WO2022118836A1 - グラフト変性体、接着剤、オレフィン系樹脂組成物および積層体 - Google Patents
グラフト変性体、接着剤、オレフィン系樹脂組成物および積層体 Download PDFInfo
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- WO2022118836A1 WO2022118836A1 PCT/JP2021/043839 JP2021043839W WO2022118836A1 WO 2022118836 A1 WO2022118836 A1 WO 2022118836A1 JP 2021043839 W JP2021043839 W JP 2021043839W WO 2022118836 A1 WO2022118836 A1 WO 2022118836A1
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- olefin
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
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- 229940069096 dodecene Drugs 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
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- 125000001153 fluoro group Chemical class F* 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
- B32B2327/18—PTFE, i.e. polytetrafluoroethylene
Definitions
- One embodiment of the present invention relates to a graft modified product, an adhesive, an olefin resin composition or a laminated body.
- Polyolefins such as polyethylene and polypropylene are excellent in mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, impact resistance at low temperatures, etc., and by utilizing these characteristics, films and sheets It is widely used as a packaging material / covering material for bottles and the like, or as a decorative material for wallpaper and the like.
- polyolefins do not contain polar groups in their molecules, they are compatible with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, modified fluororesins, and biomass plastics, as well as metals.
- polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, modified fluororesins, and biomass plastics, as well as metals.
- the adhesiveness to glass, paper, the polar resin, or the like is poor, and it is restricted to be used by blending with these materials or to be used by laminating them.
- a method of grafting a polar group-containing monomer to a polyolefin to improve the compatibility and the adhesiveness has been widely used.
- a method of grafting glycidyl (meth) acrylate or the like on a polyolefin is generally widely used (for example, Patent Document 1).
- the modified polyolefin obtained by the method described in Patent Document 1 can improve the compatibility and adhesiveness to some extent, but the compatibility and adhesiveness are not sufficient, and in particular, the adhesive strength is not sufficient. It took a long time to develop sufficient adhesive strength.
- One embodiment of the present invention provides a graft modified product capable of forming a layer having high adhesive strength against a substrate having a polar group such as polyester or polyphenylene sulfide even in a short time.
- An example of the configuration of the present invention is as follows.
- R 1 is a hydrogen atom or a methyl group
- R 2 is a hydrocarbon group which may have a substituent.
- R 3 is a hydrogen atom or a methyl group
- R 4 is a hydrocarbon group which may have a substituent
- m is an integer of 2 or more.
- a graft modified product capable of forming a layer having high adhesive strength against a substrate having a polar group such as polyester or polyphenylene sulfide even in a short time (short sealing time). can.
- the graft modified product according to the embodiment of the present invention (hereinafter, also referred to as “the present modified product”) is made of a carbodiimide monomer having a carbodiimide group and a polymerizable double bond of at least one base polymer selected from polyolefins. It is a graft-modified product, in other words, a graft-modified product in which at least one base polymer selected from polyolefin is graft-modified with a carbodiimide monomer having a carbodiimide group and a polymerizable double bond.
- the modified product is a graft modified product containing at least one base polymer moiety selected from polyolefin and a graft moiety derived from a carbodiimide monomer having a carbodiimide group and a polymerizable double bond.
- a layer having high adhesive strength can be formed on a substrate having a polar group such as polyester or polyphenylene sulfide even in a short time.
- This modified product has higher reactivity with polar groups present in polyester, polyphenylene sulfide, etc. than the grafted product made of glycidyl (meth) acrylate, and is therefore remarkably excellent in adhesion to these substrates.
- this modified product is not a block copolymer or a random copolymer of an olefin-based monomer such as ethylene or propylene and the carbodiimide monomer, but a graft modified product, the above-mentioned effect is exhibited.
- the graft ratio in the present modified product it is possible to easily obtain the graft modified product which is superior in the ease of synthesis of the main modified product, the compatibility and the adhesiveness, and the obtained graft modified product does not become too hard. From this point of view, it is preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass.
- the graft ratio is the mass of the structure derived from the carbodiimide monomer in the graft modified product, and can be determined by 1 H-NMR measurement, specifically, the method described in the following Examples.
- the carbodiimide monomer used for graft-modifying the base polymer is not particularly limited as long as it is a compound having a carbodiimide group and a polymerizable double bond, but is described below from the viewpoint of further exerting the effects of the present invention. It is preferably a compound represented by the formula (1) or (2).
- the carbodiimide monomer used for graft-modifying the base polymer may be two or more, but is usually one.
- R 1 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint that the modified product having a high graft ratio can be easily obtained.
- R 2 is a hydrocarbon group which may have a substituent.
- the hydrocarbon group include an alkyl group or an aryl group which may have a substituent.
- the alkyl group which may have the substituent may be chain-like (may be linear or may have a branch), or may contain an alicyclic.
- the hydrocarbon group which may have a substituent is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, still more preferably 8 or less.
- Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carboxylic acid ester group having 1 to 8 carbon atoms.
- Examples thereof include a phosphate ester group having 8 to 8, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.
- the above-mentioned R 2 is an aliphatic hydrocarbon having 4 to 20 carbon atoms including an alicyclic from the viewpoints of solubility of the carbodiimide monomer, availability, and purification of the obtained graft modified product. It is preferably a hydrogen group, and more preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms.
- the alicyclic ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and these rings having a hydrocarbon group.
- the alicyclic ring may be a polycyclic ring such as an adamantane ring or a methyladamantyl ring.
- R 3 is a hydrogen atom or a methyl group, and the methyl group is preferable from the viewpoint that the modified product having excellent adhesive strength to a substrate having a polar group can be easily obtained.
- R 4 is a hydrocarbon group which may have a substituent.
- the hydrocarbon group include an alkyl group or an aryl group which may have a substituent.
- the alkyl group which may have the substituent may be chain-like (may be linear or may have a branch), or may contain an alicyclic.
- the hydrocarbon group which may have a substituent is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, still more preferably 8 or less.
- Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a carboxylic acid ester group having 1 to 8 carbon atoms.
- Examples thereof include a phosphate ester group having 8 to 8, an alkylsilyl group having 1 to 8 carbon atoms, and an alkoxysilyl group having 1 to 8 carbon atoms.
- the R 4 has a branch and has a ring from the viewpoint that the modified product having excellent adhesive strength to a base material having a polar group, particularly polyester, can be easily obtained. It is preferably an alkyl group having no alkyl group, and more preferably an alkyl group having a branch and having no ring and having 3 to 7 carbon atoms.
- alkyl group having a branch and having no ring examples include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 1-methylbutyl group, and a 1,2-dimethylpropyl group.
- m is an integer of 2 or more, and is preferably an integer of 2 to 6 in terms of solubility of the carbodiimide monomer, availability, and purification of the obtained graft modified product. Yes, more preferably an integer of 2-4, and particularly preferably 2.
- the base polymer before graft modification with the carbodiimide monomer is at least one polymer selected from polyolefins.
- the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 4-methyl-1-pentene.
- the polyolefin may be a homopolymer of these olefins or a copolymer of two or more of these olefins, with one or more of these olefins and one or more of the following copolymers. It may be a copolymer of.
- the polyolefin is preferably at least one polymer selected from an ethylene-based polymer, a propylene-based polymer, and a butene-based polymer, and when a solvent is used in the graft reaction, the solvent is used. It is more preferable that the polymer is at least one selected from an ethylene-based polymer and a propylene-based polymer from the viewpoints of excellent solubility and excellent separability from impurities after the graft reaction.
- the base polymer may be two or more kinds, but usually one kind.
- the base polymer does not have at least one active hydrogen-containing group selected from a carboxy group, an acid anhydride group, an amino group, a hydroxy group and a thiol group from the viewpoint of further exerting the effect of the present invention. Is preferable. Further, from the viewpoint that the effect of the present invention is more exhibited, the base polymer can easily generate active hydrogen with water or the like, such as a carboxylic acid derivative group such as an acid halide, an amide, an imide or an ester, or an epoxy group. It is also preferable that the polymer does not have a group that is converted into a group having the group.
- the weight average molecular weight (Mw) of the base polymer is not particularly limited, but is preferably 100,000 or more, more preferably 150,000 or more, and preferably 1,000 from the viewpoint of ease of synthesis of the modified product. It is 000 or less, more preferably 700,000 or less.
- the number average molecular weight (Mn) of the base polymer is also not particularly limited, but for the same reason, it is preferably 40,000 or more, more preferably 50,000 or more, preferably 500,000 or less, and more preferably 300, It is 000 or less.
- the molecular weight distribution (Mw / Mn) of the base polymer is also not particularly limited, but is preferably 1.5 or more, more preferably 2.0 or more, preferably 6.0 or less, and more preferably 5.0 or less. ..
- the Mw and Mn are values measured under the following conditions using an HLC-8321 GPC / HT type gel permeation chromatograph (GPC) manufactured by Tosoh Corporation. Separation columns: TSKgel GMH 6 -HT (2 pcs) and TSKgel GMH 6 -HTL (2 pcs) (both 7.5 mm ID x 30 cm, manufactured by Tosoh Corporation) Column temperature: 140 ° C Mobile phase: o-dichlorobenzene (containing 0.025% dibutylhydroxytoluene (BHT)) Development rate: 1.0 mL / min Sample concentration: 0.1% (w / v) Sample injection volume: 0.4 mL Detector: Differential refractometer Calibration of device: Monodisperse polystyrene (manufactured by Tosoh Corporation, # 3std set) was used.
