JPH03143932A - Crosslinked high-density polyethylene foam - Google Patents
Crosslinked high-density polyethylene foamInfo
- Publication number
- JPH03143932A JPH03143932A JP28077089A JP28077089A JPH03143932A JP H03143932 A JPH03143932 A JP H03143932A JP 28077089 A JP28077089 A JP 28077089A JP 28077089 A JP28077089 A JP 28077089A JP H03143932 A JPH03143932 A JP H03143932A
- Authority
- JP
- Japan
- Prior art keywords
- density polyethylene
- weight
- polybutene
- foam
- low
- 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
- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 68
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 68
- 239000006260 foam Substances 0.000 title claims abstract description 48
- 229920001748 polybutylene Polymers 0.000 claims abstract description 30
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 22
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 22
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 15
- 229920001083 polybutene Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 abstract description 14
- -1 polyethylene Polymers 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- 239000004156 Azodicarbonamide Substances 0.000 abstract description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 abstract description 3
- 235000019399 azodicarbonamide Nutrition 0.000 abstract description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 17
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000001451 organic peroxides Chemical class 0.000 description 8
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 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 1
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- 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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- XQAVYBWWWZMURF-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO XQAVYBWWWZMURF-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高密度ポリエチレン架橋発泡体に関し、特に高
密度ポリエチレンの有する強度及び耐熱性を実質的に損
なうことなく、柔軟性及び成形加工性に優れた高密度ポ
リエチレン架橋発泡体に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a cross-linked high-density polyethylene foam, and particularly to a cross-linked high-density polyethylene foam that has improved flexibility and moldability without substantially impairing the strength and heat resistance of high-density polyethylene. Concerning excellent high-density polyethylene crosslinked foam.
〔従来の技術及び発明が解決しようとする課題〕ポリオ
レフィン発泡体は機械的強度、柔軟性、風合い、耐熱性
、耐薬品性等に優れており、自動車の内装材、断熱材、
スポーツ用品や食品包装の緩衝材、その他消音材や外装
材等に広く利用されている。[Prior art and problems to be solved by the invention] Polyolefin foams have excellent mechanical strength, flexibility, texture, heat resistance, chemical resistance, etc., and are used as interior materials for automobiles, insulation materials,
It is widely used in cushioning materials for sporting goods and food packaging, as well as other sound-deadening materials and exterior materials.
中でもポリプロピレン発泡体は引張強度や曲げ強度等の
機械的強度や耐熱性に（量れている。これに対して、ポ
リエチレン発泡体は融点が低い分だけ柔軟性、風合い、
伸び等に優れている。Among them, polypropylene foam has poor mechanical strength such as tensile strength and bending strength, and heat resistance.On the other hand, polyethylene foam has a low melting point, so it has low flexibility, texture, and
Excellent elongation, etc.
このポリエチレン発泡体には、一般に低密度ポリエチレ
ンが用いられており、架橋発泡成形性に優れているが、
耐熱性、引張強度、引裂強度等が劣るという問題があっ
た。Low-density polyethylene is generally used for this polyethylene foam, and it has excellent crosslinking foam moldability.
There was a problem that heat resistance, tensile strength, tear strength, etc. were inferior.
一方、高密度ポリエチレンによる架橋発泡体は、低密度
ポリエチレンと比較して強度及び耐熱性は良好であるが
、成形するのが困難であり、柔軟性に劣るという問題が
あった。On the other hand, crosslinked foams made of high-density polyethylene have better strength and heat resistance than low-density polyethylene, but have problems in that they are difficult to mold and have poor flexibility.
このような高密度ポリエチレン発泡体の問題点を解決す
るために、種々の試みがなされた。Various attempts have been made to solve these problems with high-density polyethylene foams.
特開昭５４−１５２０６８号は、密度０．９４５ ｇ／
ｃｍ以上の高密度ポリエチレン９５重量％ないし５０重
量％と、ポリブテン−１を５重量％ないし５０重量％と
の混合組成物１００重量部に対して、核形成物質０．Ｏ
ｌ〜５重量部を添加した混合物を押出機内で溶融可塑化
し、揮発性発泡剤５〜５０重量部と均一混合した後、冷
却しつつ低圧帯へ押出すことにより得られる耐熱性及び
成形性にすぐれた無架橋のポリエチレン系発泡体を開示
している。しかしながら、この発泡体は無架橋物である
ので、ｍ械的強度が十分でないという問題があった。JP-A-54-152068 has a density of 0.945 g/
For 100 parts by weight of a mixed composition of 95% to 50% by weight of high-density polyethylene of 5 cm or more and 5% to 50% by weight of polybutene-1, 0. O
The heat resistance and moldability obtained by melting and plasticizing the mixture containing 1 to 5 parts by weight in an extruder, uniformly mixing it with 5 to 50 parts by weight of a volatile blowing agent, and then extruding it to a low pressure zone while cooling. Discloses an excellent non-crosslinked polyethylene foam. However, since this foam is non-crosslinked, there is a problem in that it does not have sufficient mechanical strength.
