JPH0251387B2 - - Google Patents
Info
- Publication number
- JPH0251387B2 JPH0251387B2 JP23435083A JP23435083A JPH0251387B2 JP H0251387 B2 JPH0251387 B2 JP H0251387B2 JP 23435083 A JP23435083 A JP 23435083A JP 23435083 A JP23435083 A JP 23435083A JP H0251387 B2 JPH0251387 B2 JP H0251387B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- olefin
- elastomer
- thermoplastic elastomer
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001971 elastomer Polymers 0.000 claims description 29
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 229920000554 ionomer Polymers 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 239000000806 elastomer Substances 0.000 claims description 18
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 239000005060 rubber Substances 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- -1 polyene compounds Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RFDIBSNFDIXDCJ-UHFFFAOYSA-N 1,3-bis[2-[(2-methylpropan-2-yl)oxy]propan-2-yl]benzene Chemical compound CC(C)(C)OC(C)(C)C1=CC=CC(C(C)(C)OC(C)(C)C)=C1 RFDIBSNFDIXDCJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
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ãè¡šãDetailed Description of the Invention The present invention combines the advantages of thermoplastic elastomers such as elasticity, extrudability and heat resistance, and the advantages of ionomers or 1-olefin/(meth)acrylic acid copolymer resins such as surface gloss and scratch resistance. The object of the present invention is to provide a material that has both the following and does not have the former disadvantage of matteness and the latter disadvantage of lack of heat resistance. Thermoplastic elastomers, which have traditionally been used as sealing materials, cushioning materials, or interior and exterior materials for vehicles, ships, etc., as well as home appliance parts, sporting goods, building materials, etc., have poor surface gloss and scratch resistance, so these are the focus of attention. Protective moldings, windshield gaskets, etc. for automobiles, which are used in the field of
It was rarely used as a bumper or other material. The present inventors have found that not only can the above-mentioned drawbacks of thermoplastic elastomers be substantially eliminated by laminating them with partial ionomers or 1-olefin/(meth)acrylic acid copolymer resins, but also the drawbacks of ionomers etc. The present invention has been completed based on the discovery that it can be removed. That is, the present invention has the following technology as its content. (1) A thermoplastic elastomer layer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing free carboxyl groups or a 1-olefinã»
A laminate with good surface gloss and scratch resistance, which is formed by strongly adhering a methacrylic acid copolymer resin layer. (2) A thermoplastic elastomer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer or 1-olefin copolymer containing a free carboxyl group. A method for manufacturing a laminate in which a methacrylic acid copolymer resin is firmly adhered to the fused resin in a molten state. In addition, (meth)acrylic acid in the present invention is
It is a general term for acrylic acid and methacrylic acid. In the present invention, polyolefin and ethylene
Examples of the thermoplastic elastomer comprising a partially crosslinked α-olefin copolymer elastomer include the following compositions. () Various polyolefin resins (α 1 ) represented by homopolymers of ethylene or propylene or copolymers of these with small amounts of other monomers
and a bipolymer elastomer of ethylene and an α-olefin copolymer having 3 to 14 carbon atoms, or a partially crosslinked product of a terpolymer rubber (b 2 ) obtained by polymerizing these with various non-conjugated polyene compounds. (c 2 ) Thermoplastic elastomer composition () consisting of polyolefin resin (a 1 ) and ethylene α
- Thermoplastic elastomer composition () obtained by dynamically heat-treating a composition with olefin copolymer elastomer (b 1 ) Polyolefin resin (a 1 ) and ethylene α
- The same or different polyolefin resin (a 1 ) or (a 2 ) is added to the partially crosslinked product (c 2 ) obtained by dynamically heat-treating the composition with the olefin copolymer elastomer (b 1 ). A thermoplastic elastomer composition obtained by blending a peroxide crosslinked polyolefin resin (a 1 ) represented by a homopolymer of ethylene or a copolymer of ethylene with a small amount of other monomer (a 1 ) and a monopolymer of propylene. A composition of a peroxide non-crosslinked polyolefin resin (a 1 ) represented by a polymer or a copolymer of propylene and a small amount of other monomers and an ethylene/α-olefin copolymer rubber (b 1 ) In the present invention, the ethylene/α-olefin copolymer rubber that is the raw material for the thermoplastic elastomer refers to, for example, ethylene-propylene copolymer rubber, ethylene-propylene-conjugated diene multi-component rubber,
Ethylene-butadiene copolymer rubber, ethylene-1
-butene copolymer rubber, ethylene-1-butene-nonconjugated diene multipolymer rubber, and other substantially amorphous elastomers containing 1-olefin as a main component, or mixtures thereof. Among these, preferred are ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene multipolymer rubber. Here, non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, 2-ethylidene-5
-Norbornene, etc. Among them, a copolymer containing dicyclopentadiene and 2-ethylidene-5-norbornene as the third component is preferred. The Mooney viscosity [ML 1+4 (100â)] of these binary or polypolymers is usually 10 to 120, preferably 40.
