WO2001085815A1 - Polymere olefinique amorphe modifie et composition de resine contenant ledit polymere modifie et une resine thermoplastique - Google Patents

Polymere olefinique amorphe modifie et composition de resine contenant ledit polymere modifie et une resine thermoplastique Download PDF

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WO2001085815A1
WO2001085815A1 PCT/JP2001/003824 JP0103824W WO0185815A1 WO 2001085815 A1 WO2001085815 A1 WO 2001085815A1 JP 0103824 W JP0103824 W JP 0103824W WO 0185815 A1 WO0185815 A1 WO 0185815A1
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olefin polymer
modified
amorphous olefin
polymer
molecular weight
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PCT/JP2001/003824
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English (en)
Japanese (ja)
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Toshiki Mori
Hironobu Iyama
Shigeki Naitoh
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Sumitomo Chemical Company, Limited
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Publication of WO2001085815A1 publication Critical patent/WO2001085815A1/fr

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    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • C09J151/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention includes a modified amorphous olefin polymer obtained by graft-polymerizing an alkenyl aromatic hydrocarbon and / or an unsaturated carboxylic acid to an olefin polymer, and a modified resin containing the modified olefin polymer and a thermoplastic resin. To a resin composition to be formed.
  • Polyolefin resins such as polypropylene are widely used in housings for home appliances, exterior products for automobiles, and so on.
  • a crystalline modified product obtained by graft-polymerizing an unsaturated carboxylic acid to a crystalline olefin polymer is disclosed in, for example, Japanese Patent Application Laid-Open No. 4-46898.
  • Patent Document 1 discloses a crystalline modified product obtained by graft-polymerizing an alkenyl aromatic hydrocarbon onto a crystalline olefin polymer, for example, as disclosed in Japanese Patent Application Laid-Open No. 5-32737. Is disclosed in However, there was a problem that none of the modified products had sufficient adhesive strength.
  • thermoplastic resin is contained in a crystalline modified product obtained by graft polymerization of an unsaturated carboxylic acid to a crystalline olefin polymer.
  • a resin composition has been proposed (eg, Japanese Patent Publication No. 59-48059, Japanese Patent Publication No. 59-48060).
  • the present inventors have studied and found that the resin composition has a remarkably low adhesiveness to a polar group-containing resin.
  • a first object of the present invention is to provide a resin having excellent adhesion to an olefin resin
  • a second object is to provide an olefin resin, a metal and a resin having a polar group.
  • Another object of the present invention is to provide a resin composition having excellent adhesiveness. Under these circumstances, the present inventors have conducted intensive studies in order to find an adhesive having excellent adhesiveness to the olefin resin, and as a result, have found that the olefin polymer has an alkenyl aromatic hydrocarbon and a tertiary or non-olefin resin.
  • An amorphous modified product obtained by graft polymerization of a saturated carboxylic acid exhibits high adhesiveness to an olefin-based resin, and a resin composition of the modified product and a thermoplastic resin contains a metal and a polar resin.
  • the present inventors have found that they have excellent adhesion to a group-containing resin, and have completed the present invention.
  • the present invention relates to a modified olefin polymer which is obtained by graft-polymerizing an alkenyl aromatic hydrocarbon and Z or an unsaturated carboxylic acid to the olefin polymer, wherein the modified product has a heat of fusion or heat of crystallization of 1%.
  • the present invention also provides an adhesive comprising the modified product or a resin composition containing the modified product and a thermoplastic resin as an active ingredient.
  • the present invention further provides a laminate characterized by laminating the adhesive and a substrate.
  • the modified amorphous olefin polymer of the present invention is a modified olefin polymer obtained by graft polymerizing an alkenyl aromatic hydrocarbon and Z or an unsaturated carboxylic acid to an olefin polymer, JISK 7
  • the heat of fusion or heat of crystallization of the denatured product measured by using a differential scanning calorimeter (DSC) at 10 ° C / min according to 1 122 is 1 Vg or less. Is an olefin polymer.
  • the olefin polymer used in the present invention is usually an amorphous olefin polymer whose heat of fusion or crystallization is 1 JZg or less.
  • the heat of fusion and the heat of crystallization can be measured in the same manner as described above.
  • amorphous olefin-based polymer examples include ethylene, hyolefin, and polyolefin.
  • olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-decene, 1-decene, 1 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nasocene, 1_eicosene, etc.
  • Examples include branched ⁇ -olefins such as methyl-1-butene, 3-methyl-1-pentene, 4-methyl-11-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene.
  • linear a-olefins are preferable, and propylene, 1-butene, 11-pentene, 1-hexene, 11-heptene, 1-octene, 1-nonene and 1-decene are particularly preferable.
  • the polyene compound is, for example, a compound having a plurality of double bonds in a monomer such as a conjugated polyene compound and a non-conjugated polyene compound.