また、特開昭６３−２１３５３１ 号は、〈Ａ〉１−ブ
テン重合体８０ないし９９重量％、（Ｂ）エチレン重合
体２０ないし１重量％、及び（Ｃ）発泡剤とから構成さ
れることを特徴とする、柔軟性、耐クリープ性、クツシ
ョン性、衛生性等に優れた無架橋発泡体用組成物を開示
している。しかしながら、この組成物の発泡体も無架橋
であるので機械的強度が十分でなく、さらに１−ブテン
重合体の含有量が８０重量％以上と多いため、高密度ポ
リエチレンの有する耐熱性が十分に発揮されないという
問題があった。Furthermore, JP-A No. 63-213531 discloses that it is composed of (A) 80 to 99% by weight of a 1-butene polymer, (B) 20 to 1% by weight of an ethylene polymer, and (C) a blowing agent. Discloses a composition for non-crosslinked foam that is characterized by excellent flexibility, creep resistance, cushioning properties, hygienic properties, etc. However, since the foam of this composition is also non-crosslinked, it does not have sufficient mechanical strength, and since the content of 1-butene polymer is as high as 80% by weight or more, the heat resistance of high-density polyethylene is insufficient. There was a problem of not being able to perform well.
したがって、本発明の目的は柔軟性及び強度を有し、成
形加工性に優れ、異方性の小さい高密度ポリエチレン架
橋発泡体を提供することである。Therefore, an object of the present invention is to provide a high-density polyethylene crosslinked foam having flexibility and strength, excellent moldability, and low anisotropy.
上記課題に鑑み鋭意研究の結果、本発明者らは、高密度
ポリエチレンに、ポリブテン−１と発泡剤とを配合した
組成物からなる架橋発泡体は、柔軟性を有し、成形加工
性に優れているとともに、良好な機械的強度を有し、異
方性が小さいことを見出し、本発明に想到した。As a result of intensive research in view of the above problems, the present inventors have found that a crosslinked foam made of a composition containing high density polyethylene, polybutene-1, and a blowing agent has flexibility and excellent moldability. The inventors have discovered that the material has good mechanical strength and low anisotropy, and have devised the present invention.
すなわち、本発明の高密度ポリエチレン架橋発泡体は、
高密度ポリエチレン２０〜９５重量％と、ポリブテン−
１５〜８０重量％と、前記高密度ポリエチレン＋ポリブ
テン−１の合計１００重量部に対して３〜３０重量部の
発泡剤とを含有する組成物からなることを特徴とする。That is, the high-density polyethylene crosslinked foam of the present invention is
20-95% by weight of high-density polyethylene and polybutene
15 to 80% by weight, and 3 to 30 parts by weight of a blowing agent based on a total of 100 parts by weight of the high-density polyethylene + polybutene-1.
また本発明のもうひとつの高密度ポリエチレン架橋発泡
体は、高密度ポリエチレン２０〜８０重量％と、ポリブ
テン−１５〜７０重量％と、低密度ポリエチレン５〜６
０重量％と、前記高密度ポリエチレン＋ポリブテン−１
＋低密度ポリエチレンの合計■００重量部に対して３〜
３０重量部の発泡剤とを含有する組成物からなることを
特徴とする。Another cross-linked high-density polyethylene foam of the present invention includes 20 to 80% by weight of high-density polyethylene, 15 to 70% by weight of polybutene, and 5 to 6% by weight of low-density polyethylene.
0% by weight and the high density polyethylene + polybutene-1
+ Total amount of low density polyethylene ■ 3 to 00 parts by weight
30 parts by weight of a blowing agent.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において、高密度ポリエチレンは、エチレンの単
独重合体、もしくはエチレンを９５モル％以上含む他の
オレフィンとのランダムあるいはブロック共重合体であ
り、通常０’、 ９３０ ｇ／ ｃｉ以上、好ましくは
０．９４０ ｇ／ｃｎｆ以上の密度のものである。高密
度ポリエチレンのメルトインデックス（Ｍ＋、２゜１６
ｋｇ ／ ＣＩ＋！、１９０ ℃）は２〜４０ ｇ／
１０分であるのが好ましい。In the present invention, high-density polyethylene is an ethylene homopolymer or a random or block copolymer with other olefins containing 95 mol% or more of ethylene, and usually has a polyethylene content of 0', 930 g/ci or more, preferably 0 It has a density of .940 g/cnf or more. Melt index of high density polyethylene (M+, 2°16
kg/CI+! , 190 °C) is 2 to 40 g/
Preferably it is 10 minutes.
