JPH03124743A - Preparation of crosslinked polyolefin resin foam - Google Patents
Preparation of crosslinked polyolefin resin foamInfo
- Publication number
- JPH03124743A JPH03124743A JP1262508A JP26250889A JPH03124743A JP H03124743 A JPH03124743 A JP H03124743A JP 1262508 A JP1262508 A JP 1262508A JP 26250889 A JP26250889 A JP 26250889A JP H03124743 A JPH03124743 A JP H03124743A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- sheet
- polyolefin resin
- ethylene
- 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
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 41
- 239000006260 foam Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 24
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- 229920001897 terpolymer Polymers 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 229920005604 random copolymer Polymers 0.000 claims abstract description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 10
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 9
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 9
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 238000005187 foaming Methods 0.000 claims abstract description 7
- 239000004743 Polypropylene Substances 0.000 claims abstract description 6
- 229920001155 polypropylene Polymers 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 230000004580 weight loss Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 239000004604 Blowing Agent Substances 0.000 claims description 14
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000002411 thermogravimetry Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 16
- 239000005060 rubber Substances 0.000 abstract description 16
- 238000004132 cross linking Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 10
- 230000006378 damage Effects 0.000 description 9
- 238000000748 compression moulding Methods 0.000 description 8
- 238000007666 vacuum forming Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007652 sheet-forming process Methods 0.000 description 2
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-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
- 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000002985 plastic film Substances 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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〕
本発明は耐熱性、成形性、ゴム弾性に優れ、且つ均一微
細な気泡構造を有し、その表面に凹凸が少なく、表皮材
との貼合せ、接着、接合が容易で複合材として好適に使
用され、また基材（プラスチック成形品等）との接合が
前処理なしで真空成形、圧縮成形時に可能な架橋ポリオ
レフィン系樹脂発泡体の製造方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention has excellent heat resistance, moldability, and rubber elasticity, has a uniform fine cell structure, has few irregularities on its surface, and is suitable for adhesion to skin materials. A method for producing a crosslinked polyolefin resin foam that is easy to fit, adhere, and join, and is suitable for use as a composite material, and can be bonded to a base material (plastic molded product, etc.) during vacuum forming or compression molding without pretreatment. Regarding.
従来、各種のポリオレフィン系樹脂からなる発泡体が工
業的に広く製造販売され、真空成形や圧縮成形などによ
り、各種の形態を付与した製品として種々の用途に使用
されている。このものは、ポリ塩化ビニルかポリオレフ
ィン系などのプラスチックシートや布帛などの表皮材と
熱融着したり、接着剤などにより貼合せた複合材の形で
使用されることが多い。Conventionally, foams made of various polyolefin resins have been widely produced and sold industrially, and are used for various purposes as products given various shapes by vacuum molding, compression molding, etc. This material is often used in the form of a composite material that is heat-sealed to a skin material such as a plastic sheet or cloth made of polyvinyl chloride or polyolefin, or bonded with an adhesive.
しかしながら、これらの発泡体の中で架橋を行った後に
発泡することにより得られたポリオレフィン系樹脂発泡
体は、その表面に凹凸が発生するため前記表皮材との接
着、接合が困難になり、また成形性が不充分になったり
する。そのため、成形中又は成形製品とした後に発泡体
と表皮材とが剥離したり、破壊したりするという実用上
の問題があった。However, polyolefin resin foams obtained by crosslinking and then foaming these foams have irregularities on their surfaces, which makes adhesion and bonding with the skin material difficult, and Moldability may become insufficient. Therefore, there is a practical problem that the foam and the skin material may peel off or break during molding or after forming into a molded product.
また、これら発泡体はゴム弾性に劣り、剛性が強いため
接触した場合硬い感覚を有し、発泡倍率を大きくすると
強度が弱くなる。このため体育マット或いは人工芝の基
材の如く繰り返し圧縮が必要とされたり或いは柔らかい
感触が要求される用途には適用し難いものであった。In addition, these foams have poor rubber elasticity and high rigidity, so they feel hard when contacted, and as the expansion ratio increases, the strength becomes weaker. For this reason, it has been difficult to apply it to applications where repeated compression is required or a soft feel is required, such as sports mats or artificial turf base materials.
