るので、本発明では貯蔵弾性率E’が1MPa以上の適度に柔らかい材料であることが求められる。
このような観点から、25℃における貯蔵弾性率は、好ましくは3MPa以上100MPa以下、より好ましくは5MPa以上80MPa以下である。
本発明の粘接着剤組成物は、該組成物の固体粘弾性測定から得られる50℃における貯蔵弾性率(E’)が1MPa以上100MPa以下である。50℃(高温)での貯蔵弾性率E’が低すぎると、高温での保持力が不足するとともに糊残りが発生する一方、高すぎると粘着力やタックが不足する。ここで、50℃は、粘着テープとして耐えるべき温度であり、この温度において適度に柔らかいことが求められる。
このような観点から、50℃における貯蔵弾性率は、好ましくは1MPa以上80MPa以下、より好ましくは3MPa以上60MPa以下である。
粘弾性測定装置(エスアイアイ・ナノテクノロジー(株)製、商品名:DMS 6100(EXSTAR6000))を用いて、窒素雰囲気下で以下の条件で測定を行う。
(測定条件)
測定モード:引張モード
測定温度:-150℃~230℃のうち、25℃及び50℃の2点を観測する。
昇温速度:5℃/min
測定周波数:1Hz
試料サイズ:長さ10mm、幅4mm、厚さ1mm(プレス成形品)
本発明の粘接着剤組成物は、粘着テープやプロテクトフィルムに好適に使用することができる。
本発明の粘着テープは、上記粘接着剤組成物を粘接着層に用いたものであり、粘接着剤組成物は、支持体上に直接塗布してもよく、または補助支持体上に塗着し、それから最終的な支持体上に転写してもよい。支持体の材料は特に限定されないが、例えば、織物、ニット、スクリム、不織布、ラミネート、ネット、フィルム、紙、ティシュー、発泡体、発泡フィルム等を使用することができる。フィルムとしては、ポリプロピレン、ポリエチレン、ポリブテン、配向ポリエステル、硬質PVCおよび軟質PVC、ポリオレフィン発泡体、ポリウレタン発泡体、EPDM、クロロプレン発泡体等が挙げられる。
支持体は、粘接着剤組成物と突き合わせる前に、下塗りによって化学的に、またはコロナなどの物理的前処理によって、準備することができる。支持体の背面には、抗接着性の物理的処理またはコーティングを施すことができる。
[錯体A((1,1’-エチレン)(2,2’-テトラメチルジシリレン)ビスインデニルジルコニウムジクロライド)の製造]
500ミリリットル2口フラスコにマグネシウム(12グラム,500ミリモル)及びテトラヒドロフラン(30ミリリットル)を投入し、1,2-ジブロモエタン(0.2ミリリットル)を滴下することでマグネシウムを活性化した。ここへテトラヒドロフラン(150ミリリットル)に溶解させた2-ブロモインデン(20グラム,103ミリモル)を滴下し、室温で1時間撹拌した。その後、1,2-ジクロロテトラメチルジシラン(9.4ミリリットル,5.1ミリモル)を0℃で滴下した。反応混合物を室温で1時間撹拌した後、溶媒を留去し、残渣をヘキサン(150ミリリットル×2回)で抽出し、1,2-ジ(1H-インデン-2-イル)-1,1,2,2-テトラメチルジシランを白色固体として得た(15.4グラム,44.4ミリモル,収率86%)。
これをジエチルエーテル(100ミリリットル)に溶解し、0℃でn-ブチルリチウム(2.6モル/リットル,38ミリリットル,98ミリモル)を滴下し、室温で1時間撹拌したところ白色粉末が沈殿した。上澄みを除去し、固体をヘキサン(80ミリリットル)で洗浄して、リチウム塩を白色粉末状固体として得た(14.6グラム,33.8ミリモル,76%)。
これをテトラヒドロフラン(120ミリリットル)に溶解させ、-30℃で1,2‐ジブロモエタン(2.88ミリリットル,33.8ミリモル)を滴下した。反応混合物を室温で1時間撹拌した後、乾固し、残渣をヘキサン(150ミリリットル)で抽出することにより2架橋配位子を無色オイル状液体として得た(14.2グラム,37.9ミリモル)。
これをジエチルエーテル(120ミリリットル)に溶解させ、0℃でn-ブチルリチウム(2.6モル/リットル,32ミリリットル,84ミリモル)を滴下し、室温で1時間撹拌したところ白色粉末が沈殿した。上澄みを除去し、固体をヘキサン(70ミリリットル)で洗浄することにより2架橋配位子のリチウム塩を白色粉末として得た(14.0グラム,31ミリモル,収率81%)。
得られた2架橋配位子のリチウム塩(3.00グラム,6.54ミリモル)のトルエン(30ミリリットル)懸濁液に、-78℃で四塩化ジルコニウム(1.52グラム,6.54ミリモル)のトルエン(30ミリリットル)懸濁液をキャヌラーにより滴下した。反応混合物を室温で2時間撹拌した後、上澄み液を分離し、さらに残渣をトルエンで抽出した。