~80, and its iodine value (degree of unsaturation) is preferably 16 or less. The amount of each structural unit contained in these elastomers is such that in the 1-olefin portion, the ratio of ethylene units/α-olefin units is 50/50 to 90/10, preferably 70/30 to 85/15 (molar ratio). and
1-olefin (ethylene + α-olefin) units/non-conjugated diene units) in the case of a multicomponent polymer) is usually 98/2 to 90/10, preferably 97/3 to 94/6
(molar ratio). In the partially crosslinked thermoplastic elastomer constituting the base layer of the laminate of the present invention, the blending ratio of the polyolefin and the ethylene/α-olefin copolymer elastomer constituting the partially crosslinked product is usually based on the polyolefin/elastomer. hand,
The ratio is selected from 80/20 to 20/80, preferably from 70/30 to 30/70 (weight ratio). The above partially crosslinked product is prepared by blending organic peroxide in an amount of usually 0.1 to 2 parts by weight with respect to 100 parts by weight of the raw material elastomer, and dynamically heat-treating the mixture. Here, dynamic heat treatment means kneading in a molten state. As the kneading device, a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. can be used. Usually 150-280
â for 1 to 20 minutes. Organic peroxides used for partial crosslinking include dicumyl peroxide, di-tert-
Brutyl peroxide, 2,5-dimethyl-2;
5-bis(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane-3,1,3-bis(tert
-butylperoxyisopropyl)benzene,
1,1-bis(tert-butylperoxy)-3,
Examples include 3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, dibenzoyl peroxide, and tert-butylperoxybenzoate, among others, scorch stability due to low odor. Bisperoxide compounds are preferred because of their high properties,
1,3-bis(tert-butyloxyisopropyl)benzene is most suitable. During this partial crosslinking treatment, p, which is a crosslinking aid,
- Partially crosslinked products that achieve uniform crosslinking by using polyfunctional compounds such as quinone dioxime, p-p'-dibenzoylquinone dioxime, divinylbenzene (DVB), ethylene glycol dimethacrylate, etc. is more suitable as a raw material for the laminate of the present invention. When preparing thermoplastic elastomers, other organic peroxide non-crosslinked rubbers, such as polyisobutene and butyl rubber (isobutene-isoprene copolymers), mineral oil softeners, carbon black, talc, clay, antioxidants, and other additives may be added. Ingredients can be blended. In the present invention, polyolefin refers to a homopolymer of 1-olefin, a copolymer of two or more thereof, a copolymer of 1-olefin and a conjugated or non-conjugated diolefin, and a copolymer of 1-olefin and another polymerizable vinyl monomer. Copolymers with and modified polyolefins obtained by grafting one or more polymerizable vinyl monomers onto the above polyolefins, etc., which have a crystallinity of usually 50% or more as determined by X-ray diffraction measurement, a melt viscosity index [MI ( (190°C) or MFR (230°C)] usually about 0.1 to 50 g/10 min, preferably a peroxide decomposition type. For example, isotactic polypropylene, copolymers of propylene and up to 15 mol% of other α-olefins, such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexane copolymers. , propylene-4-methyl-1-pentene copolymer or blends thereof. The MFR (230°C) of these is preferably 5 to 20. The partial ionomer resin or 1-olefin/(meth)acrylic acid copolymer resin used in the present invention should have carboxyl groups present in the copolymer from the viewpoint of bondability with the thermoplastic elastomer and scratch resistance. The content is usually 4 to 15 mol%, preferably 6 to 10 mol%, and usually 60% or less, preferably 40% or less of the groups are alkali metal and/or alkaline earth metal ions, preferably calcium ions. Or, those bonded to zinc ions can be mentioned. In the present invention, the following methods can be exemplified as methods for laminating and molding a thermoplastic elastomer and a partial ionomer resin or a 1-olefin copolymer/(meth)acrylic acid copolymer resin. (a) Method of simultaneous multilayer extrusion of partial ionomer resin or 1-olefin/(meth)acrylic acid copolymer resin and thermoplastic elastomer (b) Partial ionomer resin or 1-olefin/(meth)acrylic acid copolymerization Method for multilayer injection molding of resin and thermoplastic elastomer (c) Ionomer resin or 1-
A method of inserting an olefin/(meth)acrylic acid copolymer resin molding and injecting and laminating a thermoplastic elastomer on its surface.