  • conjugated polyene compound examples include a linear or branched aliphatic conjugated polyene compound and an alicyclic conjugated polyene compound. Further, the conjugated polyene compound may be substituted with an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, or the like.
  • aliphatic conjugated polyene compound examples include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butane, 2-methyl-1,3-pentadiene, 2-methyl-1, 3-Hexadiene, .2-Methyl-1,3-octadiene, 2-Methyl-1,3-decadiene, 2,3-Dimethyl-1,3-pentene, 2,3-Di'methyl-1,3- Hexagen, 2,3-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-de
  • alicyclic conjugated polyene compounds include 2-methyl-1,3-cyclopentene, 2-methyl-1,3-cycl
  • 1,3-cyclopentene 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1-fluoro-1,3 —Butadiene, 2-chloro-1,3-pentadiene, 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene and the like.
  • non-conjugated polyene compound examples include a linear or branched aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene compound.
  • the non-conjugated polyene compound may be substituted with an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, or the like.
  • examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene,
  • 6-butadiene 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-butadiene, 4-methyl-1,1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethylethyl 1,4-octadiene, 5-ethylo-1,4-octadiene, 5-methyl-1,5, 1-year-old octadiene, 6-methyl-1,5-octadiene, 5-ethylo-1,5-octadiene 1,5-octadiene, 6-ethylo-1, , 5-octagen, 6-methyl-1,6-octadiene, 7-methyl-1,6, 1-year-old, 6-ethyl-1,6-octadiene, 6-propyl-1,6, 1-year-old, 6-butyl-1 , 6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl TJP01 /
  • 6-methyl-1,6-nonagen 7-methyl-1,6-nonagen, 6-ethyl 1,6-nonagen, 7-ethyl-1,6-nonagen, 7-methyl-1,
  • Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norpolene, 5-ethylidene-2-norpolene, 5-methylene-12-norpolene, 5-isoprobenil-2-norbornene, Cyclohexadiene, dicyclopentene, cyclooctadiene, 2,5-norpolnadiene, 2-methyl-2,5-norpolnadiene, 2-ethyl-2,5-norpolnadiene, 2,3-diisopropylidene 5-norpolene, 2-ethylidene-3-isopropylidene 5-norpolene, 6-chloromethyl-5-isopropylidene-2-norpolene, 1,4-dipinylcyclohexane, 1,3-dipinylcycline Mouth hexane, 1,3-divinylcyclopentane, 1,5
  • cyclic olefin examples include: norpolene, 5-methylnorporene, 5-ethylnorporene, 5-propylnorporene, 5,6-dimethylnorporene, 1-methylnorporene, 7-methylnorporene , 5,5,6-trimethylnorportene, 5-phenylnorportene, 5-benzylnorportene, 5-ethylidenenorportene, 5-vinylnorportene, 1,4,5,8 1,2,3,4,4a, 5,8,8a—Octahydronaphthalene, 2-methyl-1,4,5,8—1,2,3,4, 4a, 5,8,8a—Hydrohydronaphthylene, 2-ethyl—1,4,5,8—dimethanone 1,2,3,4,4a, 5,8,8a—Octa Hydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
  • ethylene and at least two types of olefin monomers selected from the group consisting of ⁇ -olefin having about 3 to 20 carbon atoms are obtained by copolymerization.
  • the total number of carbon atoms of the olefin monomer is preferably 6 or more.
  • the content of ethylene units in the amorphous olefin polymer is usually preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably 60 mol% or less. It is particularly preferably at most 50 mol%. When the content of the ethylene unit is at most 80 mol%, the number of crystals derived from ethylene in the olefin copolymer will be reduced, and the adhesiveness of the resulting polymer-modified product tends to be improved.
  • X represents the content (mol%) of ethylene in the amorphous olefin polymer
  • y represents the content of ⁇ -olefin having about 4 to 20 carbon atoms in the amorphous olefin polymer. Amount (mol%).
  • the molecular weight distribution of the amorphous olefin polymer that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually about 5 or less, preferably 4 or less. Particularly preferably, it is 3 or less. When the molecular weight distribution is 5 or less, the rigidity and adhesiveness of the obtained adhesive tend to be improved.
  • the above molecular weight distribution is a value measured by gel permeation chromatography (GPC).
  • the relationship between the GPC holding capacity and the molecular weight was determined using polystyrene as a molecular weight standard substance, and then the weight average molecular weight (Mw) and the weight average molecular weight (Mw) of the amorphous olefin polymer were determined from the GPC holding capacity of the amorphous olefin polymer used.
  • the number average molecular weight (Mn) can be obtained, and the molecular weight distribution (MwZMn), which is the ratio between them, can be obtained.