減圧下、上澄み液及び抽出液の溶媒を留去して乾固することにより黄色固体として下記式(1)に示す(1,1’-エチレン)(2,2’-テトラメチルジシリレン)ビスインデニルジルコニウムジクロライドを得た(2.5グラム,4.7ミリモル,収率72%)。
1H-NMR(CDCl3):δ0.617(s,6H,-SiMe2-),0.623(s,6H,-SiMe2-),3.65-3.74,4.05-4.15(m,4H,CH2CH2),6.79(s,2H,CpH),7.0-7.5(m,8H,Aromatic-H)
[錯体B(ジメチルシリレンビス(2-メチルベンゾインデニル)ジルコニウムジクロリド)]
文献(Organometallics,1994,13,954)の記載に従って下記(ジメチルシリレンビス(2-メチルベンゾインデニル)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(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D((1,2’-ジメチルシリレン)(2’,1-ジメチルシリレン)ビス(3-ネオペンチルインデニル)ジルコニウムジクロリド)]
シュレンク瓶に(1,2’-ジメチルシリレン)(2’,1-ジメチルシリレン)ビス(インデン)5.0g(14.5mmol)とエーテル40mLを入れ、0℃でn-BuLi(ヘキサン溶液,2.69M)12.0mLを滴下した後、そのまま室温まで上げて8時間撹拌した。沈殿部をろ別し、ヘキサン30mLで洗浄、減圧乾燥してリチウム塩の白色固体を得た。これをTHF40mLに溶解し、1-ヨード-2,2-ジメチルプロパン4.9mL(36.6mmol)を滴下し、4時間加熱還流した。水20mLによる加水分解後、分液し有機層を乾燥、溶媒を留去することにより(1,2’-ジメチルシリレン)(2’,1-ジメチルシリレン)ビス(3-ネオペンチルインデン)を明橙色油状物として7.1g(14.7mmol)得た。
次に、窒素気流下で、シュレンク瓶に(1,2’-ジメチルシリレン)(2’,1-ジメチルシリレン)ビス(3-ネオペンチルインデン)7.1g(14.7mmol)とエーテル40mLを添加した。0℃に冷却し、n-BuLi(ヘキサン溶液,2.69M)を12.0mL(32.3mmol)加えた後、室温で2時間撹拌した。上澄みをろ別し、得られた固体をヘキサン40mLで洗浄、乾燥することによりリチウム塩を得た。
このリチウム塩にトルエン50mLを加え、-78℃に冷却し、ここへ予め-78℃に冷却しておいた四塩化ジルコニウム3.4g(14.7mmol)のトルエン懸濁液を添加する。室温で8時間撹拌後、上澄み液をろ別し黄色沈殿物をジクロロメタン65mLで抽出、ろ過後溶媒留去することにより(1,2’-ジメチルシリレン)(2’,1-ジメチルシリレン)ビス(3-ネオペンチルインデニル)ジルコニウムジクロリドを0.7g(1.1mmol)得た。
1H NMR(CDCl3):δ0.99(6H,SiMe2),1.06(6H,SiMe2),0.85(18H,C(CH3)3),2.50,3.02(4H,CH2),7.1-7.5(8H,Aromatic-H)
[錯体E((1,2’-Ph2Si)(2’,1-Ph2Si)ビス(インデニル)ジルコニウムジクロリド)]
文献(SYNTHESIS,2006,9,1408)に記載の方法に基づき、ビス(2-インデニル)ジフェニルシランを合成した。
ビス(2-インデニル)ジフェニルシラン7.64g(18.5mmol)にエーテル100mLを加え0℃に冷却し、ここへn-BuLi(ヘキサン溶液,2.69M)を13.8mL滴下した。室温で4時間撹拌した後白色沈殿をろ別し乾燥した。この白色固体をTHF70mLに溶解させ、氷浴で冷却した。ここへジフェニルジクロロシラン3.6mL(17.3mmol)を、シリンジを用いて滴下した。反応混合物を室温に戻し、反応容器にジムロート冷却管を取り付け、7時間加熱還流を行なう。室温に戻し、生成した白色沈殿をろ別後、乾燥することにより(1,2’-Ph2Si)-(2’,1-Ph2Si)ビス(インデン)3.26g(5.5mmol)を得た。
ここへ、エーテル20mL,THF20mLを加え-78℃に冷却した。n-BuLi(ヘキサン溶液,2.69M)4.1mLを滴下後室温で2時間撹拌した。生成した白色固体をろ別し、減圧乾燥した。この白色固体にトルエン25mLを添加し-78℃に冷却し、ここへ、別に-78℃に冷却した四塩化ジルコニウム1.3g(5.5mmol)のトルエン15mL懸濁液を添加した。室温で8時間撹拌後上澄み液をろ別し、黄色沈殿をジクロロメタン30mLで抽出した。抽出液を濃縮することにより黄色固体として(1,2’-Ph2Si)(2’,1-Ph2Si)ビス(インデニル)ジルコニウムジクロリドを得た。