- Method of injection lamination of olefin copolymer/(meth)acrylic acid resin Among these, method (a) is usually used. Reference example 1 (i) Ethylene-propylene-2-ethylidene-5
-Norbornene terpolymer elastomer [ethylene content 78 mol%, iodine value 15, Mooney viscosity
ML 1+4 (100â) 70ã75 parts, (ii) Crystalline polypropyne [MFR (230â, 2.16Kg)
11, Density 0.91/cc, Yield stress 370Kg/cm 2
(ASTM-D-638) 15 parts (iii) Isobutene-isoprene copolymer elastomer [unsaturation degree 0.8 mol%, Mooney viscosity ML 1+4 (100
°C) 45] 10 parts, (iv) Antioxidant: Tetrakis [methylene (3,5
-di-tert-butyl-4-droxyphenyl)
Propionate] methane 0.3 parts. The above (i) to (iv) were charged into a Banbury mixer, kneaded for 5 minutes at 180°C in a nitrogen atmosphere, passed through a roll to form a seal, and then cut into pellets using a sheet cutter. Next, a solution prepared by dissolving and dispersing 0.3 parts of 1,3-bis(tert-butylperoxy-iso-propyl)benzene in 0.5 parts of divinylbenzene is added to the pellets, and mixed using a Henschel mixer.
The solution was applied uniformly to the pellet surface. The pellets were then extruded using an extruder in a nitrogen atmosphere at 210°C for a residence time of 5 minutes, and the resulting extrudate was dynamically heat treated to obtain a thermoplastic elastomer. Reference example 2 (i) Ethylene-propylene-dicyclopentadiene terpolymer elastomer [ethylene unit content
79mol%, iodine value 10, Mooney viscosity ML 1+4
(100°C) 70ã70 parts, (ii) 30 parts of the same polypropylene used in Reference Example 1
(iii) 0.3 parts of the same antioxidant used in Reference Example 1. The above steps (i) to (iii) were operated in the same manner as in Reference Example 1 to perform pelletization and partial crosslinking to obtain a desired thermoplastic elastomer. Reference example 3 (i) Elastomer 65 used in reference example 1
(ii) Polypropylene used in Reference Example 1
20 parts, (iii) Propylene-ethylene random copolymer [propylene unit content 55 mol%, MFR (230â)
0.5g/10min] 15 parts, (iv) 0.3 of the antioxidant used in Reference Example 1
Department. The above steps (i) to (iv) were operated in the same manner as in Reference Example 1 to perform pelletization and partial crosslinking to obtain a desired thermoplastic elastomer. The surface gloss, scratch resistance (surface strength), and interlayer adhesion of the laminate were evaluated as follows. Surface gloss: Gloss measured at a light incidence angle of 60° in accordance with JISZ-8741 (hereinafter sometimes referred to as "60° gloss") Scratch resistance: Using a scratch tester specified in JISK-5401 , pencil hardness HB, load
Scratch the surface of the molded product under 500g conditions and evaluate the marks using the following criteria. 5: No scratches observed at all 4: Slight scratches left 3: Scratches left but not scratches 2 : Shallow scratches remain 1: Deep scratches remain Interlayer adhesion: A test piece (width 20 mm x length 120 mm) is cut out from the molded product, and both layers are subjected to T-peeling at a peeling speed of 50 mm/min. Example 1 Partial ionomer resin [MI (190°C) 5g/
10mm, carboxyl group content 8mol%, neutralization degree 19%,
Zinc salt type] was melted in an extruder at 200°C in a nitrogen atmosphere, and the thermoplastic elastomer obtained in Reference Example 1 was melted in another extruder in a nitrogen atmosphere.