また本発明において、ポリブテン−１とは、ブテン−１
をチーグラーナツタ触媒等により重合させた立体規則性
重合体、あるいはブテン−ｌを５重量％以上含む他のひ
オレフィンとのランダム、ブロック又は交互共重合体で
ある。ポリブテン−１のメルトインデックス（旧、２．
１６ ｋｇ ／ ｃｔｌ、１９０ ℃）は０゜５〜２
０ｇ／１０ 分であるのが好ましい。In addition, in the present invention, polybutene-1 refers to butene-1
These are stereoregular polymers polymerized using a Ziegler-Natsuta catalyst or the like, or random, block, or alternating copolymers with other polyolefins containing 5% by weight or more of butene-1. Melt index of polybutene-1 (old, 2.
16 kg/ctl, 190℃) is 0゜5~2
Preferably it is 0 g/10 min.
高密度ポリエチレン及びポリブテン−１の配合割合は高
密度ポリエチレン＋ポリブテン−１を１００ 重量％と
して、それぞれ高密度ポリエチレンが２０〜９５重量％
、好ましくは３０〜９０重量％であり、ポリブテン−１
が５〜８０重量％、好ましくは１０〜７０重量％である
。高密度ポリエチレンの配合割合が２０重量％未満では
（ポリブテン−１が８０重量％を超えると）、高密度ポ
リエチレンの特徴である強度及び耐熱性が十分に発揮で
きず、一方９５重量％を超えると（ポリブテン−■が５
重量％を未満では） ポリブテン−１の配合量が低すぎ
るため、柔軟性、異方性等の物性の改善が十分でない。The blending ratio of high-density polyethylene and polybutene-1 is 100% by weight of high-density polyethylene + polybutene-1, and 20 to 95% by weight of each high-density polyethylene.
, preferably 30 to 90% by weight, polybutene-1
is 5 to 80% by weight, preferably 10 to 70% by weight. If the blending ratio of high-density polyethylene is less than 20% by weight (if polybutene-1 exceeds 80% by weight), the strength and heat resistance that are characteristics of high-density polyethylene cannot be fully exhibited, while if it exceeds 95% by weight, (Polybutene-■ is 5
If it is less than % by weight, the amount of polybutene-1 blended is too low, and physical properties such as flexibility and anisotropy are not sufficiently improved.
本発明においては、架橋及び発泡効率の向上を目的とし
て、高密度ポリエチレン及びポリブテン１に低密度ポリ
エチレンを配合することができる。In the present invention, low density polyethylene can be blended with high density polyethylene and polybutene 1 for the purpose of improving crosslinking and foaming efficiency.
本発明において、低密度ポリエチレンは、一般に０．９
１０〜０．９３０ ｇ／ ｃｔｌの密度を有するもので
あり、エチレンの単独重合体あるいはエチレンを９５モ
ル％以上含む他のα−オレフィンとのランダムまたはブ
ロック共重合体である。低密度ポリエチレンのメルトイ
ンデックス（旧、２．１６ ｋｇ ／ ｃｔｌ、１９０
℃）は２〜４０ｇ／１０分であるのが好ましい。In the present invention, the low density polyethylene is generally 0.9
It has a density of 10 to 0.930 g/ctl, and is an ethylene homopolymer or a random or block copolymer with other α-olefins containing 95 mol% or more of ethylene. Melt index of low density polyethylene (old, 2.16 kg/ctl, 190
C) is preferably 2 to 40 g/10 minutes.
このような低密度ポリエチレンの配合割合は、高密度ポ
リエチレン＋ポリブテンー１＋低密度ポリエチレンを１
００重量％として、５〜６０重量％である。低密度ポリ
エチレンの割合が５重量％未満ではその配合の効果が十
分でなく、また６０重量％を超えると高密度ポリエチレ
ン及び／又はポリブテン−１の配合割合が低下し過ぎる
。好ましい低密度ポリエチレンの配合割合はｌ０〜４０
重量％である。The blending ratio of such low density polyethylene is 1 part high density polyethylene + 1 part polybutene + 1 part low density polyethylene.
00% by weight is 5 to 60% by weight. If the proportion of low density polyethylene is less than 5% by weight, the effect of its blending will not be sufficient, and if it exceeds 60% by weight, the blending proportion of high density polyethylene and/or polybutene-1 will be too low. The preferred blending ratio of low density polyethylene is 10 to 40
Weight%.
なおこの場合、高密度ポリエチレン及びポリブテン−１
の配合割合は、高密度ポリエチレン＋ポリブテンー１＋
低密度ポリエチレンを１００ 重量％として、高密度ポ
リエチレン２０〜８０重量％、好ましくは３０〜７０重
量％であり、ポリブテン−１は５〜７０重量％、好まし
くは１０〜６０重量％である。高密度ポリエチレンは、
前述の樹脂成分が高密度ポリエチレンとポリブテン−１
からなる場合と同様の理由により、２０重量％以上必要
であり、ポリブテン−■は５重量％以上必要である。In this case, high-density polyethylene and polybutene-1
The blending ratio is high-density polyethylene + polybutene-1 +
When low density polyethylene is 100% by weight, high density polyethylene is 20 to 80% by weight, preferably 30 to 70% by weight, and polybutene-1 is 5 to 70% by weight, preferably 10 to 60% by weight. High density polyethylene is
The aforementioned resin components are high density polyethylene and polybutene-1.