- GPC gel permeation chromatograph
- the base polymer can be synthesized by a conventionally known method, or a commercially available product may be used.
- the conventionally known method is not particularly limited, and examples thereof include a method using a coordination polymerization catalyst system containing a transition metal.
- ethylene is present in the presence of a catalyst such as a magnesium chloride-supported titanium catalyst, a vanadium-based catalyst containing a soluble vanadium compound and an alkylaluminum halide compound, or a metallocene catalyst containing a metallocene compound and an organic aluminum oxy compound.
- a method of synthesizing by (co) polymerizing propylene and a comonomer described later, if necessary, can be mentioned.
- the ethylene-based polymer is not particularly limited as long as it is a polymer in which the content of ethylene-derived structural units in the polymer is 50% by mass or more, and may be a copolymer of ethylene. It may be a copolymer with comonomer. In the case of a copolymer, its structure is not particularly limited.
- Examples of the comonomer include at least one monomer selected from propylene, ⁇ -olefin having 4 to 20 carbon atoms and conjugated polyene, and among these, propylene and ⁇ -olefin having 4 to 20 carbon atoms are preferable. ..
- the ⁇ -olefin having 4 to 20 carbon atoms may be linear or branched, and may be, for example, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, and the like.
- the content of the constituent unit derived from the comonomer in the ethylene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 30% by mass or less from the viewpoint of easy handling without blocking of pellets and powder. It is 20% by mass or less.
- An ethylene-based polymer having a content of 50% by mass of a propylene-derived or butene-derived structural unit is referred to as an ethylene-based polymer in the present specification.
- the propylene-based polymer is not particularly limited as long as it is a polymer in which the content of the propylene-derived structural unit in the polymer is 50% by mass or more, and may be a homopolymer of propylene, and may be a homopolymer of propylene. It may be a copolymer with a comonomer.
- the structure of these (co) polymers is not particularly limited.
- Examples of the comonomer include ethylene, at least one monomer selected from ⁇ -olefins having 4 to 20 carbon atoms and conjugated polyenes, and among these, ethylene and ⁇ -olefins having 4 to 20 carbon atoms are preferable. ..
- Examples of the ⁇ -olefin having 4 to 20 carbon atoms include ⁇ -olefins similar to the ⁇ -olefins having 4 to 20 carbon atoms mentioned in the column of ethylene-based polymers.
- the content of the constituent unit derived from the comonomer in the propylene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 30% by mass or less from the viewpoint of easy handling without blocking of pellets and powder. It is 20% by mass or less.
- a propylene-based polymer having a content of a constituent unit derived from butene of 50% by mass is referred to as a propylene-based polymer in the present specification.
- butene polymer The butene-based polymer is not particularly limited as long as it is a polymer in which the content of the constituent unit derived from butene in the polymer is 50% by mass or more, and is a homopolymer of butene, particularly 1-butene. It may be a polymer of butene (particularly 1-butene) and a comonomer. The structure of these (co) polymers is not particularly limited.
- Examples of the comonomer include at least one monomer selected from ethylene, propylene, ⁇ -olefin having 5 to 20 carbon atoms and conjugated polyene, and among these, ethylene, propylene and ⁇ having 5 to 20 carbon atoms. -Ethylene is preferred.
- Examples of the ⁇ -olefin having 5 to 20 carbon atoms include ⁇ -olefins similar to the ⁇ -olefins having 5 to 20 carbon atoms mentioned in the column of ethylene-based polymers.
- the content of the constituent unit derived from the comonomer in the butene-based polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 30% by mass or less from the viewpoint of easy handling without blocking of pellets and powders. It is 20% by mass or less.
- the method for synthesizing the modified product is not particularly limited, and is not particularly limited as long as a graft-modified product obtained by graft-modifying the base polymer with the carbodiimide monomer is obtained.
- a method of adding a radical initiator and the carbodiimide monomer to a solution in which the polymer is dissolved or dispersed in a solvent, preferably a solution in which the base polymer is dissolved in an organic solvent is preferable to cause a reaction (graft reaction).
- graft reaction When a reaction device having a stirring ability capable of uniformly flowing the base polymer is used, it is not necessary to use a solvent. According to the above method, graft polymerization occurs, so that a graft modified product can be obtained.
- the modified product having a graft ratio in the above range can be easily obtained, and a polymer of the carbodiimide monomer itself (hereinafter, also referred to as “non-grafted polymer”) is produced. It is preferably 10 to 1000 mol, more preferably 10 to 800 mol, with respect to 1 mol of the base polymer, from the viewpoint of being able to suppress the above.
- radical initiator examples include organic peroxides and azo compounds, and specific examples thereof include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5.
- dicumyl peroxide di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3, 2,5-dimethyl-2,5-di (tert).
- Organic peroxides such as -butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene and tert-butylperoxyisopropyl monocarbonate are preferred.
- the radical initiator may be used alone or in combination of two or more.
- the amount of the radical initiator used in the graft reaction is preferable with respect to 1 mol of the carbodiimide monomer from the viewpoint that the graft reaction occurs efficiently and the modified product having the graft ratio in the above range can be easily obtained.
- organic solvent an organic solvent that does not significantly inhibit the graft reaction of the carbodiimide monomer and has an affinity with the base polymer in the temperature range in which the graft reaction is performed is preferable.
- organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane and methylcyclohexane.
- Alicyclic hydrocarbon solvents such as decahydronaphthalene, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene, methanol, ethanol, n-propanol, iso- Alcohol solvents such as propanol, n-butanol, sec-butanol, tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di- Examples thereof include ether solvents such as n-amyl ether, tetrahydrofuran and dioxyanisole.
- suspension polymerization and emulsion polymerization can also be carried out using water as a solvent.
- solvents may be used alone or in combination of two or more. It is preferable that the reaction solution has a uniform phase by using these solvents, but a plurality of non-uniform phases may be used.
- the concentration of the base polymer in the liquid is usually set to 50 to 500 g / L, but in order to achieve a high graft ratio, 200 is used. It is preferably ⁇ 500 g / L.
- the radical initiator and the carbodiimide monomer may be started by batch addition to the liquid containing the base polymer (or the base polymer itself), but the graft reaction may be initiated for 0.1 to 5 hours in order to achieve a high graft ratio. It is preferable to carry out the graft reaction by sequentially adding the mixture over a certain period of time.
- the order of addition thereof is not particularly limited, and for example, they are sequentially added as described above.
- the radical initiator and the carbodiimide monomer may be added sequentially, or the carbodiimide monomer may be added first, and then the radical initiator may be added sequentially.
- the graft reaction is usually carried out at a temperature of 60 ° C. or higher, preferably 100 ° C. or higher, usually 200 ° C. or lower, preferably 160 ° C. or lower, for usually 2 hours or longer, preferably 3 hours or longer, and usually 10 hours. Below, it is preferable to carry out for 8 hours or less.
- the modified product obtained by the graft reaction is subjected to filtration, centrifugation, reprecipitation operation and / or washing of the solvent used, unreacted radical initiator and carbodiimide monomer, by-produced non-grafted polymer and the like. It may be purified and isolated by using a known method such as combining if necessary.
- the content of the non-grafted polymer contained in the modified product is preferably 5% by mass or less, from the viewpoint that the modified product having better compatibility and adhesiveness can be easily obtained. It is more desirable to purify and isolate the product so that the content is 2% by mass or less.
- this modified product has excellent compatibility with polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, modified fluororesin, and biomass plastic, and olefin polymers, these polar resins and Since it has excellent adhesion to a compatibilizer for a composition containing an olefin polymer, metal, glass, paper, the polar resin, the olefin polymer, etc., an adhesive to a substrate containing these, an olefin polymer, etc.
- polar resins such as polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, modified fluororesin, and biomass plastic, and olefin polymers
- the modified product Since it has excellent dispersibility in a polymer, it can be mixed with an olefin polymer and used as an olefin resin composition or the like. Among these, the modified product has excellent adhesiveness to polyester and polyphenylene sulfide, and therefore, from the viewpoint that the effect of the present invention is more exhibited, the adhesive and olefin to polyester and polyphenylene sulfide (including the layer) are exhibited. It is preferable to use it as a based resin composition.
- the olefin-based polymer is not particularly limited as long as it is a polymer mainly composed of olefins, and various known olefin-based polymers can be used. Specifically, for example, a single or copolymer of ⁇ -olefin such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene (eg, high pressure method low density polyethylene, etc.).
- ⁇ -olefin such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene (eg, high pressure method low density polyethylene, etc.).
- Linear low density polyethylene (LLDPE), medium density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, low crystalline or amorphous ethylene / propylene random copolymer, ethylene 1-butene random copolymer, propylene / 1-butene random copolymer), ethylene / vinyl acetate copolymer (EVA) or its sacrifice, ethylene / (meth) acrylic acid copolymer or its metal salt ( Ionomer), ethylene-cyclic olefin copolymers, and polymers in which these (co) polymers are graft-modified with polar compounds such as maleic acid and silane compounds.
- LLDPE Linear low density polyethylene
- medium density polyethylene high density polyethylene
- polypropylene poly 1-butene
- poly 4-methyl-1-pentene low crystalline or amorphous ethylene / propylene random copolymer
- additives may be added to the modified product, if necessary, as long as the object of the present invention is not impaired.
- the additive include softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability-imparting agents, leveling agents, wetting agents, film-forming aids, and cross-linking agents.
