JPH01318005A - Modification of olefin polymer - Google Patents
Modification of olefin polymerInfo
- Publication number
- JPH01318005A JPH01318005A JP15011888A JP15011888A JPH01318005A JP H01318005 A JPH01318005 A JP H01318005A JP 15011888 A JP15011888 A JP 15011888A JP 15011888 A JP15011888 A JP 15011888A JP H01318005 A JPH01318005 A JP H01318005A
- Authority
- JP
- Japan
- Prior art keywords
- olefin polymer
- acid
- weight
- parts
- polymer
- 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.)
- Pending
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 26
- 238000012986 modification Methods 0.000 title description 2
- 230000004048 modification Effects 0.000 title description 2
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011521 glass Substances 0.000 abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001225 polyester resin Polymers 0.000 abstract description 5
- 239000004645 polyester resin Substances 0.000 abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000004342 Benzoyl peroxide Substances 0.000 abstract 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract 1
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract 1
- 239000004035 construction material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 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 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-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
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 102100032488 Acylamino-acid-releasing enzyme Human genes 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 101000798584 Homo sapiens Acylamino-acid-releasing enzyme Proteins 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エポキシ化された特定のオレフィン系ポリマ
ー組成物の製造方法に関し、特に、接着性の優れた原料
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a specific epoxidized olefin polymer composition, and particularly to a method for producing a raw material with excellent adhesive properties.
（従来の技術）
オレフィン系ポリマーに無水マレイン酸やアクリル酸を
グラフトする技術は、以前から知られている。例えば、
オレフィン系ポリマーにこれらの酸と有機過酸化物その
他を加えて加熱混練すれば酸グラフトポリマーが得られ
、このポリマーは、アルミニウムとポリオレフィンとの
接着その他に適用されている。また、エチレン−酢酸ビ
ニル−グリシジルメタクリレート三元共重合体もまた、
アルミニウムとポリオレフィンとの接着に利用されてい
る。しかし、これらの酸グラフトポリマーや三元共重合
体は、アルミニウム、ポリエステル樹脂あるいはガラス
との接着力が低いものしか得られていなかった。(Prior Art) The technique of grafting maleic anhydride or acrylic acid onto an olefinic polymer has been known for a long time. for example,
By adding these acids, organic peroxides, and others to an olefinic polymer and kneading them under heat, an acid graft polymer is obtained, and this polymer is used for adhesion between aluminum and polyolefin, and other applications. In addition, ethylene-vinyl acetate-glycidyl methacrylate terpolymer also has
It is used to bond aluminum and polyolefin. However, these acid graft polymers and terpolymers have only low adhesion to aluminum, polyester resins, or glass.
（発明が解決しようとする課題）
本発明は、アルミニウム、ポリエステル樹脂、ガラスそ
の他に対して強い接着力を持つオレフィン系変性ポリマ
ーを得る方法に関する。(Problems to be Solved by the Invention) The present invention relates to a method for obtaining an olefin-based modified polymer having strong adhesion to aluminum, polyester resin, glass, and the like.
（課題を解決するための手段）
本発明は、酸変性されたオレフィン系ポリマー１００重
量部に対し、０．０５〜３０重量部のグリシジル（メタ
）アクリレートと０．０１〜３重量部の有機過酸化物と
から成る組成物を加熱することを特徴とするオレフィン
系ポリマーの変性方法、並びにこのような変性されたオ
レフィン系ポリマーからなる接着剤に関する。(Means for Solving the Problems) The present invention provides glycidyl (meth)acrylate in an amount of 0.05 to 30 parts by weight and organic filtrate in an amount of 0.01 to 3 parts by weight, based on 100 parts by weight of an acid-modified olefin polymer. The present invention relates to a method for modifying an olefin polymer, which comprises heating a composition comprising an oxide, and an adhesive comprising such a modified olefin polymer.