1H NMR(CDCl3):δ6.74-7.82(30H,Aromatic-H)
(非晶質1-ブテン単独重合体の製造)
加熱乾燥した1リットルオートクレーブに、ヘプタン(200mL)、トリイソブチルアルミニウム(2M、0.2mL、0.4mmol)、ブテン-1(200mL)、錯体Aのヘプタンスラリー(10μmol/mL、0.20mL、2.0μmol)、東ソーファインケム社製MAO(2000μmol)を加え、さらに水素0.1MPa導入した。撹絆しながら温度を70℃にした後、30分間重合した。重合反応終了後、5mLのエタノールで重合を停止し、反応物を減圧下、乾燥することにより、非晶質1-ブテン単独重合体82gを得た(重合体a)。
上記重合体aについて、下記の装置及び条件にて13C-NMRスペクトルの測定を行い、メソペンタッド分率(mmmm)、メソダイアッド分率(m)、1,3-結合分率、1,4-結合分率及び2,1-結合分率を求めた。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:230mg/ミリリットル
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:10000回
[ダイアッド連鎖強度]
a(プロピレン-プロピレン連鎖):48.0~46.2ppmの積分値
b(プロピレン-ブテン連鎖):44.4~43.0ppmの積分値
c(ブテン-ブテン連鎖):40.8~39.8ppmの積分値
[ダイアッド連鎖分率(モル%)]
d(プロピレン-プロピレン連鎖分率)=a/(a+b+c)×100(モル%)
e(プロピレン-ブテン連鎖分率)=b/(a+b+c)×100(モル%)
f(ブテン-ブテン連鎖分率)=c/(a+b+c)×100(モル%)
[共重合比(モル%)]
プロピレン単位共重合比=d+e/2
1-ブテン単位共重合比=f+e/2
メソダイアッド分率(m)=(40.4~39.9ppmの積分値)/(40.4-39.9ppmの積分値+40.7~40.4ppmの積分値)
<プロピレン系重合体の場合>
1,3-結合分率=(D/2)/(A+B+C+D)×100(モル%)
2,1-結合分率=[(A+B)/2]/(A+B+C+D)×100(モル%)
A:15~15.5ppmの積分値
B:17~18ppmの積分値
C:19.5~22.5ppmの積分値
D:27.6~27.8ppmの積分値
<1-ブテン系重合体の場合>
1,4-結合分率=E/(A+B+C+D+E)×100(モル%)
2,1-結合分率={(A+B+D)/3}/(A+B+C+D)×100(モル%)
A:29.0~28.2ppmの積分値
B:35.4~34.6ppmの積分値
C:38.3~36.5ppmの積分値
D:43.6~42.8ppmの積分値
E:31.1ppmの積分値
上記重合体aについて、示差走査型熱量計(パーキン・エルマー社製、商品名:DSC-7)を用い、試料10mgを窒素雰囲気下にて-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量をΔH(J/g)として求めた。また、このとき得られる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(℃)として求めた。結果を表1に示す。
上記重合体a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)および分子量分布(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)
上記重合体a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。
(結晶性1-ブテン単独重合体の製造)
製造例1において、錯体Aに代えて錯体B(10μmol/mL、0.30mL、0.6μmol)を用い、東ソーファインケム社製MAO(2000μmol)に代えてN,N-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)ボレートのヘプタンスラリー1.8μmol(10μmol/mL、0.18mL)を用いたこと以外は製造例1と同様にして、結晶性1-ブテン単独重合体68gを得た(重合体b)。重合体bの物性について、製造例1と同様にして測定した。結果を表1に示す。
(結晶性1-ブテン単独重合体の製造)