- the olefin-based resin composition according to one embodiment of the present invention is not particularly limited as long as the modified product and one or more olefin-based polymers are included, and the modified product contained in the olefin-based resin composition. May be 1 type or 2 or more types. Further, the olefin-based resin composition may contain one or more of the above-mentioned additives, respectively.
- the olefin-based resin composition can be used not only as an adhesive (adhesive resin composition), but also as, for example, printing inks, paints, machine cleaners for polymer processing, and binders.
- the content of the modified product in the olefin resin composition is not particularly limited, but is usually 0.5% by mass or more, preferably 1% by mass, from the viewpoints of molding processability, controllability of adhesive ability, economy, and the like. It is usually 40% by mass or less, preferably 25% by mass or less.
- Examples of the olefin-based polymer contained in the olefin-based resin composition include polymers similar to the olefin-based polymer described in the column of uses of the present modified product.
- the content of the olefin polymer in the olefin resin composition is not particularly limited, but is usually 60% by mass or more, preferably 75% by mass or more from the viewpoint of molding processability, controllability of adhesive ability, economy and the like. It is usually 99.5% by mass or less, preferably 99% by mass or less.
- the adhesive (including the pressure-sensitive adhesive) according to the embodiment of the present invention is not particularly limited as long as the modified product or the olefin resin composition is included, and the modified product and the olefin contained in the adhesive are not particularly limited.
- the system resin composition may be one kind or two or more kinds, respectively.
- the adhesive may be an adhesive consisting of only the modified product, or may contain one or more of the above-mentioned olefin-based polymers and additives, respectively.
- the content of the modified product in the adhesive containing the modified product is not particularly limited, but is usually 5 to 100% by mass, preferably 10 to 100% by mass.
- the adhesive can be used in various known forms, for example, a water-dispersible adhesive, an organic solvent-type adhesive, and a hot-melt type adhesive.
- the adhesive can be adhered to, for example, metal; glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, olefin polymer, polystyrene, rubber, modified fluororesin.
- a layer containing a thermoplastic resin such as a biomass plastic or an engineering plastic other than these; a thermosetting resin; or a layer composed of these.
- the laminate according to the embodiment of the present invention is not particularly limited as long as it includes the layer (A) containing the modified product or the olefin resin composition and the base material layer (B), and the layer (A). ) May be contained in two or more layers, and the base material layer (B) may be contained in two or more layers. When two or more layers (A) are included, these layers may be the same layer or different layers. Similarly, when two or more base material layers (B) are included, these layers may be the same layer or different layers.
- the laminated body includes a layer (A) and a base material layer (B), or a base material layer (B), a layer (A), and a base material layer (B) in this order. It is preferably a body.
- the layer (A) can be obtained by using the modified product, the adhesive or the olefin resin composition. It can be determined by infrared spectroscopic analysis that the modified product is contained in the layer (A).
- the thickness of the layer (A) is not particularly limited and may be appropriately selected depending on the intended use of the laminated body, but is preferably 2 to 1000 ⁇ m. Further, the thickness of the base material layer (B) is not particularly limited and may be appropriately selected depending on the intended use of the laminated body, but is preferably 2 to 1000 ⁇ m.
- Examples of the base material layer (B) include metal; glass; wood; paper; cloth; polyester, polyphenylene sulfide, polyamide, polyacetal, polycarbonate, poly (meth) acrylate, olefin polymer, polystyrene, rubber, and modified fluorine.
- Examples thereof include a layer containing a thermoplastic resin such as a resin, a biomass plastic, and an engineering plastic other than these; a thermosetting resin; or a layer composed of these.
- thermoplastic resin examples include various known thermoplastic resins such as olefin-based polymers (eg, polymers similar to the polymers listed in the column of uses of the modified product), polyesters (eg, polyethylene terephthalate, etc.). Polybutylene terephthalate, polyethylene naphthalate), polyphenylene sulfide, polyamide (eg nylon-6, nylon-66, polymethoxylen adipamide), polyvinyl chloride, polyvinylidene chloride, polymethylmethacrylate, polyvinylacetate, thermoplastics Examples include polyimide, polyvinyl alcohol, polyacrylonitrile, polyacetal, polycarbonate, polystyrene, thermoplastic polyurethane, biodegradable plastic (eg, aliphatic polyester such as polylactic acid), modified fluororesin, biomass plastic (eg, starch resin). Be done.
- thermoplastic resins such as olefin-based polymers (eg, polymers similar to the polymers listed in the
- thermosetting resin examples include various known thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, and polyimide.
- the base material layer (B) is preferably a layer having a polar group.
- the carbodiimide group in the modified product reacts with the polar group in the base material layer (B) to be in a bonded state, so that the layer (B) The adhesiveness between A) and the base material layer (B) is further improved.
- the layer (A) includes not only the modified product but also a state in which the carbodiimide group of the modified product reacts with the polar group of the substrate layer (B).
- the polar group examples include a carboxy group, a hydroxy group, an amino group, an ester group, and a carbonyl group. Among these, a carboxy group and a hydroxy group are preferable.
- the base material layer (B) may have two or more types of polar groups.
- polyester usually has a carboxy group and a hydroxy group at the end.
- polyphenylene sulfide usually has a carboxy group at the end. Glass and metals also usually have hydroxy groups.
- the layer containing the thermoplastic resin or the thermosetting resin, or a layer composed of these, is usually added to the resin and used as a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
- a phenol-based antioxidant a phenol-based antioxidant
- a phosphorus-based antioxidant a phosphorus-based antioxidant
- a sulfur-based antioxidant a phenol-based antioxidant
- Metal compounds, metal salts of higher fatty acids and the like may be contained within a range that does not impair the object of the present invention.
- the laminated body is not limited to the shape of a laminated film (sheet), but may be any of various known shapes such as a hollow container, a cup, and a tray.
- the method for producing the laminate varies depending on the shape, size, required physical characteristics, etc. of the final product and is not particularly limited, and examples thereof include the following methods.
- (1) A method of heat-sealing using a calendar roll molding machine, a compression molding machine, or the like at a temperature equal to or higher than the temperature at which at least one of the preformed layer (A) and the base material layer (B) is melted.
- (2) A method of heat-sealing a preformed layer (A) or a substrate layer (B) to another layer that is extrusion-molded or calendar-molded.
- the laminate Since the laminate has the layer (A) containing the modified product or the olefin resin composition, it has excellent interlayer adhesiveness, and even if the laminate is heat-treated at a high temperature of, for example, 200 to 250 ° C. , It is possible to obtain a laminated body in which the interlayer adhesive strength does not easily decrease. Further, since the laminated body has the layer (A) containing the modified product or the olefin resin composition, the interlayer adhesiveness is excellent, and for example, when heat-sealing at 230 ° C., the heat-sealing time is set. A layer having high adhesive strength can be formed even in a short time of preferably 20 seconds or less, more preferably 10 seconds or less, and further preferably 5 seconds or less.
- ⁇ Measurement method of graft rate> The graft ratio was measured using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus (500 MHz) manufactured by Bruker Biospin Co., Ltd., measurement solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature: 120 ° C., spectrum. 1 H-NMR spectrum was measured under the measurement conditions of width: 20 ppm, pulse repetition time: 7.0 seconds, and pulse width: 5.00 ⁇ sec (45 ° pulse).
- Example 1 25.0 g of LLDPE (base polymer, comonomer species: 1-hexene, comonomer amount: 1.6% by mass, Mw: 164,000, Mn: 63,000, Mw / Mn: 2.60) in 1 L of autoclave. And 150 mL of toluene was charged, the inside of the autoclave was replaced with nitrogen, and then sealed. After that, the internal temperature of the autoclave was raised to 140 ° C., and while maintaining the temperature, 28.1 mmol of vinylphenylcyclohexylcarbodiimide and 2.2 mmol of dicumyl peroxide were stirred at a stirring speed of 400 rpm using a double anchor blade. Feeded over 2 hours. Then, after stirring for another 2 hours, 250 mL of toluene was fed over 15 minutes to dilute the reaction solution.
- LLDPE base polymer, comonomer species: 1-hexene, comonomer amount: 1.6% by mass,
- the internal temperature of the autoclave was cooled to 50 ° C., and after depressurization, the slurry-like reaction solution was taken out. 400 mL of acetone was added to the obtained reaction solution, and the mixture was stirred for 10 minutes, and then the stirred solution was filtered and separated into a solid content and a filtrate. The steps from the addition of this acetone to the filtration of the obtained solid content were repeated twice more.
- the solid content after the third filtration was dried in a vacuum dryer at 70 ° C. for 10 hours to obtain a graft polymer (P-1).
- the yield of the graft polymer (P-1) was 25.71 g (mass increase: 0.71 g).
- the graft ratio was 2.7% by mass.
- Example 2 In a 500 mL glass container, 25.0 g of PP (base polymer, propylene homopolymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.43) and 110 mL of xylene were charged, and the inside of the container was charged. Was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, tert-butylperoxyisopropyl monocarbonate (perbutyl I, NOF) dissolved in 28.1 mmol of vinylphenylcyclohexylcarbodiimide and 10 mL of xylene was used.