For the same reason as in the case of polybutene, 20% by weight or more is required, and polybutene-2 is required to be 5% by weight or more.
本発明において、発泡剤としては、常温では液体状また
は固体状であるが、ポリエチレン系樹脂の溶融点以上に
加熱されたときに分解または気化する化合物で、シート
化等の底形や架橋反応を実質的に妨害しないかぎり、任
意のものが使用できるが、分解温度が１８０〜２７０
℃の範囲のものが好ましい。その具体的な例としては、
アゾジカルボンアミド、アゾジカルボン酸金属塩、ジニ
トロソペンタメチレンテトラミン、ヒドラゾジカルボン
アミド、ｐ−トルエンスルホニルセミカルバジド、Ｓ−
トリヒドラジノトリアジンなどが挙げられる。In the present invention, the blowing agent is a compound that is liquid or solid at room temperature, but decomposes or vaporizes when heated above the melting point of the polyethylene resin, and is used to improve the bottom shape and crosslinking reaction of sheeting, etc. Any material can be used as long as it does not cause substantial interference, but those with a decomposition temperature of 180 to 270
Preferably, the temperature is within the range of °C. A specific example is:
Azodicarbonamide, azodicarboxylic acid metal salt, dinitrosopentamethylenetetramine, hydrazodicarbonamide, p-toluenesulfonyl semicarbazide, S-
Examples include trihydrazinotriazine.
これらの発泡剤は、樹脂成分（高密度ポリエチレン＋ポ
リブテン−１、又は高密度ポリエチレン＋ポリブテンー
１＋低密度ポリエチレン、以下同じ）１００重量部に対
して、３〜３０重量部、好ましくは５〜２５重量部の範
囲で使用し、それぞれの種類や発、９倍率によって任意
に混合量を変えることができる。These blowing agents are used in an amount of 3 to 30 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of the resin component (high density polyethylene + polybutene-1, or high density polyethylene + polybutene-1 + low density polyethylene, the same applies hereinafter). The mixing amount can be changed as desired depending on the type, exposure, and magnification.
本発明においては、上述の高密度ポリエチレン、ポリブ
テン−１、低密度ポリエチレン及び発泡剤の池に、架橋
反応を行うために過酸化物を添加することができる。た
だし架橋反応を放射線の照射により行う場合は有機過酸
化物を使用しなくてもよい。有機過酸化物を用いる場合
は、分解温度が約１７０ ℃以上のものが好ましく、具
体的な例としては、メチルエチルケトンパーオキシド（
１８２℃）、ｔ−ブチルパーオキシイソプロピルカーボ
ネート（１５３℃） ジクミルパーオキシド（１７１
℃） クメンヒドロパーオキシド（２５５℃）、２．
５−ジメチル−２，５ジ（ｔ−ブチルパーオキシ）ヘキ
サン（１７９℃）、２．５−ジメチル−２，５−ジ（ｔ
−ブチルパーオキシ）ヘキシン−３（１９’３℃）、ジ
−ｔ−ブチルバーオキシフタレ−Ｈ１５９℃）などがあ
る。これらの有機過酸化物は、樹脂成分１００重量部に
対して、０，０１〜１．０重量部、好ましくは０．０５
〜０．５重量部の割合で使用する。In the present invention, peroxide can be added to the above-mentioned high-density polyethylene, polybutene-1, low-density polyethylene, and blowing agent in order to carry out a crosslinking reaction. However, when the crosslinking reaction is carried out by irradiation with radiation, it is not necessary to use an organic peroxide. When using an organic peroxide, one with a decomposition temperature of about 170°C or higher is preferable, and specific examples include methyl ethyl ketone peroxide (
182°C), t-butyl peroxyisopropyl carbonate (153°C), dicumyl peroxide (171
℃) cumene hydroperoxide (255℃), 2.
5-dimethyl-2,5-di(t-butylperoxy)hexane (179°C), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (179°C),
-butylperoxy)hexyne-3 (19'3°C), di-t-butylperoxyphthalate-H159°C), and the like. These organic peroxides are used in an amount of 0.01 to 1.0 parts by weight, preferably 0.05 parts by weight, based on 100 parts by weight of the resin component.
It is used in a proportion of ~0.5 parts by weight.