（作用）
本発明で使用される酸変性されたオレフィン系ポリマー
は、無水マレイン酸、アクリル酸、メタクリル酸その他
の酸を結合したオレフィン系ポリマーであり、オレフィ
ン系ポリマーとしては、エチレン、プロピレン、ブテン
、ヘキセン、ブタジェン、ヘキサジエン等のオレフィン
のホモポリマー、又はこれらのオレフィンと共重合可能
なモノマー、例えば酢酸ビニル、アクリル酸メチル、ア
クリル酸エチル、アクリル酸ブチル等とのコポリマーが
挙げられ、特に好ましいものとしてはポリエチレン、ポ
リプロピレン、ポリブテン、エチレン−酢酸ビニル共重
合体、エチレン−アクリル酸メチル共重合体、エチレン
−アクリル酸エチル共重合体、エチレン−アクリル酸ブ
チル共重合体、エチレン−プロピレン共重合体、エチレ
ン−プロピレン−ジエン三元共重合体その他が挙げられ
る。(Function) The acid-modified olefin polymer used in the present invention is an olefin polymer in which maleic anhydride, acrylic acid, methacrylic acid, and other acids are bonded. , homopolymers of olefins such as hexene, butadiene, and hexadiene, or copolymers with monomers copolymerizable with these olefins, such as vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, etc., and particularly preferred ones include Examples include polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene copolymer, Examples include ethylene-propylene-diene terpolymer and others.
本発明において使用される酸変性されたオレフィン系ポ
リマーは各種の方法によって得られる。The acid-modified olefinic polymer used in the present invention can be obtained by various methods.
そのような方法としてはオレフィン系ポリマーと酸とを
有機溶媒に溶解し有機過酸化物を加えて加熱する、オレ
フィン系ポリマーと酸と有機過酸化物とを加熱混練する
、オレフィン系ポリマーに酸を加えた後に電子線や紫外
線を照射する等の方法があるが、特に、その方法は制限
されない。更に、エチレンとアクリル酸、あるいはエチ
レンとメタクリル酸を共重合させて得られる酸変性され
°たオレフィン系ポリマーを使用することもできる。Such methods include dissolving an olefinic polymer and an acid in an organic solvent, adding an organic peroxide and heating the mixture, heating and kneading the olefinic polymer, acid, and organic peroxide, and adding an acid to an olefinic polymer. There are methods such as irradiation with electron beams or ultraviolet rays after addition, but the method is not particularly limited. Furthermore, acid-modified olefin polymers obtained by copolymerizing ethylene and acrylic acid or ethylene and methacrylic acid can also be used.
本発明において、酸変性されたオレフィン系ポリマーの
酸成分含量は、オレフィン系ポリマー１００重量部に対
し、０．１〜３０重量部が望ましい、０．１重量部より
少ないと、その接着効果がほとんど無く、また、３０重
量部より多くても、その効果は増加しない。In the present invention, the acid component content of the acid-modified olefin polymer is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the olefin polymer; if it is less than 0.1 part by weight, the adhesive effect is almost negligible. Even if the amount is more than 30 parts by weight, the effect will not increase.
本発明に使用される、グリシジル（メタ）アクリレート
は、グリシジルアクリレート及びグリシジルメタクリレ
ートである。The glycidyl (meth)acrylates used in the present invention are glycidyl acrylate and glycidyl methacrylate.
本発明において、グリシジル（メタ）アクリレートの成
分比は、酸変性されたオレフィン系ポリマー１００重量
部に対し、０．０５〜３０重量部である。０．０５重量
部よりより少ないと、その接着効果がほとんど無く、ま
た、３０重量部より多くても、その効果は増加しない。In the present invention, the component ratio of glycidyl (meth)acrylate is 0.05 to 30 parts by weight based on 100 parts by weight of the acid-modified olefin polymer. If the amount is less than 0.05 parts by weight, the adhesive effect will be almost absent, and if it is more than 30 parts by weight, the effect will not increase.