- PP base polymer, propylene homopolymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.43
- xylene base polymer, propylene homopolymer, Mw: 313,000, Mn: 70,800, Mw / Mn: 4.43
- Example 3 In a 500 mL glass container, 25.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 110 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and 14 mmol of vinylphenylphenylcarbodiimide was charged while maintaining the temperature, and then tert-butylperoxyisopropyl monocarbonate (perbutyl I,) dissolved in 10 mL of xylene was charged. 1.1 mmol (manufactured by NOF CORPORATION) was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, after stirring for another 3 hours, 200 mL of xylene was fed to dilute the reaction solution.
- LLDPE the same polymer as the base polymer used in Example 1 above
- the internal temperature of the container was cooled to 50 ° C., and the slurry-like reaction solution was taken out.
- 400 mL of acetone was added to the obtained reaction solution, and the mixture was stirred for 10 minutes, and then the stirred solution was filtered and separated into a solid content and a filtrate.
- the process from the addition of this acetone to the filtration of the obtained solid content was repeated three more times.
- the solid content after the fourth filtration was dried in a vacuum dryer at 90 ° C. for 10 hours to obtain 25.62 g of the graft polymer (P-3).
- the graft ratio was 3.4% by mass.
- Example 4 A 500 mL glass container is charged with 12.5 g of 4-methylpentene homopolymer (base polymer, Mw: 671,000, Mn: 297,000, Mw / Mn: 2.26) and 50 mL of xylene, and the container is filled. The inside was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and 14 mmol of vinylphenylcyclohexylcarbodiimide was charged while maintaining the temperature, and then tert-butylperoxyisopropyl monocarbonate (perbutyl I,) dissolved in 10 mL of xylene was charged.
- base polymer base polymer, Mw: 671,000, Mn: 297,000, Mw / Mn: 2.26
- Example 5 25.0 g of EBR (base polymer, DF710, manufactured by Mitsui Chemicals, Inc.) and 110 mL of xylene were charged in a 500 mL glass container, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and 14 mmol of vinylphenylcyclohexylcarbodiimide was charged while maintaining the temperature, and then tert-butylperoxyisopropyl monocarbonate (perbutyl I,) dissolved in 10 mL of xylene was charged. 1.1 mmol (manufactured by NOF CORPORATION) was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, the mixture was further stirred for 3 hours.
- EBR base polymer, DF710, manufactured by Mitsui Chemicals, Inc.
- Example 6 In a 500 mL glass container, 25.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 110 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 33.4 mmol of ethylphenylcarbodiimide methacrylate was charged, and then tert-butylperoxyisopropyl monocarbonate dissolved in 10 mL of xylene (tert-butylperoxyisopropyl monocarbonate).
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 7 In a 500 mL glass container, 17.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 78 mL of xylene were charged, and the inside of the container was replaced with nitrogen.
- LLDPE the same polymer as the base polymer used in Example 1 above
- the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 24.5 mmol of ethylacrylic acid cyclohexylcarbodiimide was charged, and then tert-butylperoxyisopropyl monocarbonate dissolved in 10 mL of xylene (tert-butylperoxyisopropyl monocarbonate ( 1.68 mmol of Perbutyl I (manufactured by NOF CORPORATION) was added dropwise over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, after stirring for another 3 hours, 150 mL of xylene was charged to dilute the reaction solution.
- tert-butylperoxyisopropyl monocarbonate 1.68 mmol of Perbutyl I (manufactured by NOF CORPORATION) was added dropwise over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade.
- Example 8 In a 500 mL glass container, 25.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 110 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 35.0 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene.
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 9 In a 500 mL glass container, 17.1 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 73 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 23.8 mmol of ethyl methacrylate-n-butylcarbodiimide was charged, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene.
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 10 14.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 57 mL of xylene were charged in a 500 mL glass container, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 19.0 mmol of ethyl methacrylate-p-chlorophenylcarbodiimide was charged, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene.
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 11 In a 500 mL glass container, 17.0 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 73 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 22.5 mmol of ethyl methacrylate-p-methoxyphenylcarbodiimide was charged, and then tert-butylperoxy dissolved in 10 mL of xylene was charged.
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 12 In a 500 mL glass container, 20.0 g of PP (the same polymer as the base polymer used in Example 2 above) and 86 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 22.6 mmol of ethylphenylcarbodiimide methacrylate was charged, and then tert-butylperoxyisopropyl monocarbonate dissolved in 10 mL of xylene (tert-butylperoxyisopropyl monocarbonate).
- Example 13 19.0 g of PP (the same polymer as the base polymer used in Example 2 above) and 81 mL of xylene were charged in a 500 mL glass container, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 20 mmol of ethylacrylic acid cyclohexylcarbodiimide was charged, and then tert-butylperoxyisopropyl monocarbonate (perbutyl I) dissolved in 10 mL of xylene was charged.
- PP the same polymer as the base polymer used in Example 2 above
- Example 14 In a 500 mL glass container, 15.0 g of PP (the same polymer as the base polymer used in Example 2 above) and 62 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 22.1 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene.
- PP the same polymer as the base polymer used in Example 2 above
- Example 15 In a 500 mL glass container, 15.0 g of PP (the same polymer as the base polymer used in Example 2 above) and 62 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 17.8 mmol of ethyl methacrylate-p-chlorophenylcarbodiimide was charged, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene.
- PP the same polymer as the base polymer used in Example 2 above
- Example 16 In a 500 mL glass container, 20.0 g of PP (the same polymer as the base polymer used in Example 2 above) and 86 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and while maintaining the temperature, 22.5 mmol of ethyl methacrylate-p-methoxyphenylcarbodiimide was charged, and then tert-butylperoxy dissolved in 10 mL of xylene was charged.
- PP the same polymer as the base polymer used in Example 2 above
- Example 17 In a 500 mL glass container, 10.0 g of EBR (the same polymer as the base polymer used in Example 5 above) and 38 mL of xylene were charged, and the inside of the container was replaced with nitrogen. Then, the internal temperature of the container was raised to 120 ° C., and 13.4 mmol of ethyl methacrylate-tert-butylcarbodiimide was charged while maintaining the temperature, and then tert-butylperoxyisopropyl dissolved in 10 mL of xylene. 0.9 mmol of monocarbonate (Perbutyl I, manufactured by NOF CORPORATION) was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, the mixture was further stirred for 3 hours.
- EBR the same polymer as the base polymer used in Example 5 above
- Example 18 23 g of LLDPE (the same polymer as the base polymer used in Example 1 above) and 100 mL of xylene were placed in a 500 mL separable flask, the inside of the separable flask was replaced with nitrogen, and then the internal temperature was raised to 120 ° C. Then, while maintaining the temperature, 30 mmol of ethylisopropylcarbodiimide methacrylate was charged, and then 2.0 mmol of tert-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by Nichiyu Co., Ltd.) dissolved in 10 mL of xylene was added. , Using a double anchor blade, fed over 10 minutes while stirring at a stirring speed of 400 rpm. Then, after stirring for another 3 hours, 200 mL of xylene was fed to dilute the reaction solution.
- LLDPE the same polymer as the base polymer used in Example 1 above
- Example 19 13.2 g of PP (the same polymer as the base polymer used in Example 2 above) and 54 mL of xylene were placed in a 500 mL separable flask, and the inside of the separable flask was replaced with nitrogen, and then the internal temperature was raised to 120 ° C. The temperature was raised and 19.5 mmol of ethylisopropylcarbodiimide methacrylate was charged while maintaining the temperature, and then tert-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by Nichiyu Co., Ltd.) dissolved in 10 mL of xylene was added. 8.0 mmol was fed over 10 minutes while stirring at a stirring speed of 400 rpm using a double anchor blade. Then, after stirring for another 3 hours, 150 mL of xylene was fed to dilute the reaction solution.
- Perbutyl I manufactured by Nichiyu Co., Ltd.
- Example 20 11 parts by mass of the graft polymer (P-1) produced in Example 1 and 89 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were screwed at a temperature of 190 ° C. using a laboplast mill.
- the press molding machine was kneaded at a rotation speed of 60 rpm and a kneading time of 10 minutes, then press-molded under the conditions of a temperature of 180 ° C., a pressure of 4 MPa, a residual heat time of 5 minutes, and a pressurization time of 3 minutes, and then set to 20 ° C.
- the olefin resin composition C-1 (press sheet having a thickness of 500 ⁇ m, a length of 80 mm, and a width of 80 mm) was obtained by quenching with.
- the obtained olefin resin composition C-1 had an MFR (190 ° C., 2.16 kg load) of 2.7 g / 10 minutes and a density of 0.903 g / cm 3 .
- Example 21 By the same method as in Example 20 except that 12 parts by mass of the graft polymer (P-2) produced in Example 2 and 88 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-2 was obtained. The obtained olefin resin composition C-2 had an MFR (190 ° C., 2.16 kg load) of 0.6 g / 10 minutes and a density of 0.893 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 22 By the same method as in Example 20 except that 12 parts by mass of the graft polymer (P-6) produced in Example 6 and 88 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-3 was obtained. The obtained olefin resin composition C-3 had an MFR (190 ° C., 2.16 kg load) of 2.93 g / 10 minutes and a density of 0.903 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 23 In the same manner as in Example 20, except that 10 parts by mass of the graft polymer (P-7) produced in Example 7 and 90 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-4 was obtained. The obtained olefin resin composition C-4 had an MFR (190 ° C., 2.16 kg load) of 3.1 g / 10 minutes and a density of 0.902 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 24 By the same method as in Example 20 except that 16 parts by mass of the graft polymer (P-8) produced in Example 8 and 84 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-5 was obtained. The obtained olefin resin composition C-5 had an MFR (190 ° C., 2.16 kg load) of 3.5 g / 10 minutes and a density of 0.902 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 25 In the same manner as in Example 20, except that 17 parts by mass of the graft polymer (P-9) produced in Example 9 and 83 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-6 was obtained. The obtained olefin resin composition C-6 had an MFR (190 ° C., 2.16 kg load) of 2.73 g / 10 minutes.