  • a 3 mg / m 1 tetralin solution of the polymer is prepared, and then the solution is prepared as 1.SmgZml 1 .Omg / ml, 0.6 mgZml
  • the viscosity of each concentration was measured three times with an Ubbelohde viscometer in a constant temperature oil bath at 135 ° C ( ⁇ 0.1.C), and the average value and the viscosity of tetralin at 135 ° C The method to obtain from is mentioned.
  • the intrinsic viscosity of the amorphous olefin polymer measured by the above method is usually about 0.1 to 10.0 d1 Zg, preferably about 0.3 to 7.0 d1 / g, Particularly preferred is 0.5-5 OdIZg. If the intrinsic viscosity does not reach 0.1 dlZg, the low molecular weight component tends to bleed out to the surface of the obtained adhesive and the adhesiveness tends to decrease, and the intrinsic viscosity becomes 1 ODlZg. If the ratio exceeds the above, the flexibility of the obtained adhesive tends to decrease, and the adhesiveness tends to decrease, which is not preferable.
  • the amorphous olefin polymer used in the present invention for example, it can be produced by a known polymerization method using a known Ziegler-Natta type catalyst, a metallocene catalyst or the like.
  • a meta-open catalyst by using a meta-open catalyst, an amorphous olefin polymer having a heat of fusion or heat of crystallization of 1 J / g or less can be easily obtained, and has a high molecular weight, a narrow molecular weight distribution and a narrow molecular weight distribution. It is preferable because a polymer having a composition distribution can be obtained.
  • a meta-open catalyst there are few groups having a cyclopentene anion skeleton.
  • the catalyst include a transition metal complex having at least one, and containing a transition metal complex containing a transition metal atom belonging to Groups 4 to 6 of the periodic table.
  • JP-87313-A meta-cene catalyst comprising a complex described in JP-A-2000-119288 can be exemplified.
  • the intrinsic viscosity can be increased. It is preferable because [] is about 0 :! to about 10.0 d 1 / g and those having a Z or molecular weight distribution of 5 or less can be easily obtained.
  • the modified amorphous olefin polymer in the present invention refers to an amorphous olefin polymer such as an amorphous olefin polymer, which is obtained by graft-polymerizing an alkenyl aromatic hydrocarbon and / or an unsaturated rubonic acid. It is a modified olefin polymer. In particular, it is preferable that the olefin polymer is an amorphous olefin polymer.
  • a modified amorphous olefin polymer obtained by graft-polymerizing an alkenyl aromatic hydrocarbon to an olefin polymer will be described.
  • the content of the alkenyl aromatic hydrocarbon in the modified product is usually 0. It is about 01 to 20% by weight, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight.
  • the graft polymerization amount of alkenyl aromatic hydrocarbon refers to the content of the grafted component such as alkenyl aromatic hydrocarbon in the modified product
  • the adhesive strength tends to be improved, and when the content is 20% by weight or less, the thermal stability of the modified product tends to be improved.
  • the alkenyl aromatic hydrocarbon used in the present invention includes, for example, alkenyl compounds having an aromatic hydrocarbon group having about 6 to 25 carbon atoms, and specifically, a phenyl group, a trinole group, a xylyl group, Alkenyl compounds having a tertiary butyl phenyl group, a vinyl phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group and the like can be mentioned.
  • alkenyl aromatic hydrocarbons phenyl, tolyl, xylyl,
  • alkenyl aromatic hydrocarbons include styrene, p-methylstyrene, m-methylstyrene, 0-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, Alkyl styrenes such as 5-dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-1-5-ethyl styrene, p-tertiary butyl styrene, and p-secondary butyl styrene; Alkenylbenzenes such as enylpropylene and 2-phenylbutene; and pinylnaphthalenes such as 1-vinylnaphthalene.
  • alkenyl aromatic hydrocarbon two or more alkenyl aromatic hydrocarbons may be used.
  • alkenyl aromatic hydrocarbons styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tertiarybutylstyrene, 2-phenylpropylene, and 1-vinylnaphthalene are preferable, and styrene is particularly preferable. is there .
  • the content of the unsaturated carboxylic acid in the modified polymer is usually 0.0. It is from 1 to 20% by weight, preferably from 0.05 to 10% by weight, particularly preferably from 0.1 to 5% by weight.
  • the adhesive strength of the modified product tends to decrease, which is not preferable. It is not preferable because thermal stability tends to decrease.
  • unsaturated carboxylic acids used in the present invention include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, methylnadic acid, hymic acid, Unsaturated carboxylic acids such as angelic acid, tetrahydrophthalic acid, sorbic acid, and mesaconic acid; unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, methyl nadic anhydride, and hymic anhydride Materials: methyl acrylate, methyl methacrylate, ethyl acrylate, methyl ethyl methacrylate, acrylic acid JP01 / 03824
  • maleic anhydride is particularly preferred.