本発明において使用される有機過酸化物は、分解温度が
半減期１０分間で１００〜２２０℃のものであり、次の
ものが例として挙げられる。ただし、括弧内は、分解温
度（’Ｃ）である。The organic peroxide used in the present invention has a decomposition temperature of 100 to 220° C. with a half-life of 10 minutes, and examples thereof include the following. However, the value in parentheses is the decomposition temperature ('C).
コハク酸ペルオキシド（１１０） 、ペイシイルベルオ
キシド（１１０） 、 ｔ−ブチルペルオキシ−２−
エチルヘキサノエート（１１３） 、 ｐ−クロロベン
ゾイルペルオキシド（１１５） 、ｔ−ブチルペルオキ
シイソブチレート（＋＋５） 、 ｔ−ブチルペルオ
キシイソプロビルカーボネート（＋３５） 、 ｔ−
ブチルペルオキシラウレート（１４０） 、 ２．５−
ジメチル−２，５−ジ（ベンゾイルペルオキシ）ヘキサ
ン（１４０） 、 ｔ−ブチルペルオキシアセテート（
１４０） 、ジ−ｔ−ブチルジペルオキシフタレート（
１４０） 、ｔ−ブチルペルオキシマレイン酸（１４０
） 、シクロヘキサノンペルオキシド（１４５） 、ｔ
−ブチルペルオキシベンゾエート（１４５） 、ジクミ
ルペルオキシド（１５０）、２．５−ジメチル−２，５
−ジ（ｔ−ブチルペルオキシ）ヘキサン（＋５５） 、
ｔ−ブチルクミルペルオキシド（＋５５） 、 ｔ−
ブチルヒドロペルオキシド（＋５８） 、ジ−ｔ−ブチ
ルペルオキシド（１６０） 、 ２゜５−ジメチル−２
，５−ジ（ｔ−ブチルペルオキシ）ヘキシン３ （１７
０） 、ジ−イソプロピルベンゼンヒドロベルオキシド
（１７０） 、ｐ−メンタンヒドロペルオキシド（１８
０） 、２．５−ジメチルヘキサン−２，５−ジヒドロ
ペルオキシド（２１３）。Succinic acid peroxide (110), Peisyl peroxide (110), t-butylperoxy-2-
Ethylhexanoate (113), p-chlorobenzoyl peroxide (115), t-butylperoxyisobutyrate (++5), t-butylperoxyisopropyl carbonate (+35), t-
Butyl peroxylaurate (140), 2.5-
Dimethyl-2,5-di(benzoylperoxy)hexane (140), t-butylperoxyacetate (
140), di-t-butyl diperoxyphthalate (
140), t-butylperoxymaleic acid (140)
), cyclohexanone peroxide (145), t
-Butyl peroxybenzoate (145), dicumyl peroxide (150), 2,5-dimethyl-2,5
-di(t-butylperoxy)hexane (+55),
t-butylcumyl peroxide (+55), t-
Butyl hydroperoxide (+58), di-t-butyl peroxide (160), 2゜5-dimethyl-2
,5-di(t-butylperoxy)hexyne 3 (17
0), di-isopropylbenzene hydroperoxide (170), p-menthane hydroperoxide (18
0), 2,5-dimethylhexane-2,5-dihydroperoxide (213).
本発明において、有機過酸化物の成分比は、酸変性され
たオレフィン系ポリマー１００重量部に対し、０．０１
〜３重量部である。０．０１重量部より少ないと、酸変
性オレフィン系ポリマーとグリシジル（メタ）アクリレ
ートとの結合反応がほとんど起こらず、接着効果がほと
んど無く、また、３重量部より多くても、その効果はほ
とんど増加しない。In the present invention, the component ratio of the organic peroxide is 0.01 parts by weight per 100 parts by weight of the acid-modified olefin polymer.
~3 parts by weight. If it is less than 0.01 part by weight, the bonding reaction between the acid-modified olefin polymer and glycidyl (meth)acrylate will hardly occur and there will be almost no adhesive effect, and if it is more than 3 parts by weight, the effect will hardly increase. do not.