また、ポリプロピレン系樹脂発泡体は、プラスチック成
形品等と真空成形又は圧縮成形等により複合体を作成す
る際、発泡体に接着剤処理等の処理を必要とし、作業性
及び作業環境上の問題がある。In addition, when polypropylene resin foam is made into a composite with a plastic molded product by vacuum forming or compression molding, the foam needs to be treated with an adhesive, which poses problems in terms of workability and working environment. be.
これらの問題の改善方法として、特開昭６４１４２５３
号公報に示されるように、直鎖状ポリエチレン８０〜４
０重量％、エチレンプロピレンゴム２０〜６０重量％、
熱可塑性ポリエステル樹脂１〜１０重量％からなる樹脂
組成物に発泡剤、架橋剤を混和、成形した後、加熱して
架橋発泡させることにより、ゴム弾性に優れ且つ微細な
気泡を有する架橋プラスチック発泡体の製造方法がある
。また、特開昭６４−１７４０号公報に示されるように
、エチレン樹脂として０．９１０ ｇ／ｃｎ以下の密度
を有する超低密度ポリエチレンもしくはこれに他のオレ
フィン系樹脂を配合したものを用いることにより、極め
て柔軟性に冨み、また引張強度が向上した架橋発泡体を
得る方法がある。As a method to improve these problems, Japanese Patent Application Laid-Open No. 6414253
As shown in the publication, linear polyethylene 80-4
0% by weight, 20-60% by weight of ethylene propylene rubber,
A crosslinked plastic foam with excellent rubber elasticity and fine bubbles is produced by mixing a foaming agent and a crosslinking agent with a resin composition consisting of 1 to 10% by weight of a thermoplastic polyester resin, molding the mixture, and then heating it to crosslink and foam it. There is a manufacturing method. Furthermore, as shown in JP-A-64-1740, by using ultra-low density polyethylene having a density of 0.910 g/cn or less as the ethylene resin or a mixture thereof with other olefin resins, There is a method of obtaining a crosslinked foam having extremely high flexibility and improved tensile strength.
特開昭６４−１４２５３号公報に示される方法は直鎖状
低密度ポリエチレン樹脂、エチレンプロピレンゴム及び
熱可塑性ポリエステル樹脂を用いることによってゴム弾
性を有し気泡が微細な発泡体が得られるが直鎖状低密度
ポリエチレン樹脂を用いるため耐熱性に問題があり、耐
熱性が要求される分野、例えば自動車用内装材（ドアト
リム、インストルメントパネル等）としては使用できな
いという問題がある。The method disclosed in JP-A No. 64-14253 uses linear low-density polyethylene resin, ethylene propylene rubber, and thermoplastic polyester resin to obtain a foam with rubber elasticity and fine cells. Since it uses low-density polyethylene resin, there is a problem with heat resistance, and there is a problem that it cannot be used in fields that require heat resistance, such as automobile interior materials (door trims, instrument panels, etc.).
また、特開昭６４−１７４０号公報に示される方法はエ
チレン系樹脂が０．９１０ ｇ／ｃｉ以下の密度を有す
る超低密度ポリエチレンもしくはこれに他のオレフィン
系樹脂を配合したものであるが、ポリエチレン樹脂を主
体とし、さらに柔軟性を付与するためにエチレン−酢酸
ビニル共重合体を配合したものであるため耐熱性に問題
があり、耐熱性を要求される用途には使用できないとい
う問題がある。更に両方法ともプラスチック成形品等の
基材と真空成形又は圧縮成形等により複合体を作成する
際、発泡体に接着剤処理等の処理が必要であり作業性及
び作業環境上の問題がある。Furthermore, in the method shown in JP-A-64-1740, the ethylene resin is ultra-low density polyethylene having a density of 0.910 g/ci or less, or it is blended with other olefin resins. Since it is mainly made of polyethylene resin and contains an ethylene-vinyl acetate copolymer to give it flexibility, it has problems with heat resistance and cannot be used in applications that require heat resistance. . Furthermore, both methods require processing such as adhesive treatment on the foam when forming a composite with a base material such as a plastic molded product by vacuum forming or compression molding, which poses problems in terms of workability and working environment.