- Example 26 By the same method as in Example 20 except that 12 parts by mass of the graft polymer (P-10) produced in Example 10 and 88 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-7 was obtained.
- Example 27 In the same manner as in Example 20, except that 21 parts by mass of the graft polymer (P-11) produced in Example 11 and 79 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition C-8 was obtained.
- Example 28 By the same method as in Example 20 except that 12 parts by mass of the graft polymer (P-12) produced in Example 12 and 88 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-9 was obtained. The obtained C-9 had an MFR (190 ° C., 2.16 kg load) of 1.0 g / 10 minutes.
- Example 29 By the same method as in Example 20 except that 14 parts by mass of the graft polymer (P-13) produced in Example 13 and 86 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-10 was obtained. The obtained olefin resin composition C-10 had an MFR (190 ° C., 2.16 kg load) of 1.8 g / 10 minutes.
- Example 30 By the same method as in Example 20 except that 13 parts by mass of the graft polymer (P-14) produced in Example 14 and 87 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-11 was obtained. The obtained olefin resin composition C-11 had an MFR (190 ° C., 2.16 kg load) of 2.0 g / 10 minutes and a density of 0.892 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 31 By the same method as in Example 20 except that 13 parts by mass of the graft polymer (P-15) produced in Example 15 and 87 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-12 was obtained.
- Example 32 By the same method as in Example 20 except that 13 parts by mass of the graft polymer (P-16) produced in Example 16 and 87 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition C-13 was obtained.
- Example 3 By the same method as in Example 20 except that 10 parts by mass of the graft polymer (CP-1) produced in Comparative Example 1 and 90 parts by mass of LLDPE (the same polymer as the base polymer used in Example 1) were used. An olefin resin composition CC-1 was obtained. The obtained olefin resin composition CC-1 had an MFR (190 ° C., 2.16 kg load) of 3.2 g / 10 minutes and a density of 0.902 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- Example 4 By the same method as in Example 20 except that 12 parts by mass of the graft polymer (CP-2) produced in Comparative Example 2 and 88 parts by mass of PP (the same polymer as the base polymer used in Example 2) were used. An olefin resin composition CC-2 was obtained. The obtained olefin resin composition CC-2 had an MFR (190 ° C., 2.16 kg load) of 1.9 g / 10 minutes and a density of 0.892 g / cm 3 .
- MFR 190 ° C., 2.16 kg load
- ⁇ Adhesion evaluation> Preparation of press sheet
- the graft polymers obtained in Examples 1 and 3 and Comparative Example 1 were press-molded under the conditions of temperature 180 ° C., pressure 4 MPa, residual heat time 5 minutes, and pressurization time 3 minutes, and then to 20 ° C.
- a press sheet having a thickness of 500 ⁇ m, a length of 80 mm, and a width of 80 mm was produced by quenching with the set press molding machine.
- PET polyethylene terephthalate
- product name: Lumirer T60, manufactured by Toray Industries, Inc. having a thickness of 50 ⁇ m, a length of 80 mm, and a width of 80 mm was used as the base material layer.
- a PET sheet, a press sheet, and a PET sheet are stacked in this order, and the stacked products are sandwiched between Teflon (registered trademark) sheets, and the press plate (bottom) temperature is 230 ° C and the press plate (top) temperature is 230 ° C or 250 ° C.
- the heat sealer set to 1 was used for heat sealing for 5 seconds, 10 seconds or 30 seconds to prepare a laminated body consisting of three layers.
- the upper PET sheet (PET sheet on the press plate (upper) side) and the press sheet were placed in a T-shape under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 300 mm / min, and a peel width of 15 mm. By peeling, the peel strength between the PET sheet and the press sheet was measured. The results are shown in Table 1. Since the adhesive strength is strong, the case where the PET sheet itself is cut, not the interface between the PET sheet and the press sheet, is referred to as "PET resin cut”.
- a polyethylene terephthalate (PET) sheet (product name: Lumirer T60, manufactured by Toray Industries, Inc.) having a thickness of 50 ⁇ m, a length of 80 mm, and a width of 80 mm was used.
- PET sheet, a press sheet (olefin-based resin composition obtained in Examples 20 to 32 or Comparative Examples 3 to 4) and a PET sheet are stacked in this order, and the stacked products are sandwiched between Teflon (registered trademark) sheets.
- a laminated body consisting of three layers was prepared by heat-sealing for 3 seconds with a heat sealer in which the temperature above and below the press plate was set to 200 ° C. or 230 ° C. Using the prepared laminate, a peeling test was performed in the same manner as described above. The results are shown in Table 2.
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Abstract
Description
[12] 前記極性基がカルボキシ基またはヒドロキシ基である、[11]に記載の積層体。
本発明の一実施形態に係るグラフト変性体(以下「本変性体」ともいう。)は、ポリオレフィンから選ばれる少なくとも1種のベースポリマーの、カルボジイミド基と重合性二重結合とを有するカルボジイミドモノマーによるグラフト変性体であり、換言すれば、ポリオレフィンから選ばれる少なくとも1種のベースポリマーが、カルボジイミド基と重合性二重結合とを有するカルボジイミドモノマーでグラフト変性された、グラフト変性体である。また本変性体は、ポリオレフィンから選ばれる少なくとも1種のベースポリマー部分と、カルボジイミド基と重合性二重結合とを有するカルボジイミドモノマーに由来するグラフト部分とを含むグラフト変性体であるともいえる。
本変性体は、グリシジル(メタ)アクリレートによるグラフト変性体に比べ、ポリエステルやポリフェニレンサルファイドなどに存在する極性基との反応性が高いため、これらの基材への接着性に顕著に優れる。
さらに本変性体は、エチレンやプロピレン等のオレフィン系モノマーと前記カルボジイミドモノマーとのブロック共重合体やランダム共重合体ではなく、グラフト変性体であるため、前記効果を奏する。
前記グラフト率は、グラフト変性体中の、カルボジイミドモノマー由来の構造の質量であり、1H-NMR測定、具体的には下記実施例に記載の方法により求めることができる。
前記ベースポリマーをグラフト変性する際に用いられるカルボジイミドモノマーは、カルボジイミド基と重合性二重結合とを有する化合物であれば特に制限されないが、本発明の効果がより発揮される等の点から、下記式(1)または(2)で表される化合物であることが好ましい。
前記ベースポリマーをグラフト変性する際に用いられるカルボジイミドモノマーは、2種以上であってもよいが、通常1種である。
前記置換基を有してもよい炭化水素基の炭素数は、好ましくは1以上、より好ましくは3以上であり、好ましくは20以下、より好ましくは12以下、さらに好ましくは8以下である。
前記炭化水素基が有していてもよい置換基としては、例えば、ハロゲン原子、炭素数1~8の炭化水素基、炭素数1~8のアルコキシ基、炭素数1~8のカルボン酸エステル基、炭素数1~8のスルホン酸エステル基、炭素数1~8のカルボニル基、炭素数1~8のアミド基、炭素数1~8のアミノ基、炭素数1~8スルフィド基、炭素数1~8のリン酸エステル基、炭素数1~8のアルキルシリル基、炭素数1~8のアルコキシシリル基が挙げられる。
前記脂環としては、例えば、シクロブチル環、シクロペンチル環、シクロヘキシル環、シクロヘプチル環、炭化水素基を有するこれらの環が挙げられる。また、前記脂環は、アダマンチル環、メチルアダマンチル環などの多環式の環であってもよい。