本発明において、組成物を加熱する方法は、酸変性オレ
フィン系ポリマーとグリシジル（メタ）アクリレートを
有機過酸化物と共に加熱混練する、酸変性オレフィン系
ポリマーとグリシジル（メタ）アクリレートとを有機溶
媒に溶解した後に有機過酸化物を加えて加熱する等、特
に制限はない。加熱温度は、［オレフィン系ポリマーの
融点プラス１０℃以上」から３５０℃程度までが望まし
い、但し室温以上に融点の存在しないポリマーの場合は
、１００℃から３５０℃程度までが望ましい。In the present invention, the method of heating the composition includes heating and kneading the acid-modified olefin-based polymer and glycidyl (meth)acrylate together with an organic peroxide, or dissolving the acid-modified olefin-based polymer and glycidyl (meth)acrylate in an organic solvent. There are no particular restrictions, such as adding an organic peroxide and heating after that. The heating temperature is preferably from [the melting point of the olefin polymer plus 10°C or more] to about 350°C, however, in the case of a polymer that does not have a melting point above room temperature, it is preferably from about 100°C to about 350°C.
本発明の方法により得られたエポキシ化された変性オレ
フィン系ポリマーは、アルミニウム、ポリエステル樹脂
、ガラスその他の基材に対して、そのような変性処理を
受けていないポリマーよりもはるかに強い接着性を示し
、強力な接着剤となる。本発明の変性されたオレフィン
系ポリマーは、例えば、ベレット、フィルム、シート等
にした後に基材上に適用しあるいは基材間にはさんで加
圧加熱させることにより基材に強く接着することができ
、優れたホットメルト型接着剤となる。The epoxidized modified olefinic polymer obtained by the method of the present invention exhibits much stronger adhesion to aluminum, polyester resin, glass, and other substrates than polymers that have not undergone such modification treatment. and is a strong adhesive. The modified olefin polymer of the present invention can be strongly adhered to a substrate by applying it onto a substrate after forming it into a pellet, film, sheet, etc., or sandwiching it between substrates and heating it under pressure. This makes it an excellent hot melt adhesive.
本発明の接着剤においては、無機充填剤、酸化防止剤、
紫外線安定剤、顔料、粘着付与剤その他を添加しても良
い。In the adhesive of the present invention, an inorganic filler, an antioxidant,
UV stabilizers, pigments, tackifiers, etc. may also be added.
本発明の接着剤は、特に、自動車用、建材用、電線ケー
ブル用、電子部品用その他の用途に使用することができ
、強度の高い構造物を与えることができる。The adhesive of the present invention can be used particularly for automobiles, building materials, electric wires and cables, electronic parts, and other applications, and can provide structures with high strength.
（実施例）
ｌ び し １ １〜４メルトインデ
ツクス４、酢酸ビニル含量２５重量％のエチレン−酢酸
ビニル共重合体ベレット（以下ＥＶＡという）１００重
量部に対し、アクリル酸０．５重量部、ｔ−ブチルペル
オキシイソプロビルカーボネート０．０５重量部および
酸化防止剤（２，６−ジーｔ−ブチル−ｐ−クレゾール
）０．１重量部をヘンシェルミキサーで６０℃で１０分
間混合したものを、−昼夜放置した後、２軸押用機で１
７０℃で押し出し、ペレット化した（以下このように処
理されたポリマーをＡＥＶＡという）。なお、この時の
組成物の押出機での平均滞留時間は、およそ３分であっ
た。(Example) 1 to 4 Melt index 4, 0.5 parts by weight of acrylic acid to 100 parts by weight of ethylene-vinyl acetate copolymer pellet (hereinafter referred to as EVA) having a vinyl acetate content of 25% by weight, A mixture of 0.05 parts by weight of t-butylperoxyisopropyl carbonate and 0.1 parts by weight of an antioxidant (2,6-di-t-butyl-p-cresol) at 60°C for 10 minutes in a Henschel mixer was mixed with - After leaving it for day and night, it is
It was extruded at 70° C. and pelletized (hereinafter, the polymer treated in this way will be referred to as AEVA). Note that the average residence time of the composition in the extruder at this time was approximately 3 minutes.