また架橋反応をスムーズに効率良く行うために、架橋助
剤を添加するのが好まし°、）。本発明に使用し得る架
橋助剤の例としては、トリメチロールプロパントリメタ
クリレート、トリメチロールプロパントリアクリレート
、ペンタエリスリトールペンタアクリレート、ジアリル
フタレート、ジアリルマレエート等がある。架橋に有機
過酸化物を用いる場合、架橋助剤の添加量は、樹脂成分
１００ 重量部に対して、０．１〜５．０ 重量部、好
ましくは０゜３〜３．０重量部である。In order to carry out the crosslinking reaction smoothly and efficiently, it is preferable to add a crosslinking aid. Examples of crosslinking aids that can be used in the present invention include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, diallyl phthalate, diallyl maleate, and the like. When using an organic peroxide for crosslinking, the amount of crosslinking aid added is 0.1 to 5.0 parts by weight, preferably 0.3 to 3.0 parts by weight, based on 100 parts by weight of the resin component. .
その他車発明においては、高密度ポリエチレン架橋発泡
体の特性改良などの目的のために、池の各種配合剤、具
体的にはゴム性物質、他の樹脂、顔料、各種充填剤、難
燃性物質、酸化防止剤などを適宜混合することができる
。In other car inventions, various compounding agents such as rubber substances, other resins, pigments, various fillers, and flame retardant substances are used for purposes such as improving the characteristics of high-density polyethylene cross-linked foam. , antioxidant, etc. can be mixed as appropriate.
次に、上述したような高密度ポリエチレン、ポリブテン
−１、低密度ポリエチレン、発泡剤、及び必要に応じて
配合される有機過酸化物、架橋助剤、その他の配合剤等
を用いて本発明の高密度ポリエチレン架橋発泡体を製造
する方法を説明する。Next, using the above-mentioned high-density polyethylene, polybutene-1, low-density polyethylene, a blowing agent, and organic peroxides, crosslinking aids, other compounding agents, etc., which are blended as necessary, the present invention is prepared. A method for producing a high-density polyethylene crosslinked foam will be described.
まず、上記高密度ポリエチレン、ポリブテン−１１発泡
剤、及び必要に応じて配合される低密度ポリエチレン、
有機過酸化物、架橋助剤、その他の配合剤等をニーダ、
ヘンシェルミキサー、押出機等により１４０〜１７０
℃で混練する。First, the above-mentioned high-density polyethylene, polybutene-11 foaming agent, and low-density polyethylene blended as necessary,
Organic peroxides, crosslinking aids, other compounding agents, etc. are kneaded,
140-170 depending on Henschel mixer, extruder, etc.
Knead at ℃.
次に、この混練物を押出機等のダイスより押出し、シー
ト等の成形体に底形する。・この際押出し温度は、樹脂
成分に応じて適宜制御するのが好ましい。Next, this kneaded material is extruded from a die such as an extruder to form a molded product such as a sheet. - At this time, it is preferable to control the extrusion temperature as appropriate depending on the resin component.
このようにして得られた成形体に次いで架橋を行うが、
架橋構造の形成方法としては、前述のように有機過酸化
物を用いる方法の他、α線、β線（電子線）、Ｔ線等の
電離放射線の照射による方法、加熱による方法等従来か
ら利用されている方法を採用することができる。これら
の方法の中では電離放射線の照射による方法が好ましく
、特に電子線照射による架橋が最も好ましい。放射線の
照射量は有機過酸化物及び架橋助剤の種類や量、及び架
橋の度合い等により異なるが、一般に０．１〜５０ Ｍ
ｒ ａ ｄ、好ましくは１〜３０Ｍｒａｄである。The molded body thus obtained is then crosslinked,
As for the formation method of the crosslinked structure, in addition to the method using organic peroxide as mentioned above, there are conventional methods such as irradiation with ionizing radiation such as alpha rays, beta rays (electron beams), and T rays, and methods using heating. The method described can be adopted. Among these methods, a method by irradiation with ionizing radiation is preferred, and crosslinking by electron beam irradiation is particularly preferred. The amount of radiation irradiated varies depending on the type and amount of the organic peroxide and crosslinking aid, and the degree of crosslinking, but is generally 0.1 to 50 M.
r a d, preferably 1 to 30 Mrad.
続いて、上述の高密度ポリエチレン架橋組成物の発泡を
行う。発泡は、樹脂成分の融点より高い温度、好ましく
は２００ ℃以上、より好ましくは２３０〜２７０ ℃
の温度に加熱することにより行うことができる。発泡に
要する加熱時間は通常０．５〜５分である。Subsequently, the above-described high-density polyethylene crosslinked composition is foamed. Foaming is carried out at a temperature higher than the melting point of the resin component, preferably 200°C or higher, more preferably 230-270°C.
This can be done by heating to a temperature of The heating time required for foaming is usually 0.5 to 5 minutes.
このようにして本発明の高密度ポリエチレン架橋発泡体
を得ることができる。In this way, the high-density polyethylene crosslinked foam of the present invention can be obtained.