前記置換基を有してもよい炭化水素基の炭素数は、好ましくは1以上、より好ましくは3以上であり、好ましくは20以下、より好ましくは12以下、さらに好ましくは8以下である。
前記炭化水素基が有していてもよい置換基としては、例えば、ハロゲン原子、炭素数1~8の炭化水素基、炭素数1~8のアルコキシ基、炭素数1~8のカルボン酸エステル基、炭素数1~8のスルホン酸エステル基、炭素数1~8のカルボニル基、炭素数1~8のアミド基、炭素数1~8のアミノ基、炭素数1~8スルフィド基、炭素数1~8のリン酸エステル基、炭素数1~8のアルキルシリル基、炭素数1~8のアルコキシシリル基が挙げられる。
前記カルボジイミドモノマーでグラフト変性される前のベースポリマーは、ポリオレフィンから選ばれる少なくとも1種のポリマーである。
該オレフィンの具体例としては、エチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン、4-メチル-1-ペンテンが挙げられる。
前記ポリオレフィンは、これらのオレフィンの単独重合体であってもよく、2種以上のこれらのオレフィンの共重合体であってもよく、1種以上のこれらのオレフィンと、1種以上の下記コポリマーとの共重合体であってもよい。これらの中でも、前記ポリオレフィンとしては、エチレン系重合体、プロピレン系重合体、ブテン系重合体から選ばれる少なくとも1種のポリマーであることが好ましく、グラフト反応の際に溶媒を用いる場合、該溶媒への溶解性に優れ、かつ、グラフト反応後の不純物との分離性に優れる等の点から、エチレン系重合体、プロピレン系重合体から選ばれる少なくとも1種のポリマーであることがより好ましい。
前記ベースポリマーは、2種以上であってもよいが、通常1種である。
また、前記ベースポリマーは、本発明の効果がより発揮される等の点から、酸ハライド、アミド、イミド、エステルなどのカルボン酸誘導体基や、エポキシ基等の、水などにより容易に活性水素を持つ基に変換される基を有さないポリマーであることも好ましい。
前記ベースポリマーの数平均分子量(Mn)も特に制限されないが、同様の理由から、好ましくは40,000以上、より好ましくは50,000以上であり、好ましくは500,000以下、より好ましくは300,000以下である。
前記ベースポリマーの分子量分布(Mw/Mn)も特に制限されないが、好ましくは1.5以上、より好ましくは2.0以上であり、好ましくは6.0以下、より好ましくは5.0以下である。
分離カラム:TSKgel GMH6-HT(2本)とTSKgel GMH6-HTL(2本)(いずれも7.5mmI.D.×30cm、東ソー(株)製)
カラム温度:140℃
移動相:o-ジクロロベンゼン(0.025%ジブチルヒドロキシトルエン(BHT)含有)
展開速度:1.0mL/分
試料濃度:0.1%(w/v)
試料注入量:0.4mL
検出器:示差屈折計
装置の較正:単分散ポリスチレン(東ソー(株)製、#3std set)を用いた
前記従来公知の方法としては特に制限されず、例えば、遷移金属を含む配位重合触媒系を用いる方法が挙げられる。具体的には、塩化マグネシウム担持型チタン触媒、可溶性バナジウム化合物とアルキルアルミニウムハライド化合物とを含むバナジウム系触媒、または、メタロセン化合物と有機アルミニウムオキシ化合物とを含むメタロセン触媒等の触媒の存在下に、エチレンまたはプロピレンと、必要に応じて後述のコモノマーとを(共)重合させることで合成する方法が挙げられる。
前記エチレン系重合体は、該重合体中のエチレン由来の構成単位の含有量が50質量%以上である重合体であれば特に制限されず、エチレンの単独重合体であってもよく、エチレンとコモノマーとの共重合体であってもよい。共重合体の場合、その構造は特に制限されない。
前記炭素数4~20のα-オレフィンとしては、直鎖状であっても分岐状であってもよく、例えば、1-ブテン、2-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセンが挙げられる。
前記エチレン系重合体中の前記コモノマー由来の構成単位の含有量は、ペレットやパウダーのブロッキングが無く取り扱いやすい等の点から、好ましくは50質量%以下、より好ましくは30質量%以下、特に好ましくは20質量%以下である。なお、プロピレン由来やブテン由来の構成単位の含有量が50質量%のエチレン系重合体は、本明細書では、エチレン系重合体という。
前記プロピレン系重合体は、該重合体中のプロピレン由来の構成単位の含有量が50質量%以上である重合体であれば特に制限されず、プロピレンの単独重合体であってもよく、プロピレンとコモノマーとの共重合体であってもよい。これら(共)重合体の構造は特に制限されない。
前記炭素数4~20のα-オレフィンとしては、エチレン系重合体の欄で挙げた炭素数4~20のα-オレフィンと同様のα-オレフィン等が挙げられる。
前記プロピレン系重合体中の前記コモノマー由来の構成単位の含有量は、ペレットやパウダーのブロッキングが無く取り扱いやすい等の点から、好ましくは50質量%以下、より好ましくは30質量%以下、特に好ましくは20質量%以下である。なお、ブテン由来の構成単位の含有量が50質量%のプロピレン系重合体は、本明細書では、プロピレン系重合体という。
前記ブテン系重合体は、該重合体中のブテン由来の構成単位の含有量が50質量%以上である重合体であれば特に制限されず、ブテン、特に1-ブテンの単独重合体であってもよく、ブテン(特に1-ブテン)とコモノマーとの共重合体であってもよい。これら(共)重合体の構造は特に制限されない。
前記炭素数5~20のα-オレフィンとしては、エチレン系重合体の欄で挙げた炭素数5~20のα-オレフィンと同様のα-オレフィン等が挙げられる。
前記ブテン系重合体中の前記コモノマー由来の構成単位の含有量は、ペレットやパウダーのブロッキングが無く取り扱いやすい等の点から、好ましくは50質量%以下、より好ましくは30質量%以下、特に好ましくは20質量%以下である。
本変性体の合成方法は特に制限されず、前記ベースポリマーを前記カルボジイミドモノマーでグラフト変性したグラフト変性体が得られれば特に制限されないが、本変性体を容易に合成できる等の点から、前記ベースポリマーを溶剤に溶解または分散した液、好ましくは前記ベースポリマーを有機溶剤に溶解した溶液に、ラジカル開始剤および前記カルボジイミドモノマーを添加して反応(グラフト反応)させる方法が好ましい。なお、ベースポリマーを均質に流動させることができる攪拌能力を有する反応装置を用いる場合には、溶剤を用いなくてもよい。
前記方法によれば、グラフト重合が起こるため、グラフト変性体が得られる。
前記ラジカル開始剤は、1種単独で用いてもよく、2種以上を用いてもよい。
なお、ベースポリマーまたはベースポリマーを溶剤に溶解または分散した液にラジカル開始剤およびカルボジイミドモノマーを添加する場合には、これらの添加順は特に制限されず、例えば、前記のようにこれらを逐次的に添加する場合、ラジカル開始剤およびカルボジイミドモノマーを逐次的に添加してもよいし、先にカルボジイミドモノマーを添加した後、ラジカル開始剤を逐次的に添加してもよい。
この場合、前記相容性や接着性により優れる本変性体を容易に得ることができる等の点から、本変性体中に含まれる非グラフト化ポリマーの含有量が、好ましくは5質量%以下、より好ましくは2質量%以下となるように、精製・単離することが望ましい。
本変性体は、ポリエステル、ポリフェニレンサルファイド、ポリアミド、ポリアセタール、ポリカーボネート、ポリ(メタ)アクリレート、変性フッ素樹脂、バイオマスプラスチックなどの極性樹脂やオレフィン系重合体との相容性に優れるため、これら極性樹脂やオレフィン系重合体を含む組成物の相容化剤、金属、ガラス、紙、または、前記極性樹脂やオレフィン系重合体などとの接着性に優れるため、これらを含む基材に対する接着剤、オレフィン系重合体への分散性に優れるため、オレフィン系重合体と混合して、オレフィン系樹脂組成物などとして用いることができる。
これらの中でも、本変性体は、ポリエステル、ポリフェニレンサルファイドへの接着性に優れるため、本発明の効果がより発揮される等の点からは、ポリエステルやポリフェニレンサルファイド(を含む層)に対する接着剤、オレフィン系樹脂組成物として用いることが好ましい。
該添加剤としては、例えば、軟化剤、安定剤、充填剤、酸化防止剤、結晶核剤、ワックス、増粘剤、機械的安定性付与剤、レベリング剤、濡れ剤、造膜助剤、架橋剤、防腐剤、防錆剤、顔料、分散剤、凍結防止剤、消泡剤、粘着性付与剤、他の熱可塑性重合体、水、有機溶媒が挙げられ、これらはそれぞれ、1種単独で用いてもよく、2種以上を用いてもよい。
本発明の一実施形態に係るオレフィン系樹脂組成物は、前記本変性体と、1種以上のオレフィン系重合体とを含めば特に制限されず、該オレフィン系樹脂組成物に含まれる本変性体は、1種でも、2種以上でもよい。
また、前記オレフィン系樹脂組成物は、前述の添加剤をそれぞれ、1種または2種以上含んでいてもよい。
前記オレフィン系樹脂組成物中におけるオレフィン系重合体の含有量は特に制限されないが、成形加工性や接着能の制御性、経済性等の点から、通常60質量%以上、好ましくは75質量%以上であり、通常99.5質量%以下、好ましくは99質量%以下である。
本発明の一実施形態に係る接着剤(感圧接着剤を含む)は、前記本変性体または前記オレフィン系樹脂組成物を含めば特に制限されず、該接着剤に含まれる本変性体およびオレフィン系樹脂組成物はそれぞれ、1種でも、2種以上でもよい。
前記接着剤は、本変性体のみからなる接着剤であってもよく、前述のオレフィン系重合体や添加剤をそれぞれ、1種または2種以上含んでいてもよい。
前記本変性体を含む接着剤中における前記本変性体の含有量は特に制限されないが、通常5~100質量%、好ましくは10~100質量%である。
本発明の一実施形態に係る積層体は、前記本変性体または前記オレフィン系樹脂組成物を含む層(A)と、基材層(B)とを含めば特に制限されず、該層(A)を2層以上含んでいてもよく、該基材層(B)を2層以上含んでいてもよい。2層以上の層(A)を含む場合、これらの層は、同一の層であってもよく、異なる層であってもよい。また、2層以上の基材層(B)を含む場合も同様に、これらの層は、同一の層であってもよく、異なる層であってもよい。
前記積層体としては、層(A)と基材層(B)とを含む積層体、または、基材層(B)と層(A)と基材層(B)とをこの順で含む積層体であることが好ましい。
また、前記基材層(B)の厚さも特に制限されず、積層体の用途により適宜選択すればよいが、好ましくは2~1000μmである。
このような基材層(B)を用いると、前記本変性体中のカルボジイミド基が、該基材層(B)中の極性基と反応し、結合している状態となるため、前記層(A)と前記基材層(B)との接着性がより向上する。この場合、前記層(A)中には、本変性体だけでなく、本変性体のカルボジイミド基が基材層(B)の極性基と反応した状態も含まれる。
例えば、ポリエステルは通常、末端にカルボキシ基、ヒドロキシ基を有する。また、ポリフェニレンサルファイドは通常、末端にカルボキシ基を有する。ガラスや金属も通常、ヒドロキシ基を有する。
(1)予め成形された層(A)および基材層(B)の少なくとも一方の層が溶融する温度以上の温度でカレンダーロール成形機、圧縮成形機などを用いて熱融着する方法。
(2)予め成形された層(A)または基材層(B)を、押出成形、カレンダー成形をしている他の層に熱融着する方法。
(3)基材層(B)として、熱可塑性樹脂を含む層を用いる場合は、多層押出成形機で層(A)と基材層(B)とを同時に押出成形して熱融着(共押出成形)する方法。
(4)基材層(B)として、熱可塑性樹脂を含む層を用いる場合は、溶融した層(A)形成材料と、溶融した基材層(B)形成材料とを、射出のタイミングをずらして金型内に射出(例:2層射出成形、サンドイッチ射出成形)する方法。
さらに、前記積層体は、前記本変性体または前記オレフィン系樹脂組成物を含む層(A)を有するので、層間接着性に優れ、しかも、例えば、230℃でヒートシールする場合、ヒートシール時間を、好ましくは20秒以下、より好ましくは10秒以下、さらに好ましくは5秒以下という短時間としても、接着強度の高い層を形成することができる。
グラフト率は、ブルカー・バイオスピン(株)製、AVANCEIIIcryo-500型核磁気共鳴装置(500MHz)を用い、測定溶媒:1,1,2,2-テトラクロロエタン-d2、測定温度:120℃、スペクトル幅:20ppm、パルス繰り返し時間:7.0秒、パルス幅:5.00μsec(45°パルス)の測定条件下にて、1H-NMRスペクトルを測定した。得られたスペクトルにおいて、3.0ppm~4.0ppmに存在するカルボジイミド基に結合した炭化水素基のプロトンと、0.3ppm~2.5ppmに存在する原料ポリマー由来の全ての炭化水素基に結合したプロトンのピーク強度比率から、グラフト率を算出した。
1Lのオートクレーブに、LLDPE(ベースポリマー、コモノマー種:1-ヘキセン、コモノマー量:1.6質量%、Mw:164,000、Mn:63,000、Mw/Mn:2.60)を25.0gおよびトルエンを150mL装入し、オートクレーブ内を窒素置換した後、密閉した。その後、オートクレーブの内温を140℃まで昇温し、その温度を維持しながら、ビニルフェニルシクロヘキシルカルボジイミド28.1mmolおよびジクミルペルオキシド2.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、2時間かけてフィードした。その後、さらに2時間攪拌した後、トルエンを15分かけて250mLフィードし、反応液を希釈した。
前記3回目の濾過後の固形分を、70℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-1)を得た。グラフトポリマー(P-1)の収量は25.71gであった(質量増加量:0.71g)。また、グラフト率は2.7質量%であった。