また、ＥＶＡ１００重量部に対し、グリシジルメタクリ
レート５重量部、酸化防止剤［テトラキス［メチレン（
３，５−ジ−ｔ−ブチル−４−ヒドロキシハイドロシン
ナメート）］３２２１００．１重量をヘンシェルミキサ
ーで６０℃で１０分間混合したものを、−昼夜放置した
後、２軸押用機で１７０℃で押し出し、ペレット化した
（以下このように処理されたポリマーをＧＥＶＡという
）、なお、この時の組成物の押出機での平均滞留時間は
、およそ５分であった。In addition, for 100 parts by weight of EVA, 5 parts by weight of glycidyl methacrylate, an antioxidant [tetrakis[methylene]
3,5-di-t-butyl-4-hydroxyhydrocinnamate)] 322100.1 weight was mixed at 60°C for 10 minutes in a Henschel mixer, and after being left to stand day and night, it was mixed at 170°C in a twin-screw extrusion machine. (hereinafter, the polymer treated in this way will be referred to as GEVA), and the average residence time of the composition in the extruder was approximately 5 minutes.
次に、ＡＥＶＡ１００重量部に対し、グリシジルメタク
リレート５重量部、酸化防止剤［テトラキス［メチレン
（３，５−ジ−ｔ−ブチル−４−ヒドロキシハイドロシ
ンナメート）］３２２１００．１重量をヘンシェルミキ
サーで６０℃で１０分間混合したものを、−昼夜放置し
た後、２軸押用機で１７０℃で押し出し、ペレット化し
た（以下このように処理されたポリマーをＧＡＥＶＡ
という）。Next, to 100 parts by weight of AEVA, 5 parts by weight of glycidyl methacrylate and 322,100.1 parts by weight of an antioxidant [tetrakis[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] were added to 100 parts by weight of AEVA using a Henschel mixer. The mixture was mixed at ℃ for 10 minutes, left for day and night, and then extruded at 170℃ using a twin-screw extrusion machine to form pellets.
).
なお、この時の組成物の押出機での平均滞留時間は、お
よそ５分であった。Note that the average residence time of the composition in the extruder at this time was approximately 5 minutes.
これらのポリマーのシートを各種基材にはさみ、加圧加
熱接着し、その接着強度を測定した。Sheets of these polymers were sandwiched between various base materials and bonded under pressure and heat, and the adhesive strength was measured.
接着強度の測定は、 ＪＩＳＫ６８５４に準じて行なっ
た。即ち、各ベレットをＴダイ製膜法により、厚さ０．
５ｍｍのシートとし、このシートを１００ｍｍＸ、１５
０ｍｍの大きさに裁断した。The adhesive strength was measured according to JIS K6854. That is, each pellet was formed into a film having a thickness of 0.5 mm using the T-die film forming method.
5mm sheet, and this sheet is 100mmX, 15
It was cut into a size of 0 mm.
（ａ）上記の各シートを厚さ０．２ ｍｍの２枚のアル
ミシートの間にはさみ、１７０℃で、予熱５分後、１０
ｋｇ／ｃｍ２の圧力で１分間加圧し、接着強度測定用
試料とした。(a) Each of the above sheets was sandwiched between two aluminum sheets with a thickness of 0.2 mm, and after preheating at 170°C for 5 minutes,
A pressure of kg/cm2 was applied for 1 minute to prepare a sample for measuring adhesive strength.