製造例1において、錯体Aに代えて錯体C(10μmol/mL、0.04mL、0.4μmol)を用い、東ソーファインケム社製MAO(2000μmol)に代えてN,N-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)ボレートのヘプタンスラリー(10μmol/mL、0.12mL、1.2μmol)を用い、重合温度を52℃にしたこと以外は製造例1と同様にして、結晶性1-ブテン単独重合体83gを得た(重合体c)。重合体cの物性について、製造例1と同様にして測定した。結果を表1に示す。
(非晶質1-ブテン-プロピレン共重合体の製造)
加熱乾燥した1リットルオートクレーブに、ヘプタン(300mL)、トリイソブチルアルミニム(2M、0.2mL、0.4mmol)、ブテン-1(60mL)、錯体Cのヘプタンスラリー(10μmol/mL、0.02mL、0.2μmol)、N,N-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)ボレートのヘプタンスラリー(10μmol/mL、0.06mL、0.6μmol)を加え、さらに水素0.05MPa導入した。撹絆しながら温度を60℃にすると同時にプロピレンを導入することにより、全圧を0.8MPaとした。その後、20分間重合した後、5mLのエタノールで重合を停止し、反応物を減圧下、乾燥することにより、非晶質1-ブテン-プロピレン共重合体57gを得た(重合体d)。重合体dの物性について、製造例1と同様にして測定した。結果を表1に示す。
加熱乾燥した1リットルオートクレーブに、ヘプタン(400mL)、トリイソブチルアルミニウム(0.5mmol)、N,N-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(0.8μmol)、錯体D(0.2μmol)を加え、更に、水素0.05MPaを導入し、プロピレン導入して全圧を0.8MPaとして、70℃で30分間重合した。重合反応終了後、反応物を減圧下で乾燥させることにより、結晶性プロピレン単独重合体90gを得た(重合体e)。重合体eの物性について、製造例1と同様にして測定した。結果を表1に示す。
(非晶質プロピレン単独重合体の製造)
加熱乾燥した1リットルオートクレーブに、ヘプタン(400mL)、トリイソブチルアルミニウム(2M、0.2mL、0.4mmol)、錯体A(10μmol/mL、0.20mL、2.0μmol)、東ソーファインケム社製MAO(2000μmol)を加え、更に水素0.1MPa導入した。撹拌しながらプロピレンを張り込み、全圧0.7MPaまで昇圧し、温度50℃で60分重合した。重合反応終了後、プロピレン、水素を脱圧し、重合液を加熱、減圧下にて乾燥することにより、非晶質プロピレン単独重合体105gを得た(重合体f)。重合体fの物性について、製造例1と同様にして測定した。結果を表1に示す。
(1)固体触媒成分の調製
内容積0.5リットルの撹拌機付三つ口フラスコを窒素ガスで置換した後、脱水処理したヘプタン20ミリリットル、ジエトキシマグネシウム4g、及びフタル酸ジブチル1.6gを加え、系内を90℃に保ち、撹拌下、四塩化チタン4ミリリットルを滴下した。さらに、四塩化チタン111ミリリットルを滴下投入して110℃に昇温した。得られた固相部に四塩化チタン115ミリリットルを加え、110℃でさらに2時間反応させた。反応終了後、生成物を精製ヘプタン100ミリリットルで数回洗浄して固体触媒成分を得た。
(2)予備重合触媒成分の調製
内容積0.5リットルの撹拌機付三つ口フラスコを窒素ガスで置換した後、脱水処理したヘプタン300ミリリットル、及び上記(1)で調製した固体触媒成分10gを加えた。系内を15℃にした後、トリエチルアルミニウム4.2ミリモル、及びシクロヘキシルメチルジメトキシシラン(CHMDS)1.1ミリモルを加え、撹拌しながらプロピレンを導入した。2時間後、撹拌を停止し、結果的に固体触媒成分1g当たり2gのプロピレンが重合した予備重合触媒成分を得た。
(3)プロピレン重合体の合成
内容積10リットルの撹拌機付ステンレス製オートクレーブを十分乾燥し、窒素置換した後、プロピレン2kg、トリエチルアルミニウム6ミリモル、ジシクロペンチルジメトキシシラン(DCPDS)3.0ミリモルを加え、65℃に昇温した。次いで、上記(2)で調製した予備重合触媒成分0.12gを投入し、70℃で3時間重合した。その結果、結晶性プロピレン単独重合体パウダー960gを得た(重合体g)。重合体gの物性について、製造例1と同様にして測定した。結果を表1に示す。
製造例5において、重合温度を65℃に変更したこと以外は製造例5と同様にして、結晶性プロピレン単独重合体85gを得た(重合体h)。重合体hの物性について、製造例1と同様にして測定した。結果を表1に示す。