500mLのガラス容器に、PP(ベースポリマー、プロピレン単独重合体、Mw:313,000、Mn:70,800、Mw/Mn:4.43)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、ビニルフェニルシクロヘキシルカルボジイミド28.1mmol、および、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)2.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-2)を25.13g得た。なお、グラフト率は1.5質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、ビニルフェニルフェニルカルボジイミドを14mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.1mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-3)を25.62g得た。なお、グラフト率は3.4質量%であった。
500mLのガラス容器に、4-メチルペンテン単独重合体(ベースポリマー、Mw:671,000、Mn:297,000、Mw/Mn:2.26)を12.5gおよびキシレンを50mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、ビニルフェニルシクロヘキシルカルボジイミドを14mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.1mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-4)を12.71g得た。なお、グラフト率は1.4質量%であった。
500mLのガラス容器に、EBR(ベースポリマー、DF710、三井化学(株)製)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、ビニルフェニルシクロヘキシルカルボジイミドを14mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.1mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-5)を26.08g得た。なお、グラフト率は3.3質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルフェニルカルボジイミドを33.4mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)2.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけて滴下した。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-6)を25.87g得た。なお、グラフト率は2.4質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を17.0gおよびキシレンを78mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルシクロヘキシルカルボジイミドを24.5mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.68mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけて滴下した。その後、さらに3時間攪拌した後、キシレンを150mL装入し、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-7)を17.49g得た。なお、グラフト率は3.0質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-tert-ブチルカルボジイミドを35.0mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)2.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-8)を25.49g得た。なお、グラフト率は1.7質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を17.1gおよびキシレンを73mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-n-ブチルカルボジイミドを23.8mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.6mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-9)を17.38g得た。なお、グラフト率は1.6質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を14.0gおよびキシレンを57mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-p-クロロフェニルカルボジイミドを19.0mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.3mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-10)を14.43g得た。なお、グラフト率は2.8質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を17.0gおよびキシレンを73mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-p-メトキシフェニルカルボジイミドを22.5mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)1.5mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-11)を17.37g得た。なお、グラフト率は1.6質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を20.0gおよびキシレンを86mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルフェニルカルボジイミドを22.6mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)9.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-12)を19.89g得た。なお、グラフト率は1.5質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を19.0gおよびキシレンを81mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルシクロヘキシルカルボジイミドを20mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)9.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-13)を18.89g得た。なお、グラフト率は1.4質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を15.0gおよびキシレンを62mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-tert-ブチルカルボジイミドを22.1mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)9.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-14)を15.37g得た。なお、グラフト率は1.3質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を15.0gおよびキシレンを62mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-p-クロロフェニルカルボジイミドを17.8mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)6.9mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-15)を14.60g得た。なお、グラフト率は1.6質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を20.0gおよびキシレンを86mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-p-メトキシフェニルカルボジイミドを22.5mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)9.2mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-16)を20.30g得た。なお、グラフト率は1.6質量%であった。
500mLのガラス容器に、EBR(前記実施例5で用いたベースポリマーと同じポリマー)を10.0gおよびキシレンを38mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチル-tert-ブチルカルボジイミドを13.4mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)0.9mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-17)を18.91g得た。なお、グラフト率は4.1質量%であった。
500mLのセパラブルフラスコに、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を23gおよびキシレンを100mL装入し、セパラブルフラスコ内を窒素置換した後、内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルイソプロピルカルボジイミドを30mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)2.0mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを200mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-18)を23.54g得た。なお、グラフト率は1.7質量%であった。
500mLのセパラブルフラスコに、PP(前記実施例2で用いたベースポリマーと同じポリマー)を13.2gおよびキシレンを54mL装入し、セパラブルフラスコ内を窒素置換した後、内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸エチルイソプロピルカルボジイミドを19.5mmol装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)8.0mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した後、キシレンを150mLフィードし、反応液を希釈した。
前記4回目の濾過後の固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(P-19)を13.29g得た。なお、グラフト率は1.7質量%であった。
500mLのガラス容器に、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)を25.0gおよびキシレンを110mL装入し、容器内を窒素置換した。その後、容器の内温を120℃に昇温し、メタクリル酸グリシジル33.4mmolを容器内に装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)2.21mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけてフィードした。その後、さらに3時間攪拌した。
得られたグラフトポリマー(CP-1)の収量は25.95gであった。また、グラフト率は2.4質量%であった。
500mLのガラス容器に、PP(前記実施例2で用いたベースポリマーと同じポリマー)を25.0gおよびキシレンを120mL装入し、容器内を窒素置換した。その後、容器の内温を120℃まで昇温し、その温度を維持しながら、メタクリル酸グリシジル33.4mmolを装入し、次いで、キシレン10mLに溶解したtert-ブチルパーオキシイソプロピルモノカーボネート(パーブチルI、日油(株)製)11mmolを、ダブルアンカー翼を用い、攪拌速度400rpmで攪拌しながら、10分かけて滴下した。その後、さらに3時間攪拌した。
得られた固形分を、90℃の真空乾燥機で10時間乾燥することで、グラフトポリマー(CP-2)を25.26g得た。なお、グラフト率は1.0質量%であった。
実施例1で製造したグラフトポリマー(P-1)11質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)89質量部とを、ラボプラストミルを用いて温度190℃、スクリュー回転数60rpm、混錬時間10分にて混錬し、次いで、温度180℃、圧力4MPa、余熱時間5分、加圧時間3分の条件でプレス成形し、その後20℃に設定したプレス成形機で急冷することにより、オレフィン系樹脂組成物C-1(厚さ500μm、長さ80mm、幅80mmのプレスシート)を得た。
得られたオレフィン系樹脂組成物C-1は、MFR(190℃、2.16kg荷重)が2.7g/10分であり、密度が0.903g/cm3であった。
実施例2で製造したグラフトポリマー(P-2)12質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)88質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-2を得た。
得られたオレフィン系樹脂組成物C-2は、MFR(190℃、2.16kg荷重)が0.6g/10分であり、密度が0.893g/cm3であった。