本発明の目的は耐熱性、成形性、ゴム弾性に優れ、且つ
均一微細な気泡構造を有し、その表面に凹凸が少なく、
表皮材との貼合せ、接着、接合が容易であり、また基材
（プラスチック成形品等）との接合が前処理なしで真空
成形、圧縮成形時に可能な架橋ポリレフイン樹脂発泡体
の製造方法を提供するものである。The object of the present invention is to have excellent heat resistance, moldability, and rubber elasticity, and to have a uniform and fine cell structure, with little unevenness on the surface.
Provides a method for producing a crosslinked polyrefin resin foam that can be easily laminated, adhered, and bonded to a skin material, and that can be bonded to a base material (plastic molded product, etc.) during vacuum molding or compression molding without pretreatment. It is something to do.
このような目的は、プロピレンランダム共重合体、プロ
ピレンブロック共重合体にエチレンプロピレンゴム及び
エチレン・アクリル酸エステル・無水マレイン酸三元共
重合体を配合し、次いで有機過酸化物及び有機シランを
配合してシリル変成ポリオレフィン樹脂を形成した後、
シリル変成ポリオレフィン系樹脂に発泡剤を配合し成形
シートを作成し、架橋発泡せしめることによって達成す
ることができる。For this purpose, propylene random copolymer or propylene block copolymer is blended with ethylene propylene rubber and ethylene/acrylic acid ester/maleic anhydride terpolymer, and then organic peroxide and organic silane are blended. After forming a silyl-modified polyolefin resin,
This can be achieved by blending a foaming agent with a silyl-modified polyolefin resin, creating a molded sheet, and crosslinking and foaming it.
本発明の架橋ポリオレフィン系樹脂発泡体の製造方法に
使用する樹脂は、０．１〜１５重量部％のエチレン単位
を含有するプロピレンランダム共重合体１００〜２０重
量部、好ましくは８０．〜４０重量部、０．１〜１５重
量％のエチレン単位を含有するプロピレンブロック共重
合体０〜８０重量部、好ましくは２０〜６０重量部を配
合したポリプロピレン樹脂９０〜４０重量部に対し、エ
チレン・プロピレンゴム５〜４０重量部、エチレン・ア
クリル酸エステル・無水マレイン酸三元共重合体を５〜
２０重量部を添加した配合樹脂組成物を用いる。ここで
０．１〜１５重量％のエチレン単位を含有するプロピレ
ンランダム共重合体、プロピレンブロック共重合体を使
用するのは、ホモプロピレン樹脂はＤＳＣ法でｔ、が１
６３ ”Ｃと高いため、押出機でシート作成時アゾジカ
ルボンアミド等の発泡剤が初期分解を起こすのでエチレ
ン単位を含有するプロピレンランダム共重合体、プロピ
レンブロック共重合体を使用することによりｔ、を低下
させ、シート成形時に発泡剤の初期分解を防止するため
である。また、プロピレンブロック共重合体の配合量が
８０重量部を超えると押出温度を高くせねばならず発泡
剤が分解するため押出しが不安定になる。The resin used in the method for producing a crosslinked polyolefin resin foam of the present invention is a propylene random copolymer containing 0.1 to 15 parts by weight of ethylene units, preferably 100 to 20 parts by weight, preferably 80. ~40 parts by weight, 90 to 40 parts by weight of a polypropylene resin blended with 0 to 80 parts by weight, preferably 20 to 60 parts by weight, of a propylene block copolymer containing 0.1 to 15% by weight of ethylene units,・5 to 40 parts by weight of propylene rubber, 5 to 40 parts by weight of ethylene/acrylic acid ester/maleic anhydride terpolymer
A blended resin composition containing 20 parts by weight is used. The propylene random copolymer and propylene block copolymer containing 0.1 to 15% by weight of ethylene units are used here because the homopropylene resin has a t value of 1 according to the DSC method.