製造例5において、錯体Dに代えて錯体Eを用いたこと以外は製造例5と同様にして、結晶性プロピレン単独重合体84gを得た(重合体i)。重合体iの物性について、製造例1と同様にして測定した。結果を表1に示す。
製造例9において、重合温度を65℃に変更したこと以外は製造例9と同様にして、結晶性プロピレン単独重合体80gを得た(重合体j)。重合体jの物性について、製造例1と同様にして測定した。結果を表1に示す。
(粘接着剤組成物及び粘着テープの作製)
製造例1で製造した重合体a 7.0g及び製造例5で製造した重合体e 3.0gを、50mLのサンプル瓶に入れ、180℃で30分加熱して溶融させた後、金属スプーンで十分に混合・撹拌し、粘接着剤組成物を作製した。
得られた粘着組成物を基材用PETフィルム(東レ(株)製、商品名:ルミラーS10、厚み50μm)と離型用PETフィルムとで挟み、110℃に加熱されたホットロールコーターにて、粘着層厚みが30μm程度になるように、塗布した後、離型用PETフィルムを剥がし、室温で一日状態安定させ、粘着テープの試験片を得た。
粘弾性測定装置(エスアイアイ・ナノテクノロジー(株)製、商品名:DMS 6100(EXSTAR6000))を用いて、窒素雰囲気下で以下の条件で測定を行った。
<測定条件>
測定モード:引張モード
測定温度:-150℃~230℃のうち、25℃及び50℃の2点を観測した。
昇温速度:5℃/min
測定周波数:1Hz
試料サイズ:長さ10mm、幅4mm、厚さ1mm(プレス成形品)
粘着力の評価はJIS Z 0237に準拠して行った。粘着層が形成されている粘着テープを、被着体用のPETフィルム(東レ(株)製、商品名:ルミラーS10、厚み50μm)に貼り合わせ、幅25mm、長さ200mmのサイズに切削した後、張り合わせ部を2.0kg/25mmの力で2回ゴムローラーにて力を加え、粘着させた。測定温度0℃及び23℃において、引張試験機((株)島津製作所製、商品名:オートグラフAG-I)を用いて、初期長L0を120mmに設定し、速度300mm/minで引張り、T字剥離試験を行った。剥離試験の際の、平均的な荷重を5点取り、その平均を粘着力とした。また、剥離試験の際、スリップスティックやジッピングが起きた場合は、応力値のバラつきが大きくなるため、最大値及び最小値のそれぞれ4番目の数値の平均値を粘着力とした。結果を表2に示す。
また、粘着力評価後の被着体への糊残りの有無を目視観察した。結果を表2に示す。
保持力の測定はJIS Z 0237に準拠して行った。粘着層が形成されている粘着テープを、接着面積が25mm×25mmになるように、被着体用のPETフィルム(東レ(株)製、商品名:ルミラーS10、厚み50μm)に貼り合わせ、張り合わせ部を2.0kg/25mmの力で2回ゴムローラーにて力を加え、粘着させた。得られた試験片を、温度50℃、湿度30%の環境下で、1kgの重りをかけ、重りが被着体から落下する時間を測定した。結果を表2に示す。
実施例1において、重合体eの代わりに製造例3で製造した重合体cを用いたこと以外は実施例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例1において、重合体eの代わりに製造例2で製造した重合体bを用いたこと以外は実施例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
製造例1で製造した重合体a 6.0g、製造例2で製造した重合体b 2.0g及び粘着性付与材(出光興産(株)製、商品名:アイマーブP-100)2.0gを、50mLのサンプル瓶に入れ、180℃で30分加熱して溶融させた後、金属スプーンで十分に混合・撹拌し、粘接着剤組成物を作製した。試験片の評価結果を表2に示す。
得られた粘着組成物を用いたこと以外は実施例1と同様にして、粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例1において、重合体aの代わりに製造例4で製造した重合体dを用いたこと以外は実施例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
製造例1で製造した重合体a 1.5g、製造例5で製造した重合体e 7.0g及びプロセスオイル(出光興産(株)製、商品名:ダイアナプロセスオイルPW-90)1.5gを、50mLのサンプル瓶に入れ、180℃で30分加熱して溶融させた後、金属スプーンで十分に混合・撹拌し、粘接着剤組成物を作製した。試験片の評価結果を表2に示す。