（ｂ）同様にして、各シートを厚さ０．０７５ｍｍの２
枚のポリエチレンテレフタレートのシートの間にはさみ
、１７０℃で、予熱５分後、１０ ｋｇ／ｃｍ”の圧力
で１分間加圧し、接着強度測定用試料とした。(b) Similarly, each sheet was made into 2 sheets with a thickness of 0.075 mm.
The sample was sandwiched between two polyethylene terephthalate sheets, preheated at 170°C for 5 minutes, and then pressed at a pressure of 10 kg/cm'' for 1 minute to prepare a sample for adhesive strength measurement.
（Ｃ）同様にして、各シートを厚さ０．０７５ｉ＋ｍの
ポリエチレンテレフタレートのシートと厚さ３ｍｍのガ
ラス板との間にはさみ、１７０℃で予熱５分後、１０
ｋｇ／ｃｍ”の圧力で１分間加圧し、接着強度測定用試
料とした。(C) In the same manner, each sheet was sandwiched between a polyethylene terephthalate sheet with a thickness of 0.075i+m and a glass plate with a thickness of 3mm, and after preheating at 170°C for 5 minutes,
A pressure of 100 kg/cm'' was applied for 1 minute to prepare a sample for measuring adhesive strength.
これらの試料について、試料中１５ｍｍ、引張速度２０
０ ｍｍ／ｍｉｎ、測定温度２３℃で接着強度測定を行
なった。For these samples, 15 mm in the sample and a tensile speed of 20
The adhesive strength was measured at a speed of 0 mm/min and a measurement temperature of 23°C.
また、エチレン−酢酸ビニル−グリシジルメタクリレー
ト三元共重合体が主成分と推定される、Ｂｏｎｄｆａｓ
ｔ Ａ （住友化学工業製）の厚さ０．５ ｍｍのフィ
ルム（以下市販品）についても、その接着強度を測定し
た。In addition, Bondfas, whose main component is estimated to be an ethylene-vinyl acetate-glycidyl methacrylate terpolymer,
The adhesive strength of a 0.5 mm thick film (hereinafter referred to as a commercial product) made by tA (manufactured by Sumitomo Chemical Industries) was also measured.
これらの試料の、接着強度測定結果を表１に示す。Table 1 shows the results of measuring the adhesive strength of these samples.
表１
接着強度（ｋｇ／ １．５ｃｍ）
ポリ？−（ａ） （ｂ） （ｃ）実施
例Ｉ ＧＡＥＶＡ ２０．０ １５．０ ２３．
０比較例Ｉ ＥＶＡ ２．０ ＜０．１ ２．
０比較例２ ＡＥＶＡ ４．３ ０．３ ５
．８比較例３ ＧＥＶＡ １５．０ ８．０
２０．０比較例４ 市販品 １３．０ ？、０
＋７．０２ び １５
実施例１と同様にして、ＥＶＡの代りに、メルトインデ
ックス６、アクリル酸エチル含量１８重量％のエチレン
−アクリル酸エチル共重合体（以下ＥＥＡという）を使
用し、アクリル酸変性ＥＥＡ （以下ＡＥＥＡという）
及びＡＥＥＡのグリシジルメタクリレート変性品（以下
ＧＡＥＥＡという）を得、接着強度を測定した。測定結
果を表２に示す。Table 1 Adhesive strength (kg/1.5cm) Poly? -(a) (b) (c) Example I GAEVA 20.0 15.0 23.
0 Comparative Example I EVA 2.0 <0.1 2.
0 Comparative Example 2 AEVA 4.3 0.3 5
．． 8 Comparative Example 3 GEVA 15.0 8.0
20.0 Comparative Example 4 Commercial product 13.0 ? ,0
+7.02 and 15 In the same manner as in Example 1, an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) having a melt index of 6 and an ethyl acrylate content of 18% by weight was used instead of EVA, and acrylic acid modified EEA (hereinafter referred to as AEEA)
A glycidyl methacrylate modified product of AEEA (hereinafter referred to as GAEEA) was obtained, and the adhesive strength was measured. The measurement results are shown in Table 2.