63"C, foaming agents such as azodicarbonamide cause initial decomposition during sheet production using an extruder. Therefore, by using propylene random copolymers and propylene block copolymers containing ethylene units, T. This is to prevent the initial decomposition of the blowing agent during sheet molding.Also, if the amount of propylene block copolymer blended exceeds 80 parts by weight, the extrusion temperature must be raised and the blowing agent will decompose, making extrusion difficult. becomes unstable.
本発明においてエチレンプロピレンゴムを配合する理由
は発泡体としてのゴム弾性、柔軟性を付与するとともに
耐熱性の低下を防止するためである。さらにエチレン・
アクリル酸エステル・無水マレイン酸三元共重合体を配
合する理由は発泡体としてのゴム弾性、柔軟性を付与す
ると共に配合樹脂の相溶性を向上させるとともに発泡後
の発泡品と基材（プラスチック成形品等）との接合が前
処理なしで真空成形、圧縮成形時に可能にするためであ
る。配合部数をエチレン・プロピレンゴム５〜４０重量
部、エチレン・アクリル酸エステル・無水マレイン酸三
元共重合体を５〜２０重量部とし、さらに両者の配合部
数の合計がポリプロピレン樹脂配合物９０〜４０重量部
に対して１０〜６０重量部配合する。The reason why ethylene propylene rubber is blended in the present invention is to impart rubber elasticity and flexibility as a foam and to prevent a decrease in heat resistance. In addition, ethylene
The reason for blending the acrylic acid ester/maleic anhydride terpolymer is that it gives the foam rubber elasticity and flexibility, improves the compatibility of the blended resin, and improves the compatibility between the foamed product and the base material (plastic molding) after foaming. This is to enable bonding with products (such as products, etc.) during vacuum forming or compression molding without pretreatment. The blended parts are 5 to 40 parts by weight of ethylene/propylene rubber, 5 to 20 parts by weight of the ethylene/acrylic acid ester/maleic anhydride terpolymer, and the total number of blended parts of both is 90 to 40 parts by weight of the polypropylene resin blend. It is blended in 10 to 60 parts by weight.
ここでエチレン・プロピレンゴム及びエチレン・アクリ
ル酸エステル・無水マレイン酸三元共重合体の両者の配
合部数の合計を１０〜６０重量部と限定したのは、１０
重量部未満では柔軟性の効果が少なく、６０重量部を超
えるとシート成形性、耐熱性、発泡性等に問題があるか
らである。またエチレン・アクリル酸エステル・無水マ
レイン酸三元共重合体を５〜２０重量部としたのはエチ
レン・プロピレンゴムを多量に前記ポリプロピレン樹脂
に配合すると相溶性に問題が発生するがエチレン・アク
リル酸エステル・無水マレイン酸三元共重合体を併用す
ることにより相溶性が改善できること及び基材（プラス
チック成形品等）との接合が前処理なしで真空成形、圧
縮成形時に可能になるからである。Here, the total number of blended parts of both the ethylene/propylene rubber and the ethylene/acrylic acid ester/maleic anhydride terpolymer was limited to 10 to 60 parts by weight.
This is because if it is less than 60 parts by weight, the flexibility effect will be small, and if it exceeds 60 parts by weight, there will be problems with sheet formability, heat resistance, foamability, etc. Also, the reason why the terpolymer of ethylene/acrylic acid ester/maleic anhydride is 5 to 20 parts by weight is because if a large amount of ethylene/propylene rubber is blended into the polypropylene resin, problems will occur in compatibility, but ethylene/acrylic acid This is because by using the ester/maleic anhydride terpolymer together, compatibility can be improved and bonding with a base material (plastic molded product, etc.) can be performed during vacuum forming or compression molding without pretreatment.