  • a method for producing the modified amorphous olefin polymer of the present invention for example, after melting the amorphous olefin polymer, an alkenyl aromatic hydrocarbon and Z or an unsaturated carboxylic acid are added, followed by grafting.
  • the above production method is usually performed at a temperature of about 40 to 350 ° C.
  • the polymerization is usually carried out in the presence of a radical initiator.
  • the amount of the radical initiator to be used is generally about 0.01 to 0.5 mol, preferably about 0.05 to 0.1 mol, per 1 kg of the olefin polymer.
  • Radical initiators include, for example, methyl ethyl ketone peroxide, cyclo Methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1-bis (tert-butylbenzyloxy) -1,3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) octane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2_bis ( tert-butyl peroxy) butane, tert-butyl halide peroxide, cumenehydride peroxide, diisopropyl
  • the modified amorphous olefin polymer according to the present invention usually has a molecular weight distribution (Mw ZMn) of about 5 or less, preferably 4 or less, particularly preferably 3 or less. When the molecular weight distribution is about 5 or less, the adhesiveness of the modified product tends to be improved.
  • Mw ZMn molecular weight distribution
  • the molecular weight distribution can be measured in the same manner as the molecular weight distribution of the amorphous olefin polymer.
  • the intrinsic viscosity [77] (135 ° C) of the modified amorphous olefin polymer is usually about 0.1 to 10.0 d 1 / g, preferably 0.3 to 7.0 dL / g. / g, particularly preferably 0.5 to 5.0 dlZg.
  • the intrinsic viscosity is 0.1 ldl / g or more, a decrease in adhesion due to bleed-out of the low molecular weight component to the surface of the modified product tends to be suppressed, and the intrinsic viscosity is 10 dlZg. Due to the following, the flexibility of the modified product is increased and the adhesiveness tends to be improved. This intrinsic viscosity can be measured in the same manner as the intrinsic viscosity of the amorphous olefin polymer.
  • the resin composition of the present invention contains the modified amorphous olefin polymer thus obtained and a thermoplastic resin.
  • a thermoplastic resin a polar group-containing resin containing a polar group such as an ester group, a propyloxyl group, a propylonyl group, an ether group, an amide group, a hydroxyl group, a nitrile group; polyethylene, polypropylene, Ethylene propylene copolymer, ethylene / 1-butene copolymer, ethylene 1-hexene copolymer, ethylene propylene / tobutene copolymer, ethylene / propylene / gen copolymer, polyvinyl chloride And aliphatic olefin-based resins such as polyvinylidene; aromatic vinyl resins.
  • thermoplastic resin two or more kinds of thermoplastic resins may be used.
  • thermoplastic resin a polar group-containing resin and an aromatic Biel resin are preferable, and a polar group-containing resin is particularly preferable.
  • the polar group-containing resin examples include polyester resin; polypropionate resin; vinyl acetate resin; (meth) acrylic acid resin; ethylene 'vinyl acetate copolymer, ethylene' (meth) acrylic acid Ester-based copolymers, ethylene '(meth) Ethylene-caprolactone-containing monomer copolymers such as acrylic acid-based copolymers; polyether-based resins such as polyphenylene ether; ⁇ -force prolactam and hexame Polyamide-based resin obtained using tylenediamine / adipate as a raw material; resin obtained by reacting a polyamide-based resin such as polyethylene oxide and ⁇ or polypropylene oxide; polyvinyl alcohol; polyacrylonitrile; No.
  • polyester resin and an ethylene / resulfonyl group-containing monomer copolymer are preferred.
  • polyester resin examples include a polycondensate of a dicarboxylic acid unit and a diol unit, and a polycondensate of a polycarboxylic acid unit. Among them, a polycondensate of a dicarboxylic acid unit and a diol unit is preferable.
  • examples of the dicarboxylic acid unit constituting the polyester resin include an azelaic acid unit, an adipic acid unit, a sebacic acid unit, and a dodecanedicarboxylic acid.
  • Aliphatic dicarboxylic acid unit having about 2 to 20 carbon atoms such as unit, isophthalic acid unit, terephthalic acid unit, phthalic acid unit, bis (4-carboxyphenyl) methane unit, 1, Alicyclic groups such as aromatic dicarboxylic acid units such as 2-bis (4-carboxyphenyl) ethane unit, 4,4'-dicarboxybiphenyl ether unit and naphthalenedicarboxylic acid unit, and cyclohexanedicarboxylic acid unit Dicarboxylic acid units.
  • the dicarboxylic acid unit two or more dicarboxylic acid units may be used.
  • terephthalic acid units are contained in the dicarboxylic acid units in an amount of 30 mol% or more.