３ び ６
実施例１と同様にして、ＥＶＡの代りに、メルトインデ
ックス４、密度０．９３５の低圧法低密度ポリエチレン
（エチレン−ブテン共重合体）（以下ＦＥＢという）を
使用し、アクリル酸変性ＰＥＢ （以下ＡＰＥＢとい
う）及びＡＰＥＢのグリシジルメタクリレート変性品（
以下ＧＡＰＥＢという）を得、接着強度を測定した。但
し押出温度は１９０℃であった。測定結果を表２に示す
。3 and 6 In the same manner as in Example 1, low-pressure low-density polyethylene (ethylene-butene copolymer) (hereinafter referred to as FEB) with a melt index of 4 and a density of 0.935 was used instead of EVA, and modified with acrylic acid. PEB (hereinafter referred to as APEB) and glycidyl methacrylate modified products of APEB (
(hereinafter referred to as GAPEB) was obtained, and the adhesive strength was measured. However, the extrusion temperature was 190°C. The measurement results are shown in Table 2.
−４び ７
実施例１と同様にして、ＥＶＡの代りに、メルトインデ
ックス２、密度０．９２５の低圧法低密度ポリエチレン
（エチレン−ヘキセン共重合体）（以下ＰＥＨという）
を使用し、アクリル酸変性ＰＥＨ（以下ＡＰＥＨという
）及び八ＰＥＨのグリシジルメタクリレート変性品（以
下ＧＡＰＥ）Ｉという）を得、接着強度を測定した。但
し押出温度は１９０℃であった。測定結果を表２に示す
。-4 and 7 In the same manner as in Example 1, instead of EVA, low-pressure low-density polyethylene (ethylene-hexene copolymer) (hereinafter referred to as PEH) with a melt index of 2 and a density of 0.925 was used.
were used to obtain acrylic acid-modified PEH (hereinafter referred to as APEH) and a glycidyl methacrylate-modified product of 8PEH (hereinafter referred to as GAPE I), and the adhesive strength was measured. However, the extrusion temperature was 190°C. The measurement results are shown in Table 2.
−５び ８
実施例１と同様にして、ＥＶＡの代りに、メルトインデ
ックス９、密度０．９００のポリプロピレン（以下ＰＰ
という）を使用し、アクリル酸変性ＰＰ（以下ＡＰＰと
いう）及びＡＰＰのグリシジルメタクリレート変性品（
以下ＧＡＰＰという）を得、接着強度を測定した。但し
押出温度は２１０℃であった。測定結果を表２に示す。-5 and 8 In the same manner as in Example 1, polypropylene (hereinafter referred to as PP) having a melt index of 9 and a density of 0.900 was used instead of EVA.
acrylic acid-modified PP (hereinafter referred to as APP) and glycidyl methacrylate-modified products of APP (hereinafter referred to as APP).
(hereinafter referred to as GAPP) was obtained, and the adhesive strength was measured. However, the extrusion temperature was 210°C. The measurement results are shown in Table 2.
−６び ９
実施例１と同様にして、ＥＶＡの代りに、日本合成ゴム
側製エチレンープロピレン−ジエン共重合体ＥＰ５７Ｇ
（以下ＥＰＤＭという）を使用し、アクリル酸変性
ＥＰＤＭ （以下ＡＥＰＤＭという）及びＡＥＰＤＭの
グリシジルメタクリレート変性品（以下ＧＡＥＰＤＭと
いう）を得、接着強度を測定した。測定結果を表２に示
す。-6 and 9 In the same manner as in Example 1, ethylene-propylene-diene copolymer EP57G manufactured by Japan Synthetic Rubber Co., Ltd. was used instead of EVA.
(hereinafter referred to as EPDM) to obtain acrylic acid-modified EPDM (hereinafter referred to as AEPDM) and a glycidyl methacrylate modified product of AEPDM (hereinafter referred to as GAEPDM), and the adhesive strength was measured. The measurement results are shown in Table 2.