They were melted at 230°C and both were extruded into the same mold to perform simultaneous two-layer molding. Table 1 shows the evaluation results of the obtained two-layer laminate. From the same table, it can be seen that the surface gloss and scratch resistance of the partial ionomer layer of the product of the present invention are equivalent to those of the normal ionomer (Comparative Example 2), and the interlayer adhesion strength of the product of the present invention is comparable. It can be seen that it far exceeds that of Example 2 and is substantially equivalent when compared with the thermoplastic elastomer (Comparative Example 1). In other words, since both layers in Comparative Example 1 are made of the same thermoplastic elastomer, the interlayer adhesion force should be the maximum, and the value
Interlayer adhesion strength of the present invention product for 3.5Kg/cm
3.3Kg/cm is almost the same. Comparative Example 3 is an evaluation result of a laminate of EVA (ethylene-vinyl acetate copolymer), which has a reputation for excellent interlayer adhesion, and the thermoplastic elastomer in Reference Example 1. This is an example to show that even though the adhesive strength between the adhesive and the adhesive is equivalent to that of the product of the present invention, the scratch resistance may be significantly inferior. Example 2 A two-layer laminate was obtained in the same manner as in Example 1 using the same partially ionomer resin used in Example 1 and the thermoplastic elastomer of Reference Example 2. Table 1 shows the evaluation results of the obtained laminate. From the same table, it can be seen that the 60° gloss and scratch resistance on the glossy side of the laminate are exactly the same as those of ordinary ionomer resin, and the interlayer adhesion strength far exceeds that of Comparative Example 2. I understand. Example 3 A two-layer laminate was obtained using the same partial ionomer resin as used in Example 1 and the thermoplastic elastomer of Reference Example 3 and operating as in Example 1. Table 1 shows the evaluation results of the obtained laminate. From the same table, it can be seen that the 60° gloss and scratch resistance on the glossy side of the laminate are exactly the same as those of ordinary ionomer resin, and the interlayer adhesion strength far exceeds that of Comparative Example 2. I understand. Comparative Example 1 A laminate was obtained by simultaneous two-layer extrusion using the thermoplastic elastomer obtained in Reference Example 1 for both layers. The evaluation results are shown in Table 1. Comparative example 2 Ionomer resin [MI (190°C) 10g/10min,
Carboxy group content 10 mol%, neutralization degree 72%, sodium ion type] was melted in an extruder at 200°C in a nitrogen atmosphere, and the following operations were performed in the same manner as in Example 1 to obtain a two-layer laminate. . Table 1 shows the evaluation results of the obtained laminate. Comparative Example 3 Ethylene-vinyl acetate copolymer [vinyl acetate unit content 14 wt%, density 0.93 g/cc, MI (190°C)
1.4 g/10 min] was melted during extrusion at 200° C. in a nitrogen atmosphere, and the following operations were performed in the same manner as in Example 1 to obtain a two-layer laminate. Table 1 shows the evaluation results of the obtained laminate. ãtableã
Claims (1)
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ã©ããæ§ã®è¯å¥œãªç©å±€äœã®è£œé æ¹æ³ã[Scope of Claims] 1. A thermoplastic elastomer layer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing free carboxyl groups. or 1-olefin (meta)
A laminate with good surface gloss and scratch resistance, which is formed by strongly bonding an acrylic acid copolymer resin layer. 2. A thermoplastic elastomer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing a free carboxyl group or a 1-olefin (meth) elastomer. ) A method for producing a laminate with good surface gloss and scratch resistance, characterized by strongly bonding the acrylic acid copolymer resin with an acrylic acid copolymer resin in a molten state.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23435083A JPS60127149A (en) | 1983-12-14 | 1983-12-14 | Laminate having excellent surface gloss and surface hardnessand manufacture thereof |
US06/680,644 US4656098A (en) | 1983-12-14 | 1984-12-11 | Laminate excellent in surface gloss and surface harness, and preparation process and use thereof |
CA000469985A CA1226709A (en) | 1983-12-14 | 1984-12-13 | Laminate excellent in surface gloss and surface hardness, and preparation process and use thereof |
DE8484308689T DE3480696D1 (en) | 1983-12-14 | 1984-12-13 | LAMINATE, ITS PRODUCTION AND USE. |
EP19840308689 EP0146349B1 (en) | 1983-12-14 | 1984-12-13 | Laminate, preparation and use thereof |
US07/003,713 US4800130A (en) | 1983-12-14 | 1987-01-15 | Laminate excellent in surface gloss and surface hardness, and preparation process and use thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23435083A JPS60127149A (en) | 1983-12-14 | 1983-12-14 | Laminate having excellent surface gloss and surface hardnessand manufacture thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60127149A JPS60127149A (en) | 1985-07-06 |
JPH0251387B2 true JPH0251387B2 (en) | 1990-11-07 |
Family
ID=16969616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23435083A Granted JPS60127149A (en) | 1983-12-14 | 1983-12-14 | Laminate having excellent surface gloss and surface hardnessand manufacture thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60127149A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1964671B1 (en) | 2005-12-16 | 2014-03-26 | Nichiban Co. Ltd. | Tipping film |
EP3677640B1 (en) | 2017-08-28 | 2023-12-13 | Dow-Mitsui Polychemicals Co., Ltd. | Resin composition, molded object, and production method for resin composition |
-
1983
- 1983-12-14 JP JP23435083A patent/JPS60127149A/en active Granted
Also Published As
Publication number | Publication date |
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JPS60127149A (en) | 1985-07-06 |
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