エチレン・プロピレンゴムとしてはＥＰＰＬＬして各社
から市販されており、例えば住友化学「ニスプレン」が
好適に用いられる。また、エチレン・アクリル酸エステ
ル・無水マレイン酸共重合体としては住友化学から「ボ
ンダインＪの商品名で販売されているものが好適に用い
られる。Ethylene-propylene rubber is commercially available as EPPLL from various companies, and for example, Sumitomo Chemical's "Nisprene" is preferably used. Furthermore, as the ethylene/acrylic acid ester/maleic anhydride copolymer, one sold under the trade name "Bondine J" by Sumitomo Chemical is suitably used.
プロピレンランダム共重合体、プロピレンブロック共重
合体、エチレン・プロピレンゴム、エチレン・アクリル
酸エステル・無水マレイン酸三元共重合体からなる配合
樹脂にベンゾイルパーオキサイド、ジクミルパーオキサ
イド、ターシャリブチルパーオキサイド、ジターシャリ
ブチルパーオキサイド、ジ−ターシャリブチルパーオキ
シイソフタレート等の有機過酸化物とビニルトリメトキ
シシラン、ビニルトリエトキシシラン等の有機シラン化
合物とを過酸化物１００重量部に対して有機シラン化合
物が１００〜７００重量部になるような割合で上記配合
樹脂１００重量部に対し０．５〜５重量部、好ましくは
０．７〜２．０重量部配合する。また、シリル変成ポリ
オレフィン樹脂形成時の高温時での酸化劣化を防止する
とともに後工程での熱劣化防止のため、必要に応じ、テ
トラキス〔メチレン（３，５−ジーＬ−ブチルー４−ヒ
ドロキシハイドロシンナメート〕メタン、１，３゜５−
トリス（３，５−ジーも一ブチルー４−ヒドロキシベン
ジル）−８−トリアジン−２，４，６（ＬＨ，３Ｈ，５
Ｈ）−トリオン、１，１．３トリス（２−メチル−４−
ヒドロキシ−５−を−ブチルフェニル）ブタン等の酸化
防止剤を上記ポリオレフィン樹脂配合物１００重量部に
対し０．１〜０．６重量部配合してもよい。Compounded resin consisting of propylene random copolymer, propylene block copolymer, ethylene/propylene rubber, ethylene/acrylic acid ester/maleic anhydride ternary copolymer, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxide. , di-tert-butyl peroxide, di-tert-butyl peroxyisophthalate, and other organic peroxides, and vinyltrimethoxysilane, vinyltriethoxysilane, and other organic silane compounds per 100 parts by weight of peroxide. The compound is added in an amount of 0.5 to 5 parts by weight, preferably 0.7 to 2.0 parts by weight, per 100 parts by weight of the above-mentioned blended resin, in such a proportion that the compound becomes 100 to 700 parts by weight. In addition, in order to prevent oxidative deterioration at high temperatures during the formation of the silyl-modified polyolefin resin, and to prevent thermal deterioration in the subsequent process, tetrakis [methylene (3,5-di-L-butyl-4-hydroxyhydrosynthene]) is added as necessary. mate] methane, 1,3゜5-
Tris(3,5-di-butyl-4-hydroxybenzyl)-8-triazine-2,4,6(LH,3H,5
H)-trione, 1,1.3 tris(2-methyl-4-
An antioxidant such as hydroxy-5-butylphenyl)butane may be added in an amount of 0.1 to 0.6 parts by weight per 100 parts by weight of the polyolefin resin composition.