  • diol unit for example, 1,2-ethanediol unit, 1,2-propanediol unit, 1,3-propanediol unit, 1,4-butanediol unit, 1,5-pentanediol unit, 1,6 -Hexanediol unit, 1, 10-decanediol unit, linear or branched aliphatic diol unit having about 2 to 20 carbon atoms, such as neopentyldaricol unit, 1,4-cyclo Diol units containing alicyclic groups such as hexanediol units, 1,4-cyclohexanejetanol units, etc., polyethylene glycol units with an average molecular weight of about 400 to 6000, polypropylene glycol units, polytetramethylene glycol units, etc. Examples thereof include a chain glycol unit, and among them, a 1,2-ethanediol unit and a 1,4-butanediol
  • the reduced viscosity of the polyester resin is usually about 0.5 or more.
  • mechanical properties such as adhesiveness, blocking resistance, and workability of the resin composition of the present invention are improved.
  • the polyester resin is usually contained in an amount of about 30 to 200 parts by weight, preferably about 40 to 150 parts by weight, based on 100 parts by weight of the modified amorphous olefin polymer.
  • Examples of the monomer copolymer containing an ethylene-caprolponyl group used as a thermoplastic resin include, for example, an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-persert acid biel copolymer, and an ethylene- (meth) acrylic acid copolymer.
  • ethylene 'Biel acetate copolymer, ethylene' An ethylene / biel acetate copolymer such as a vinyl acetate / pinyl versatate copolymer is preferred.
  • the ethylene content of the ethylene-hydroxyluponyl group-containing monomer copolymer is usually about 50 to 99% by weight, and preferably 55 to 95% by weight.
  • the ethylene-caprolponin-containing monomer copolymer is composed of a modified amorphous olefin polymer 1
  • the amount is usually about 5 to 100 parts by weight, preferably about 10 to 80 parts by weight, per 100 parts by weight.
  • the aromatic vinyl resin used as the thermoplastic resin is a resin containing the alkenyl aromatic hydrocarbon described above, and among them, styrene and o-methylstyrene are preferable.
  • aromatic biel resins include, for example, polymers of aromatic biel compounds such as polystyrene and styrene ' ⁇ -methylstyrene copolymer; acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene block copolymer, Styrene ⁇ butadiene ⁇ styrene block copolymer, styrene ⁇ isoprene • Styrene block copolymer, styrene ⁇ ethylene ⁇ butylene ⁇ styrene block copolymer, styrene ⁇ ethylene ⁇ propylene ⁇ styrene block copolymer A block copolymer of a polymer and a rubbery polymer; and a graft copolymer of a polymer of an aromatic pinyl compound such as polybutadiene rubber-modified aromatic vinyl resin (HIPS) and a
  • examples of the rubbery polymer include gen-based rubbery polymers such as polybutadiene, polyisoprene, and natural rubber, ethylene-propylene copolymer, ethylene-propylene-conjugated gen copolymer, and acrylic rubber. Non-gen-based rubbery polymers and the like can be mentioned. In addition, a mixture of two or more rubbery polymers may be used as the rubbery polymer.
  • aromatic vinyl resin a mixture of a polymer of an aromatic biel compound and a rubbery polymer may be used.
  • the content of the aromatic biel resin in the polymer is usually about 5 to 200 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the modified amorphous olefin polymer. It is about a part.
  • the method for producing the resin composition of the present invention includes, for example, melt-kneading a modified amorphous olefin polymer and a thermoplastic resin using a single-screw or twin-screw extruder, a panbury mixer, various kinds of kneaders, rolls, and the like. And a method of dissolving or dispersing the modified amorphous olefin polymer and the thermoplastic resin in a solvent such as toluene, xylene or water.
  • the production temperature of the resin composition is usually about 40 to 350 ° C.
  • modified amorphous olefin polymer and the resin composition containing the modified amorphous olefin polymer and the thermoplastic resin may be used, for example, as an active ingredient such as an adhesive. Can be.
  • This adhesive can usually be obtained by molding a modified amorphous olefin polymer or a resin composition into a sheet and a film by hot pressing, extrusion molding or the like.
  • the adhesive may be a modified amorphous olefin polymer or a solution obtained by dissolving or dispersing the resin composition in a solvent such as toluene, xylene, or water.
  • the adhesive of the present invention includes various stabilizers such as a phenol-based stabilizer, a phosphite-based stabilizer, an amine-based stabilizer, an amide-based stabilizer, an anti-aging agent, and a weather-resistant stabilizer, as long as the adhesiveness is not impaired.
  • Additives such as powders, lubricants, nucleating agents, flame retardants, oils, paints, dyes, glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate Contains inorganic and organic reinforcing agents, fillers, etc., such as, clay, kaolin, finely divided silica, myriki, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, and ceramic You may.
  • the laminate of the present invention is obtained by laminating an adhesive and a substrate. '
  • the base material examples include polyolefin resins such as polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / propylene / gen copolymer, styrene / butadiene / styrene copolymer, polyester, and polyvinyl chloride.