本発明においては、高密度ポリエチレンと、ポリブテン
−ｌとを配合し、これに発泡剤を添加した組成物を架橋
発泡して高密度ポリエチレン架橋発泡体としている。In the present invention, a composition in which high-density polyethylene and polybutene-1 are blended and a foaming agent is added thereto is cross-linked and foamed to obtain a high-density polyethylene cross-linked foam.
この本発明の高密度ポリエチレン架橋発泡体は、柔軟性
を有する粘り強いフオームであり、かつ高密度ポリエチ
レンの特性である強度、耐熱性を有する。The high-density polyethylene crosslinked foam of the present invention is a flexible and tenacious foam, and has strength and heat resistance, which are characteristics of high-density polyethylene.
また、この高密度ポリエチレン架橋発泡体の組成物は、
高密度ポリエチレンをベースとして使用しても、発泡成
形性が良好である。In addition, the composition of this high-density polyethylene crosslinked foam is
Even when high-density polyethylene is used as a base, foam moldability is good.
このように本発明の発泡体が種々の特性を有する理由は
、強度及び耐熱性を有する高密度ポリエチレンに、柔軟
性を有するとともに、破壊エネルギーが高く、融点が１
１５ ℃程度と低いという特性を有するポ、リブテン−
１を配合した樹脂を架橋発泡体としているためと考えら
れる。The reason why the foam of the present invention has such various properties is that high-density polyethylene, which has strength and heat resistance, has flexibility, high fracture energy, and a melting point of 1.
Polybutene, which has the characteristic of being as low as 15°C.
This is thought to be because the resin containing No. 1 is used as a crosslinked foam.
また、ポリブテン−１の配合により、組成物の異方性を
小さくすることができるので、配向性も改善される。Further, by blending polybutene-1, the anisotropy of the composition can be reduced, so that the orientation is also improved.
本発明を以下の具体的実施例によりさらに詳細に説明す
る。The present invention will be explained in more detail by the following specific examples.
なお、各実施例及び比較例において原料樹脂としては以
下のものを用いた。In each of the Examples and Comparative Examples, the following resins were used as raw material resins.
［１］ 高密度ポリエチレン
・ＨＤＰＥ ： （Ｊ６３１１ 、東燃石油化学■製
、密度０．９５５ ｇ／ｃｄ、 ｌ ル） インチ−／
クス （旧、１９０ ℃、２．１６ｋｇ荷重）９ｇ
／１０分〕
［２］ 低密度ポリエチレン
・ＬＤＰＥ ： ［ＤＦＯＩＮ 、日本ユニカー■製
、密度０．９２４ ｇ／ ｃ＋＋！ 、メルトインテッ
クス （旧、１９０ ℃、２．１６ｋｇ荷重）３ｇ／
１０分〕
［３］ ポリブテン−１
・Ｐ Ｂ−１： ［Ｍ８３４０ 、三井石油化学工業
■製、メルトインデックス（Ｍｒ、１９０ ℃、２．
１６ｋｇ荷重）４ｇ／１０分〕
実施例１〜４及び比較例１．２
第１表に示す配合割合で、高密度ポリエチレン、ポリブ
テン−１及び低密度ポリエチレンを配合してなる樹脂成
分１００重量部に対して、発泡剤としてアゾジカルボン
アミド（水和化学■製）１５重量部と、架橋助剤として
トリメチロールプロパントリメタクリレート（新中村化
学■製）１．０重量部と、酸化防止剤としてテトラキス
〔メチレン−３（３５−ジ−ｔ−ブチル−４−ヒドロキ
シフェニル）プロピオネートコメタン（Ｉγｇａｎｏｘ
ｌθ１θ、チバガイギー製）１．０重量部とを加え、ヘ
ンシェルミキサーを用いて、３０℃、５００ｒｐｍで２
分間混合した後、Ｔダイを有する５０ｍｍφ、長さ／直
径（Ｌ／Ｄ ） ＝２８の押出機に供給し、押出温度１
５０ ℃で押し出し、厚さ１、Ｑｍｍのシートを作成し
た。[1] High-density polyethylene/HDPE: (J6311, manufactured by Tonen Petrochemical ■, density 0.955 g/cd, l) inch-/
Kusu (old, 190℃, 2.16kg load) 9g
/10 minutes] [2] Low density polyethylene/LDPE: [DFOIN, manufactured by Nippon Unicar■, density 0.924 g/c++! , Melt Intex (old, 190℃, 2.16kg load) 3g/
10 minutes] [3] Polybutene-1/P B-1: [M8340, manufactured by Mitsui Petrochemical Industries, Ltd., melt index (Mr, 190 °C, 2.