プロピレンランダム共重合体、プロピレンブロック共重
合体、エチレン・プロピレンゴム、エチレン・アクリル
酸エステル・無水マレイン酸三元共重合体からなる配合
樹脂と有機シラン化合物とを有機過酸化物の如き遊離基
発生剤の存在下で反応せしめることによって容易にシリ
ル変成ポリオレフィン樹脂になる。本発明の製造方法に
おいては、このようなシリル変成ポリオレフィン樹脂に
対し、発泡剤として熱重量分析（ＴＧＡ）法で測定され
る減量開始温度が１６０℃以上であり、減量率１％に達
する温度が１８０℃以上であり、１６５゛Ｃにおける減
量率１％に達する時間が８分以上である熱分解性能を有
するアゾジカルボンアミドを発泡剤として配合し、得ら
れた配合物を成形してシートを形成する。シート成形特
番こ押出機の温度条件、機内における樹脂混合物の滞留
時間等を調整して、シートのみかけ密度が０．９０ ｇ
／ ｃａ以上になるように調整する点に大きな特徴が
ある。Compound resins consisting of propylene random copolymer, propylene block copolymer, ethylene/propylene rubber, ethylene/acrylic acid ester/maleic anhydride ternary copolymer and organic silane compound are combined to generate free radicals such as organic peroxide. A silyl-modified polyolefin resin can be easily obtained by reacting in the presence of a silyl-modified polyolefin resin. In the production method of the present invention, the silyl-modified polyolefin resin used as a blowing agent has a weight loss initiation temperature of 160°C or higher as measured by thermogravimetric analysis (TGA), and a temperature at which a weight loss rate of 1% is reached. Azodicarbonamide, which has thermal decomposition performance at 180°C or higher and takes 8 minutes or more to reach a weight loss rate of 1% at 165°C, is blended as a foaming agent, and the resulting mixture is molded to form a sheet. do. By adjusting the temperature conditions of the extruder, the residence time of the resin mixture inside the machine, etc., the apparent density of the sheet was 0.90 g.
The major feature is that it is adjusted to be equal to or higher than /ca.
シートのみかけ密度が０．９０ ｇ ／ｃｎ１未満では
得られた発泡体の気泡構造が粗大のものと微細なものと
が混在するものとなり、断面気泡数もバラツキが大きく
１０〜５０個／ ｃｍとなり、外観も悪いものとなる。If the apparent density of the sheet is less than 0.90 g/cn1, the cell structure of the obtained foam will be a mixture of coarse and fine cells, and the number of cross-sectional cells will vary widely, ranging from 10 to 50 cells/cm. , the appearance is also bad.
さらにシートのみかけ密度が０．８５ｇ／ｃｉ以下とな
ると、シート成形時の発泡度が大きくなり、成形シート
の外観が悪化するとともに得られた発泡体の気泡構造が
より粗大化する傾向がある。且つシート成形工程のロン
グラン性の面からシートみかけ密度の影響が大きく、シ
ート成形工程のロングラン性が低下し、製造効率の面で
も問題が発生する。Further, if the apparent density of the sheet is 0.85 g/ci or less, the degree of foaming during sheet molding increases, the appearance of the molded sheet deteriorates, and the cell structure of the resulting foam tends to become coarser. In addition, the apparent density of the sheet has a large influence on the long-run performance of the sheet forming process, reducing the long-run performance of the sheet forming process and causing problems in terms of manufacturing efficiency.