  • polyolefin resins such as polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / propylene / gen copolymer, styrene / butadiene / styrene copolymer, polyester, and polyvinyl chloride.
  • Polyamide resin (meth) acrylate resin, ethylene '(meth) acrylate copolymer, thermoplastic resin such as ethylene'vinyl acetate copolymer, phenol resin, melamine resin, alkyd resin, diaryl phthalate resin, epoxy Thermosetting resins such as resin, urethane resin and urea resin; metals such as aluminum, aluminum alloy, iron, copper, copper alloy, lead, carbon steel, low alloy steel, stainless steel; inorganic materials such as glass and cement And the like. 'Further, the same type of base material may be stacked on the laminate, or different types of base materials may be stacked.
  • the substrate is preferably a thermoplastic resin, and particularly preferably a polyolefin resin.
  • the base material is preferably a thermoplastic resin or a metal.
  • Aliphatic polyolefin resin, polystyrene resin, (meth) acrylic acid resin, and metal are preferred.
  • Examples of the method for producing the laminate of the present invention include a method of preparing a sheet of an adhesive, then sequentially laminating a substrate, an adhesive, and a substrate, followed by heat breathing, and a solution bonding method on the substrate. Applying agent, drying solvent and laminating other base material, Applying solution adhesive on base material, drying solvent and laminating thermoplastic resin paint, base material, bonding And a method of laminating an agent and a base material by co-extrusion.
  • ethylene / propylene / tobutene copolymerization was continuously performed. That is, hexane was added from the lower part of the polymerization reactor at 54.7 parts / hour, Len 4.5 hours, propylene 11.0 parts / hour, tobutene 10.2 parts, dimethylsilyl (tetramethylcyclopentagenenyl) -1- (3-tert-butyl-5-methyl-1-2-) phenoxy) titanium dichloride, Torifuenirume Chirutetorakisu (pen evening fluorophenyl) Poreto, triisobutyl aluminum two ⁇ beam respectively 0. 012X 10- 3 parts / hour, 0.
  • the polymerization liquid taken out of the polymerization vessel was terminated by adding a small amount of ethanol to stop the polymerization reaction.After removing the monomer and washing with water, the solvent was removed by steam in a large amount of water, and the copolymer was taken out. And dried under reduced pressure day and night. By the above operation, an ethylene / propylene / tobutene copolymer was obtained at a rate of 4.4 parts Z hour.
  • ethylene / propylene / tobutene copolymer was dissolved in 5 ml of o-dichlorobenzene.
  • a gel permeation chromatograph (GPC, Waters, 150C) equipped with a Shodex Packed Column A-80M (Showa Denko) column and a refractive index detector was used to measure the elution temperature.
  • the dissolution solution 4001 was injected at 140 ° C. and the elution solvent flow rate was set at 1.0 m 1 Zmin.
  • the relationship between the molecular weight and the retention time of GPC was determined in advance using the molecular weight standard material polystyrene (manufactured by Tosoichi Co., Ltd., molecular weight 688-400,000), and the ethylene / propylene '1-- obtained based on the relationship was determined.
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution of the butene copolymer were determined.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution in the following Examples and Comparative Examples were also determined by the same method.
  • the obtained ethylene / propylene / 1-butene copolymer 3 O Omg was dissolved in 100 ml of tetralin to prepare a 3 mg / ml solution.
  • the solution was further diluted with tetralin and diluted to 1.5 mg / ml, 1.0 mgZml, and 0.6 mgZml, and each was diluted with a Ubbelohde viscometer in a thermostatic oil bath at 135 ° C ( ⁇ 0.1 ° C).
  • the viscosity at each concentration was measured three times, and the intrinsic viscosity [7] was determined from the average value and the viscosity at 135 X of tetralin. (The intrinsic viscosity [ ⁇ ] in the following Examples and Comparative Examples was also determined by the same method.)
  • the obtained ethylene / propylene / 1-butene copolymer was measured with a differential scanning calorimeter (DSC, Seiko Denshi Kogyo Co., Ltd., DSC22 OC) at a rate of 10 ° CZ for both the heating and cooling processes. The measurement was performed, and no heat of fusion or heat of crystallization of 1 J / g or more was found. (Note that DSC in the following Examples and Comparative Examples was also obtained by the same method.)
  • the filtered product was dried under reduced pressure at 100 ° C for 1 day to obtain a denatured product (A-la).