16 kg load) 4 g/10 minutes] Examples 1 to 4 and Comparative Example 1.2 100 parts by weight of a resin component made by blending high density polyethylene, polybutene-1 and low density polyethylene at the blending ratios shown in Table 1. On the other hand, 15 parts by weight of azodicarbonamide (manufactured by Hydration Kagaku ■) as a blowing agent, 1.0 parts by weight of trimethylolpropane trimethacrylate (manufactured by Shin Nakamura Kagaku ■) as a crosslinking aid, and tetrakis [manufactured by Shin Nakamura Chemical ■] as an antioxidant. Methylene-3(35-di-t-butyl-4-hydroxyphenyl)propionate comethane (Iγganox
lθ1θ, manufactured by Ciba Geigy) and 2 parts by weight at 30°C and 500 rpm using a Henschel mixer.
After mixing for a minute, the mixture was fed to a 50 mmφ extruder with a T-die, length/diameter (L/D) = 28, and the extrusion temperature was 1.
A sheet with a thickness of 1, Q mm was produced by extrusion at 50°C.
原反シートの成形性を以下の基準により評価した。The moldability of the raw sheet was evaluated based on the following criteria.
○：良好。○: Good.
△；シート成形がやや困難。△; Sheet molding is somewhat difficult.
×゛ンート成形困難。×Difficulty forming the point.
結果を第１表にあわせて示す。The results are also shown in Table 1.
次にこのシートに、７５０ｋＶ の電子線を８ Ｍｒａ
ｄのｉｔで照射し、架橋を行った。その後２５０ ℃の
エアーオーブンに１．５分間入れて発泡剤を分解し、約
３０倍に発泡させた。Next, a 750 kV electron beam was applied to this sheet at 8 Mra.
It was irradiated at d to perform crosslinking. Thereafter, it was placed in an air oven at 250° C. for 1.5 minutes to decompose the foaming agent and foam to about 30 times its original size.
このようにして得られた各架橋発泡シートのゲル分率は
、いずれも約４０％であった。また各架橋発泡シートに
ついて、発泡後の密度、２３℃における引張強度、引張
伸度及び引裂強度、耐熱性、圧縮強度及び圧縮永久歪率
をそれぞれ測定した。The gel fraction of each crosslinked foam sheet thus obtained was about 40%. Further, for each crosslinked foam sheet, the density after foaming, tensile strength at 23°C, tensile elongation and tear strength, heat resistance, compressive strength and compression set were measured, respectively.
なお、圧縮強度及び圧縮永久歪率は、発泡体の柔軟性を
示し得るものであり、圧縮強度においてはその数値が小
さいものほど柔軟でかつ弾性体であり、また圧縮永久歪
率においてもその数値が小さいものほど柔軟である。The compressive strength and compression set rate can indicate the flexibility of the foam, and the smaller the value of the compressive strength, the more flexible and elastic the material is. The smaller the value, the more flexible it is.
なお、上記圧縮強度及び圧縮永久歪率の測定は、各実施
例及び比較例において発泡シートを重ね合わせ、厚さ１
５ｍｍの発泡体としたものに対して行った。In addition, in each example and comparative example, the compression strength and compression set rate were measured by overlapping the foam sheets to a thickness of 1
The test was carried out on a 5 mm foam.
結果を第１表にあわせて示す。The results are also shown in Table 1.
（ＤＪＩＳ Ｋ６７６７ により測定した値であり、長
平方向（ＭＯ） ／幅方向（ＴＤ）の値を示す。(This is a value measured by DJIS K6767, and shows the value in the longitudinal direction (MO)/width direction (TD).
（２）ＪＩＳ Ｋ６７６７ により測定した値であり、
長手方向（ＭＯ） ／幅方向（ＴＯ）の値を示す。(2) Values measured according to JIS K6767,
Indicates the value in the longitudinal direction (MO)/width direction (TO).
（３）ＪＩＳ Ｋ６７６７ により測定した値であり、
長手方向（ＭＯ）／幅方向（ＴＯ）の値を示す。(3) Values measured according to JIS K6767,
Indicates the value in the longitudinal direction (MO)/width direction (TO).
（４）９０℃で、２２時間放置した後の長手方向（ＭＯ
）／幅方向（ＴＯ）の収縮率（％）を示す。(4) Longitudinal direction (MO
)/Shrinkage percentage (%) in the width direction (TO).
（５）ＪＩＳ Ｋ６７６７ により測定した値である。(5) Value measured according to JIS K6767.
（６）ＪＩＳ Ｋ６７６７ により測定した値であり、
次式による圧縮永久歪率（％）を示す。(6) Values measured according to JIS K6767,
The compression set rate (%) is shown by the following formula.
以上の結果から、各実施例の高密度ポリエチレン架橋発
泡シートの圧縮強度及び圧縮永久歪率の値は、十分に小
さく、本発明の発泡体が良好な柔軟性を有することがわ
かる。From the above results, it can be seen that the values of compressive strength and compression set rate of the high-density polyethylene crosslinked foam sheets of each example are sufficiently small, and the foam of the present invention has good flexibility.