得られた粘着組成物を用いたこと以外は実施例1と同様にして、粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例5において、重合体dの代わりに製造例6で製造した重合体fを用いたこと以外は実施例5と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例7において、重合体eの代わりに製造例8で製造した重合体hを用いたこと以外は実施例7と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例7において、重合体eの代わりに製造例9で製造した重合体iを用いたこと以外は実施例7と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例7において、重合体eの代わりに製造例10で製造した重合体jを用いたこと以外は実施例7と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例1において、重合体aの配合量を10.0gとし、重合体eを用いなかったこと以外は実施例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例1において、重合体eの代わりに粘着性付与材(出光興産(株)製、商品名:アイマーブP-100)を用いたこと以外は実施例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
比較例1において、重合体aの代わりに製造例6で製造した重合体fを用いたこと以外は比較例1と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
実施例7において、重合体eの代わりに製造例7で製造した重合体gを用いたこと以外は実施例7と同様にして、粘接着剤組成物及び粘着テープ試験片を得た。試験片の評価結果を表2に示す。
また、融点が160℃を超える結晶性ポリプロピレン(重合体g)を用いた比較例4では、塗工性が大きく損なわれ、110℃に加熱されたホットロールコーターでは塗工できなかった。なお、ホットロールコーターの温度を200℃程度まで上げれば、塗工することはできるが、基材に用いるPETフィルムやOPPフィルムも変形したり、溶けたりしてしまう。また、トルエン等の溶剤に粘着剤を溶解させて塗工する方法もあるが、前記結晶性ポリプロピレンは溶剤溶解性も悪く、当方法でも塗工性は悪い。
これに対し、特定の非晶質ポリオレフィンと特定の結晶性ポリオレフィンとを含む組成物を粘接着剤に用いた実施例1~10では、粘着力と保持力、糊残りのバランスに優れた粘着基材を提供することができた。
Claims (8)
- (1)示差走査型熱量計(DSC)による融点が観測されないか又は融点が20℃未満であり、かつ、ΔHが5J/g未満であるポリオレフィン5~95質量%と、
(2)融点が20℃以上160℃以下であり、かつ、ΔHが5J/g以上100J/g以下であるポリオレフィン95~5質量%と
を含む粘接着剤組成物であって、
該組成物の固体粘弾性測定から得られる25℃における貯蔵弾性率が1MPa以上200MPa以下であり、50℃における貯蔵弾性率が1MPa以上100MPa以下である、粘接着剤組成物。 - (1)示差走査型熱量計(DSC)による融点が観測されないか又は融点が20℃未満であり、かつ、ΔHが5J/g未満であるポリオレフィン5~95質量%と、
(3)ガラス転移温度が50℃以上150℃以下である熱可塑性エラストマー95~5質量%と
を含む粘接着剤組成物であって、
該組成物の固体粘弾性測定から得られる25℃における貯蔵弾性率が1MPa以上200MPa以下であり、50℃における貯蔵弾性率が1MPa以上100MPa以下である、粘接着剤組成物。 - 前記ポリオレフィン(1)が、炭素数2~12のオレフィンの重合体である、請求項1又は2に記載の粘接着剤組成物。
- 前記ポリオレフィン(1)が、炭素数3~12のα-オレフィンの重合体である、請求項1~3のいずれかに記載の粘接着剤組成物。
- 前記ポリオレフィン(1)が、1-ブテン単独重合体、プロピレン単独重合体及び1-ブテン-プロピレン共重合体からなる群から選ばれる少なくとも1種である、請求項1~4のいずれかに記載の粘接着剤組成物。
- 前記ポリオレフィン(1)が、GPC法により測定した重量平均分子量(Mw)が5,000~1,000,000である、請求項1~5のいずれかに記載の粘接着剤組成物。
- 粘着性付与材を更に含む、請求項1~6のいずれかに記載の粘接着剤組成物。
- 請求項1~7のいずれかに記載の粘接着剤組成物を粘接着層に用いた粘着テープ。
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