  • the modified polymer (A-la) had a graft polymerization amount of styrene of 3.9%, the polystyrene content was 2.5%, and the modified polymer (A-la) was measured by GPC.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • MwZMn molecular weight distribution
  • the intrinsic viscosity [ ⁇ ] of (A-la) is 1.30. According to DSC measurement, the modified product ( ⁇ la) has no heat of fusion and heat of crystallization of 1 J / g or more. Did not. (Example 2)
  • the amount of styrene charged was 30 parts
  • the amount of the xylene solution for diluting styrene was 1, and the radical initiator 1, 1
  • a modified amorphous olefin polymer was obtained in the same manner as in Example 1 except that the amount of the xylene solution of monobis (tert-butylbenzyloxy) -3> 3,5-trimethylcyclohexane was adjusted.
  • the grafted amount of maleic anhydride in the resulting modified product (A-lb) was 0.49%, and the modified product (A-lb) was measured by GPC.
  • the filtrate was dried under reduced pressure at 100 ° C for 1 day to obtain 101 parts of a modified product (A-2a).
  • the graft polymerization of maleic anhydride in the modified product (A-2a) was 1.34%, and the weight average molecular weight (Mw) of the modified product (A-2a) was measured by GPC.
  • the intrinsic viscosity [??] of (A-2a) is 1.07.
  • the modified substance (A-2a) has a heat of fusion and heat of crystallization of 1 J / g or more. Was not found. (Examples 4 and 5)
  • Example 3 Synthesis example of amorphous olefin polymer / maleic anhydride modified product (A-2a)
  • Amorphous olefin polymer / maleic anhydride modified product (A—) in the same manner as in Example 3 except that the amount of xylene solution of 1,3,3,5-trimethylcyclohexane was adjusted.
  • 2b) and (A-2c) were obtained.
  • Table 1 shows the number average molecular weight, weight average molecular weight, and graft polymerization amount of the resulting modified product. In any case, no heat of fusion or heat of crystallization of 1 J / g or more was found.
  • a pressure-resistant reaction vessel was charged with 400 parts of toluene and 80 parts of an ethylene / propylene / tributene copolymer obtained in a synthesis example of an amorphous olefin polymer, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the temperature of the reaction solution was raised to 105 ° C, and the mixture was stirred for 1 hour to obtain a uniform olefin polymer toluene solution. Subsequently, a solution of 9.8 parts of maleic anhydride dissolved in 80 parts of toluene, and 0.64 part of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane in toluene were added.
  • the resulting reaction solution was dropped into a large amount of acetone to obtain a filtered product containing the desired amorphous ethylene / propylene / tobutene copolymer modified with styrene and maleic anhydride (A-3). .
  • the filtered product was dried under reduced pressure at 100 ° C for 1 day to obtain a modified product (A-3).
  • the graft polymerization amount of styrene was 1.9%
  • the graft polymerization amount of maleic anhydride was 1.4%
  • the polystyrene content was 1.2%.
  • Table 1 shows the number average molecular weight, weight average molecular weight, and graft polymerization amount of the resulting modified product. According to the DSC measurement, no heat of fusion or heat of crystallization of 1 J / g or more was found in the modified product (A-3).
  • This modified product ( ⁇ ⁇ ⁇ ⁇ '-1) had a graft polymerization amount of styrene of 4.5% and a polystyrene content of 3.4%.
  • the modified product was measured by GP, and as a result, the weight average molecular weight (Mw) was 97,000.
  • the number average molecular weight (Mn) was 10,000, and the molecular weight distribution (MwZMn) was 9.8.
  • the intrinsic viscosity [7?] Of the modified product ( ⁇ '-1) is 0.35, and the DSC measurement shows that the heat of fusion of the modified product ( ⁇ '-1) is 11.3 JZg.
  • the heat of crystallization was 12.5 J / g. .
  • the modified product ( ⁇ '—2) had a maleic anhydride polymerization amount of 0.83%, and the modified product was measured by GPC.
  • the intrinsic viscosity [ ⁇ ?] Of ( ⁇ '— 2) is 0.43. According to DSC measurement, the heat of fusion of ( ⁇ ' -2) is 16.8 J / g, and the heat of crystallization was 18.9 J / g.
  • the modified products obtained in Examples 1 and 2 and Comparative Example 1 were converted into a sheet-like adhesive having a thickness of 50 ⁇ xm by a hot press molding machine at a temperature of 180 ° C. and a pressure of about 10 MPa.
  • the aluminum foil, PET sheet (50 m thick, Lumira, manufactured by Toray Industries, Inc.) the adhesive sheet, the base material, and the aluminum foil are laminated in this order, and the heat-seal tes- ),
  • the adhesive was held at the bonding temperature of 180 ° C and a pressure of 0.3 MPa for 3 seconds from above.
  • the aluminum foil of the obtained laminate was peeled off, and left still at room temperature of 23 ° C. and humidity of 50% for 1 hour. Thereafter, the laminate was cut into a width of 10 mm, and a 180 ° peel test (peel speed: 100 mm / sec) was performed at a temperature of 23 ° C and a humidity of 50%.