また本発明の高密度ポリエチレン架橋発泡体は、高密度
ポリエチレンをベースとしているにもかかわらず、原反
シートの成形性が良好である。Further, the high-density polyethylene crosslinked foam of the present invention has good moldability into a raw sheet, although it is based on high-density polyethylene.
さらに、本発明の組成物によるポリプロピレン架橋発泡
シートは、高密度ポリエチレン１００ 重量％を樹脂成
分とする比較例１のシートと比べて、長手方向くＭＯ）
と幅方向（ＴＯ＞での各種物性の差が小さく、異方性が
低下していることがわかる。Furthermore, the polypropylene crosslinked foam sheet made of the composition of the present invention has a higher MO in the longitudinal direction than the sheet of Comparative Example 1 whose resin component is 100% by weight of high-density polyethylene.
It can be seen that the differences in various physical properties in the width direction (TO>) are small, and the anisotropy is reduced.
以上の実施例において、本発明の発泡体をシートに底形
した場合について説明したが、本発明の発泡体はこれに
限定されることなく、種々の形状とすることができる。In the above embodiments, the case where the foam of the present invention is formed into a sheet with a bottom shape has been described, but the foam of the present invention is not limited to this and can be made into various shapes.
以上詳述した通り、本発明の高密度ポリエチレン架橋発
泡体は、高密度ポリエチレンにポリブテン−１と発泡剤
とを配合しているので、得られる高密度ポリエチレン架
橋発泡体は、強度、耐熱性及び柔軟性を有し、さらに異
方性が低下している。As detailed above, the high-density polyethylene cross-linked foam of the present invention contains polybutene-1 and a blowing agent in high-density polyethylene, so the resulting high-density polyethylene cross-linked foam has excellent strength, heat resistance and It has flexibility and also has reduced anisotropy.
また本発明の発泡体の組成物は、成形加工性に優れてい
る。Furthermore, the foam composition of the present invention has excellent moldability.
出 願 人 東燃石油化学株式会社Applicant: Tonen Petrochemical Co., Ltd.
Claims (2)
テン−１５〜８０重量％と、前記高密度ポリエチレン＋
ポリブテン−１の合計１００重量部に対して３〜３０重
量部の発泡剤とを含有する組成物からなることを特徴と
する高密度ポリエチレン架橋発泡体。(1) 20-95% by weight of high-density polyethylene, 15-80% by weight of polybutene, and the above-mentioned high-density polyethylene +
A high-density polyethylene crosslinked foam characterized by comprising a composition containing 3 to 30 parts by weight of a blowing agent based on a total of 100 parts by weight of polybutene-1.
テン−１５〜７０重量％と、低密度ポリエチレン５〜６
０重量％と、前記高密度ポリエチレン＋ポリブテン−１
＋低密度ポリエチレンの合計１００重量部に対して３〜
３０重量部の発泡剤とを含有する組成物からなることを
特徴とする高密度ポリエチレン架橋発泡体。(2) 20-80% by weight of high-density polyethylene, 15-70% by weight of polybutene, and 5-6% by weight of low-density polyethylene
0% by weight and the high density polyethylene + polybutene-1
+ 3 to 100 parts by weight of low density polyethylene
A high-density polyethylene crosslinked foam characterized by comprising a composition containing 30 parts by weight of a blowing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28077089A JPH03143932A (en) | 1989-10-27 | 1989-10-27 | Crosslinked high-density polyethylene foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28077089A JPH03143932A (en) | 1989-10-27 | 1989-10-27 | Crosslinked high-density polyethylene foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03143932A true JPH03143932A (en) | 1991-06-19 |
Family
ID=17629720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28077089A Pending JPH03143932A (en) | 1989-10-27 | 1989-10-27 | Crosslinked high-density polyethylene foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03143932A (en) |
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|---|---|---|---|---|
| JP2017066404A (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| WO2017057628A1 (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| JP2017066403A (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| CN112778621A (en) * | 2020-12-31 | 2021-05-11 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
-
1989
- 1989-10-27 JP JP28077089A patent/JPH03143932A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017066404A (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| WO2017057628A1 (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| JP2017066403A (en) * | 2015-09-29 | 2017-04-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| EP3357958A4 (en) * | 2015-09-29 | 2019-04-24 | Sekisui Chemical Co., Ltd. | Polyolefin resin foamed sheet and adhesive tape |
| JP2019070156A (en) * | 2015-09-29 | 2019-05-09 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| JP2019085576A (en) * | 2015-09-29 | 2019-06-06 | 積水化学工業株式会社 | Polyolefin resin foamed sheet and adhesive tape |
| US11352525B2 (en) | 2015-09-29 | 2022-06-07 | Sekisui Chemical Co., Ltd. | Polyolefin resin foamed sheet and adhesive tape |
| CN112778621A (en) * | 2020-12-31 | 2021-05-11 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
| CN112778621B (en) * | 2020-12-31 | 2023-01-10 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
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