これらの点からも本発明に用いる発泡剤はできるだけ分
解開始温度及び減量率１％に達する温度が高温である発
泡剤が、均一気泡微細化、押出工程のロングラン性の製
造効率及び押出条件の安定性の面から非常に有利である
。なお、本発明においては発泡剤として、熱重量分析（
ＴＧＡ）法で測定される減量開始温度が１６０℃以上で
あり、減量率１％に達する温度が１８０℃以上であり、
１６５℃における減量率１％に達する時間が８分以上で
ある熱分解性能を有するアゾジカルボンアミドを用いる
ことを必須とするものであるが、成形シートのみかけ密
度が０．９０ ｇ ／ｃ１以上になるような条件であれ
ば、これより低温度で分解する発泡剤を上記発泡剤に対
し１０重量％未満の範囲内で使用することができる。From these points of view, it is recommended that the blowing agent used in the present invention has a high decomposition start temperature and a temperature at which the weight loss rate reaches 1% as high as possible to achieve uniform cell refinement, long-run production efficiency in the extrusion process, and stability of extrusion conditions. Very advantageous from a sexual standpoint. In addition, in the present invention, thermogravimetric analysis (
The weight loss starting temperature measured by the TGA) method is 160°C or higher, and the temperature at which the weight loss rate reaches 1% is 180°C or higher,
It is essential to use azodicarbonamide with thermal decomposition performance that takes 8 minutes or more to reach a weight loss rate of 1% at 165°C, but if the apparent density of the molded sheet is 0.90 g / c1 or more. Under such conditions, a blowing agent that decomposes at a lower temperature can be used in an amount of less than 10% by weight based on the blowing agent.
また、このようなアゾジカルボンアミドの前記シリル変
性ポリオレフィン樹脂に対する配合量は通常１〜３０重
量％の範囲、好ましくは５〜２５重量％の範囲である。Further, the amount of such azodicarbonamide blended in the silyl-modified polyolefin resin is usually in the range of 1 to 30% by weight, preferably in the range of 5 to 25% by weight.
前記シリル変成ポリオレフィン樹脂、発泡剤は混合機で
充分に混和する。次いで混合物を押出機に投入し、成形
シートのみかけ密度が０．９０ｇ／−以上の成形シート
とする。これらの工程において水分や湿気ができるだけ
介在しないように注意する。これはシリル変成ポリオレ
フィン樹脂に架橋結合が生じないようにするためである
。押出機のシリンダー温度等の条件は発泡剤の分解温度
、剪断による樹脂の内部発熱の程度、押出速度、押出機
内における樹脂の滞留時間などを考慮して調節され゛る
が、要点は押出成形シートのみかけ密度が０．９０ ｇ
／ｃｆｆ１以上に保つことである。The silyl-modified polyolefin resin and the blowing agent are thoroughly mixed in a mixer. Next, the mixture is put into an extruder to form a molded sheet having an apparent density of 0.90 g/- or more. Care should be taken to avoid moisture or moisture from entering into these processes as much as possible. This is to prevent crosslinking from occurring in the silyl-modified polyolefin resin. Conditions such as the cylinder temperature of the extruder are adjusted by considering the decomposition temperature of the blowing agent, the degree of internal heat generation of the resin due to shearing, the extrusion speed, and the residence time of the resin in the extruder, but the main point is that the extrusion molded sheet Apparent density is 0.90 g
/cff1 or higher.
次に成形シートに架橋構造を導入する。Next, a crosslinked structure is introduced into the formed sheet.
シリル変成ポリオレフィン樹脂の成形シートへの架橋構
造の導入は、シリル変成ポリオレフィン樹脂の軟化温度
以下で水分の存在下で実施する。The introduction of the crosslinked structure into the molded sheet of the silyl-modified polyolefin resin is carried out in the presence of moisture at a temperature below the softening temperature of the silyl-modified polyolefin resin.
ここで処理温度を軟化温度以下と規定した理由は成形シ
ートの厚みの変化を防止し、発泡品の厚み精度を保つた
めである。The reason why the processing temperature is specified to be below the softening temperature is to prevent changes in the thickness of the molded sheet and maintain the thickness accuracy of the foamed product.
ここでいう水分の存在下における処理とは簡単には熱水
、温水、水蒸気などに直接ばくろするだけでよい。温度
は上記軟化温度を超えない範囲で、高い方が架橋速度が
大きく好都合である。The treatment in the presence of moisture simply involves direct exposure to hot water, hot water, steam, etc. The temperature is within a range that does not exceed the above-mentioned softening temperature, and the higher the temperature, the higher the crosslinking rate, which is advantageous.