  • Example 1 A'-1 Styrene 4.5 10,000 97,0UU 9.7 1 1, 3 ⁇ 1j o.0 180 13.8
  • Example 3 A-2a.Maleic anhydride 1.34 154,000 311,000 2.0 0 0 120 10.9
  • Example 4 Maleic anhydride 0.49 160,000 329,000 2.1 0 0 120 7.6 on Example 5 Maleic anhydride 1.12 Sir 00 267,000 2.0 0 0 120 9.3 Comparative example 2 AT-2 Maleic anhydride 0.83 15,000 91,000 9.7 16.8 18.9 120 5.4 Styrene 1.9
  • Example 6 A-3 111,000 320,000 2.9 0 0 180 19.6 Maleic anhydride 1.4
  • A-1 Amorphous olefin polymer ⁇ styrene modified product
  • A- 2 Amorphous olefin polymer ⁇ maleic anhydride modified product
  • A- 3 Amorphous olefin polymer 'Styrene ⁇ Modified with maleic anhydride
  • a 1 crystalline olefin polymer ⁇ styrene modified product
  • a '— 2 Crystalline olefin polymer' Modified maleic anhydride
  • thermoplastic resin (Thermoplastic resin)
  • thermoplastic resins used in the resin composition.
  • B-2 Polyester resin, manufactured by B0stik, Vite14400B
  • Amorphous olefin polymer / maleic anhydride-modified product (A-2a) obtained in Example 3 was mixed with 100 parts of the thermoplastic resin in the number shown in Table 2 in a Toyo Seiki Co., Ltd. The mixture was melt-kneaded at 60 ° C. for 10 minutes at ° C. to obtain a resin composition.
  • the modified amorphous olefin polymer of the present invention can be used as an active ingredient of an adhesive having excellent adhesiveness to a thermoplastic resin such as an olefin resin. Further, the resin composition of the present invention can be used as an adhesive having excellent adhesiveness to an olefin resin, a metal, and a polar group-containing resin.
  • a packaging material for example, by laminating a decorative film or applying a paint on the adhesive of the present invention, a packaging material, a building material, a housing of a home appliance, a pump, a door molding, a door miller, a door underer It can be used for a polypropylene resin laminate for automobile exterior such as one cover, electronic parts and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un polymère oléfinique amorphe modifié obtenu en polymérisant par greffage un hydrocarbone aromatique, substitué par alkényle, et/ou un acide carboxylique insaturé avec un polymère oléfinique. Ce polymère oléfinique amorphe modifié, qui présente une chaleur de fusion ou une chaleur de cristallisation inférieure ou égale 1 J/g, peut être utilisé comme principe actif pour un adhésif présentant une excellente adhésion aux résines thermoplastiques telles que les résines oléfiniques. L'invention concerne également une composition de résine contenant ledit polymère oléfinique amorphe modifié et une résine thermoplastique, qui peut être utilisée comme principe actif pour un adhésif à propriété d'adhésion excellente sur les résines oléfiniques, les métaux, les résines à groupes polaires, etc.
PCT/JP2001/003824 2000-05-08 2001-05-07 Polymere olefinique amorphe modifie et composition de resine contenant ledit polymere modifie et une resine thermoplastique WO2001085815A1 (fr)

Applications Claiming Priority (4)

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JP2000-134492 2000-05-08
JP2000134492 2000-05-08
JP2000-240867 2000-08-09
JP2000240867 2000-08-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1308470A3 (fr) * 2001-11-01 2004-01-14 Mitsubishi Chemical Corporation Polymer de propylène modifié, composition contenant celui-ci et son utilisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61126120A (ja) * 1984-11-22 1986-06-13 Mitsui Petrochem Ind Ltd 液状変性エチレン系ランダム共重合体
JPH0532737A (ja) * 1991-08-01 1993-02-09 Mitsui Toatsu Chem Inc 接着性ポリオレフイン樹脂組成物
JPH08217835A (ja) * 1995-02-15 1996-08-27 Ube Ind Ltd 改質された非晶質重合体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61126120A (ja) * 1984-11-22 1986-06-13 Mitsui Petrochem Ind Ltd 液状変性エチレン系ランダム共重合体
JPH0532737A (ja) * 1991-08-01 1993-02-09 Mitsui Toatsu Chem Inc 接着性ポリオレフイン樹脂組成物
JPH08217835A (ja) * 1995-02-15 1996-08-27 Ube Ind Ltd 改質された非晶質重合体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1308470A3 (fr) * 2001-11-01 2004-01-14 Mitsubishi Chemical Corporation Polymer de propylène modifié, composition contenant celui-ci et son utilisation
EP1541602A1 (fr) * 2001-11-01 2005-06-15 Mitsubishi Chemical Corporation Polymer de propylène modifié, composition contenant celui-ci et son utilisation

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