実施例6で製造したグラフトポリマー(P-6)12質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)88質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-3を得た。
得られたオレフィン系樹脂組成物C-3は、MFR(190℃、2.16kg荷重)が2.93g/10分であり、密度が0.903g/cm3であった。
実施例7で製造したグラフトポリマー(P-7)10質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)90質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-4を得た。
得られたオレフィン系樹脂組成物C-4は、MFR(190℃、2.16kg荷重)が3.1g/10分であり、密度が0.902g/cm3であった。
実施例8で製造したグラフトポリマー(P-8)16質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)84質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-5を得た。
得られたオレフィン系樹脂組成物C-5は、MFR(190℃、2.16kg荷重)が3.5g/10分であり、密度が0.902g/cm3であった。
実施例9で製造したグラフトポリマー(P-9)17質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)83質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-6を得た。
得られたオレフィン系樹脂組成物C-6は、MFR(190℃、2.16kg荷重)が2.73g/10分であった。
実施例10で製造したグラフトポリマー(P-10)12質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)88質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-7を得た。
実施例11で製造したグラフトポリマー(P-11)21質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)79質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-8を得た。
実施例12で製造したグラフトポリマー(P-12)12質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)88質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-9を得た。
得られたC-9は、MFR(190℃、2.16kg荷重)が1.0g/10分であった。
実施例13で製造したグラフトポリマー(P-13)14質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)86質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-10を得た。
得られたオレフィン系樹脂組成物C-10は、MFR(190℃、2.16kg荷重)が1.8g/10分であった。
実施例14で製造したグラフトポリマー(P-14)13質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)87質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-11を得た。
得られたオレフィン系樹脂組成物C-11は、MFR(190℃、2.16kg荷重)が2.0g/10分であり、密度が0.892g/cm3であった。
実施例15で製造したグラフトポリマー(P-15)13質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)87質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-12を得た。
実施例16で製造したグラフトポリマー(P-16)13質量部と、PP(前記実施例2で用いたベースポリマーと同じポリマー)87質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物C-13を得た。
比較例1で製造したグラフトポリマー(CP-1)10質量部と、LLDPE(前記実施例1で用いたベースポリマーと同じポリマー)90質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物CC-1を得た。
得られたオレフィン系樹脂組成物CC-1は、MFR(190℃、2.16kg荷重)が3.2g/10分であり、密度が0.902g/cm3であった。
比較例2で製造したグラフトポリマー(CP-2)12質量部とPP(前記実施例2で用いたベースポリマーと同じポリマー)を88質量部とを用いた以外は実施例20と同様の方法でオレフィン系樹脂組成物CC-2を得た。
得られたオレフィン系樹脂組成物CC-2は、MFR(190℃、2.16kg荷重)が1.9g/10分であり、密度が0.892g/cm3であった。
・プレスシートの作製
実施例1、3および比較例1で得たグラフトポリマーそれぞれを、温度180℃、圧力4MPa、余熱時間5分、加圧時間3分の条件でプレス成形し、その後20℃に設定したプレス成形機にて急冷することにより、厚さ500μm、長さ80mm、幅80mmのプレスシートを作製した。
基材層として、厚さ50μm、長さ80mm、幅80mmのポリエチレンテレフタレート(PET)シート(製品名:ルミラーT60、東レ(株)製)を用いた。
PETシート、プレスシートおよびPETシートの順に重ね、これらを重ねたものをテフロン(登録商標)シートで挟んで、プレス板(下)温度を230℃、プレス板(上)温度を230℃または250℃に設定したヒートシーラーにて、5秒、10秒または30秒間ヒートシールを行い、3層からなる積層体を作製した。
作製した積層体について、上側のPETシート(プレス板(上)側のPETシート)とプレスシートとを、剥離雰囲気温度23℃、剥離速度300mm/分、ピール幅15mmの条件でT型剥離することで、該PETシートとプレスシートとの剥離強度を測定した。結果を表1に示す。なお、接着力が強いため、PETシートとプレスシートとの界面ではなく、PETシート自体が切れた場合を「PET樹脂切れ」と示す。
基材層として、厚さ50μm、長さ80mm、幅80mmのポリエチレンテレフタレート(PET)シート(製品名:ルミラーT60、東レ(株)製)を用いた。
PETシート、プレスシート(実施例20~32または比較例3~4で得られたオレフィン系樹脂組成物)およびPETシートの順に重ね、これらを重ねたものをテフロン(登録商標)シートで挟んで、プレス板上下温度を200℃または230℃に設定したヒートシーラーにて、3秒間ヒートシールを行い、3層からなる積層体を作製した。
作製した積層体を用いて、前記と同様にして剥離試験を行った。結果を表2に示す。
Claims (12)
- ポリオレフィンから選ばれる少なくとも1種のベースポリマーの、カルボジイミド基と重合性二重結合とを有するカルボジイミドモノマーによるグラフト変性体。
- 前記R2が、脂環を含む炭素数4~20の脂肪族炭化水素基である、請求項2に記載のグラフト変性体。
- 前記R3はメチル基であり、R4は、分岐を有し、かつ、環を有さないアルキル基であり、mは2である、請求項4に記載のグラフト変性体。
- 前記ベースポリマーが、カルボキシ基、酸無水物基、アミノ基、ヒドロキシ基およびチオール基から選ばれる少なくとも1つの活性水素含有基を有さないポリマーである、請求項1~5のいずれか1項に記載のグラフト変性体。
- 前記ポリオレフィンが、エチレン系重合体およびプロピレン系重合体から選ばれる少なくとも1種である、請求項1~6のいずれか1項に記載のグラフト変性体。
- 請求項1~7のいずれか1項に記載のグラフト変性体と、1種以上のオレフィン系重合体とを含む、オレフィン系樹脂組成物。
- 請求項1~7のいずれか1項に記載のグラフト変性体または請求項8に記載のオレフィン系樹脂組成物を含む、接着剤。
- 請求項1~7のいずれか1項に記載のグラフト変性体を含む層、および、請求項8に記載のオレフィン系樹脂組成物を含む層から選ばれる1つの層(A)と、基材層(B)とを含む、積層体。
- 前記基材層(B)が極性基を有する層である、請求項10に記載の積層体。
- 前記極性基がカルボキシ基またはヒドロキシ基である、請求項11に記載の積層体。
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JP2022566932A JPWO2022118836A1 (ja) | 2020-12-04 | 2021-11-30 | |
KR1020237017195A KR20230093011A (ko) | 2020-12-04 | 2021-11-30 | 그래프트 변성체, 접착제, 올레핀계 수지 조성물 및 적층체 |
US18/038,683 US20240026054A1 (en) | 2020-12-04 | 2021-11-30 | Graft-modified product, adhesive, olefin resin composition, and laminate |
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WO2023182467A1 (ja) * | 2022-03-25 | 2023-09-28 | 三井化学株式会社 | 積層体、積層体の製造方法および接着組成物 |
WO2023229006A1 (ja) * | 2022-05-26 | 2023-11-30 | 三井化学株式会社 | 積層体および積層体の製造方法 |
WO2023229012A1 (ja) * | 2022-05-26 | 2023-11-30 | 三井化学株式会社 | 積層体および積層体の製造方法 |
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JPH06145260A (ja) | 1992-10-30 | 1994-05-24 | Tonen Corp | 変性ポリオレフィン |
JP2005048127A (ja) * | 2003-07-31 | 2005-02-24 | Mitsubishi Paper Mills Ltd | カルボジイミド化合物および重合体、ゲル状組成物、イオン伝導性組成物、電気化学素子および表面修飾基材 |
WO2007040261A1 (ja) * | 2005-10-06 | 2007-04-12 | Mitsui Chemicals, Inc. | 接着剤およびそれを用いた積層体 |
JP2019135698A (ja) * | 2018-02-05 | 2019-08-15 | 藤森工業株式会社 | 電極リード線部材、及び電池 |
WO2020145239A1 (ja) * | 2019-01-07 | 2020-07-16 | 三井化学株式会社 | 接着性樹脂組成物および積層体 |
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- 2021-11-30 US US18/038,683 patent/US20240026054A1/en active Pending
- 2021-11-30 KR KR1020237017195A patent/KR20230093011A/ko unknown
- 2021-11-30 CN CN202180077047.6A patent/CN116438076A/zh active Pending
- 2021-11-30 EP EP21900589.9A patent/EP4257357A1/en active Pending
- 2021-12-02 TW TW110144934A patent/TW202235450A/zh unknown
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JPH06145260A (ja) | 1992-10-30 | 1994-05-24 | Tonen Corp | 変性ポリオレフィン |
JP2005048127A (ja) * | 2003-07-31 | 2005-02-24 | Mitsubishi Paper Mills Ltd | カルボジイミド化合物および重合体、ゲル状組成物、イオン伝導性組成物、電気化学素子および表面修飾基材 |
WO2007040261A1 (ja) * | 2005-10-06 | 2007-04-12 | Mitsui Chemicals, Inc. | 接着剤およびそれを用いた積層体 |
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WO2020145239A1 (ja) * | 2019-01-07 | 2020-07-16 | 三井化学株式会社 | 接着性樹脂組成物および積層体 |
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WO2023182467A1 (ja) * | 2022-03-25 | 2023-09-28 | 三井化学株式会社 | 積層体、積層体の製造方法および接着組成物 |
WO2023229006A1 (ja) * | 2022-05-26 | 2023-11-30 | 三井化学株式会社 | 積層体および積層体の製造方法 |
WO2023229012A1 (ja) * | 2022-05-26 | 2023-11-30 | 三井化学株式会社 | 積層体および積層体の製造方法 |
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JPWO2022118836A1 (ja) | 2022-06-09 |
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US20240026054A1 (en) | 2024-01-25 |
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