表２
接着強度（ｋｇ／ １．５ｃｍ）
ポリマー （ａ） （ｂ）
（ｃ）実施例２ ＧＡＥＥＡ １３．７
５．４ ８．０実施例３ ＧＡＰＥＢ ５．２
１．５ ０．４実施例４ ＧＡＰＥＨ５，５１，４
０゜５実施例５ ＧＡＰＰ ６．７ ２．３
１．８実施例６ ＧＡＥＰＤＭ ６．０ ２
．０ ０．４比較例５ ＡＥＥＡ ＋０．２
３．０ ４．３比較例６ ＡＰＥＢ ３．６
０．８ ＜０．１比較例７ ＡＰＥＨ３，８０，
８＜０．１比較例８ ＡＰＰ ５．４ １．
２ ＜０．１比較例９ ＡＥＰＤＭ ５．０
０．９ ＜０．１（発明の効果）
本発明により、アルミニウム、ポリエステル樹脂、ガラ
スその他に対して強い接着力を持つ接着剤が得られ、自
動車用、建材用、電線ケーブル用、電子部品用その他の
分野に信頼度の高い構造物を提供することができる。Table 2 Adhesive strength (kg/1.5cm) Polymer (a) (b)
(c) Example 2 GAEEA 13.7
5.4 8.0 Example 3 GAPEB 5.2
1.5 0.4 Example 4 GAPEH5,51,4
0゜5 Example 5 GAPP 6.7 2.3
1.8 Example 6 GAEPDM 6.0 2
．． 0 0.4 Comparative Example 5 AEEA +0.2
3.0 4.3 Comparative Example 6 APEB 3.6
0.8 <0.1 Comparative Example 7 APEH3,80,
8<0.1 Comparative Example 8 APP 5.4 1.
2 <0.1 Comparative Example 9 AEPDM 5.0
0.9 <0.1 (Effect of the invention) According to the present invention, an adhesive having strong adhesion to aluminum, polyester resin, glass, etc. can be obtained, and can be used for automobiles, building materials, electric wires and cables, and electronic parts. Highly reliable structures can be provided in other fields.
Claims (1)
対し、０．０５〜３０重量部のグリシジル（メタ）アク
リレートと０．０１〜３重量部の有機過酸化物とから成
る組成物を加熱することを特徴とするオレフィン系ポリ
マーの変性方法。 ２、酸変性されたオレフィン系ポリマーをこのポリマー
１００重量部に対して０．０５〜３０重量部の量のグリ
シジル（メタ）アクリレートで変性することによって得
られるエポキシ化されたオレフィン系ポリマーからなる
接着剤。[Claims] 1. Consisting of 0.05 to 30 parts by weight of glycidyl (meth)acrylate and 0.01 to 3 parts by weight of an organic peroxide based on 100 parts by weight of acid-modified olefin polymer. A method for modifying an olefin polymer, the method comprising heating a composition. 2. An adhesive made of an epoxidized olefin polymer obtained by modifying an acid-modified olefin polymer with 0.05 to 30 parts by weight of glycidyl (meth)acrylate per 100 parts by weight of this polymer. agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15011888A JPH01318005A (en) | 1988-06-20 | 1988-06-20 | Modification of olefin polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15011888A JPH01318005A (en) | 1988-06-20 | 1988-06-20 | Modification of olefin polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01318005A true JPH01318005A (en) | 1989-12-22 |
Family
ID=15489880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15011888A Pending JPH01318005A (en) | 1988-06-20 | 1988-06-20 | Modification of olefin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01318005A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6126609A (en) * | 1984-07-16 | 1986-02-05 | Nippon Petrochem Co Ltd | Adherent resin and laminate |
-
1988
- 1988-06-20 JP JP15011888A patent/JPH01318005A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6126609A (en) * | 1984-07-16 | 1986-02-05 | Nippon Petrochem Co Ltd | Adherent resin and laminate |
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