本発明において好適な架橋度は３０〜８０％、好ましく
は４０〜７０％である。架橋度がこれより大きいときに
は樹脂が発泡成長時の伸びに追随できずに割れることが
あり好ましくない。ここで架橋度とは沸騰キシレン（１
４０”Ｃ）中、８時間の抽出残渣の供試試料に対する重
量分率で示した値をいう。A suitable degree of crosslinking in the present invention is 30 to 80%, preferably 40 to 70%. If the degree of crosslinking is greater than this, the resin may not be able to follow the elongation during foam growth and may crack, which is not preferable. Here, the degree of crosslinking refers to boiling xylene (1
40"C) for 8 hours, expressed as a weight fraction of the extraction residue relative to the test sample.
このように架橋したポリオレフィン樹脂成形物は次いで
常圧下で加熱して未分解の発泡剤を完全に分解し、高発
泡体とする。その結果として気泡数の多い、すなわち均
一分散した微細気泡発泡体を安定に得ることができる。The thus crosslinked polyolefin resin molded product is then heated under normal pressure to completely decompose the undecomposed foaming agent and form a highly foamed product. As a result, a fine cell foam with a large number of cells, that is, uniformly dispersed cells, can be stably obtained.
加熱方法としては赤外線、電熱器などの輻射を用いる方
法の他、熱風炉、加熱液体温などによる方法などがある
。Heating methods include methods using radiation such as infrared rays and electric heaters, as well as methods using hot air ovens, heating liquid temperature, and the like.
なお、本発明の目的を損なわない範囲においてシリル変
性ポリオレフィン樹脂には、着色剤、難燃剤、架橋促進
剤その他の各種添加剤を配合することができる。In addition, a coloring agent, a flame retardant, a crosslinking accelerator, and other various additives can be blended with the silyl-modified polyolefin resin within a range that does not impair the purpose of the present invention.
以下実施例に基づき本発明を更に説明する。The present invention will be further explained below based on Examples.
実施例１〜１０
第１−１表に示すように、５重量％のエチレン単位を含
有するプロピレンランダム共重合体、６゜５重量％のエ
チレン単位を含有するプロピレンブロック共重合体、エ
チレン・プロピレンゴム（密度０．８８□ｇ／ｃｄ、Ｍ
１０．７１ｇ／１０分（ａ ｔ ２３０ ’Ｃ）住友化
学、ニスプレンＥ８０８） 、及びエチレン・アクリル
酸・無水マレイン酸三元共重合体（コモノマー含量３２
重量％、Ｍ １７． Ｏ１密度０．９５ｇ／ａｆｌ住友
化学、ボンダインＡＸ８３９０）の各配合について、ジ
ターシャリブチルパーオキサイド１００！量部に対しビ
ニルメトキシシラン２５０重量部の割合でブレンドした
ものを上記配合ポリオレフィン樹脂１００重量部に対し
て１．０重量部添加する。酸化防止剤として１，３゜５
−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベ
ンジル）−３−トリアジン−２，４，６（ＬＨ，３Ｈ，
５Ｈ）−）リオンをポリオレフィン樹脂１００重量部に
対し０．３重量部配合し、２軸押出機を用いてシリル変
性ポリオレフィン樹脂を形成した。得られたシリル変性
ポリオレフィン樹脂１００重量部に対し、発泡剤として
熱重量分析（ＴＧＡ）法で測定される減量開始温度が１
８０℃で、減量率１％に達する温度が２０７℃であり１
６５℃におけるＭｌ率１％に達する時間が約１３分であ
る熱分解特性を有するアゾジカルボンアミドを１３３重
量部配し、均一に混合した後、押出機を用いて、樹脂温
度が１６０〜１６５℃１機内の滞留時間が５〜６分程度
になるよう調整して成形シートを形成した。得られたシ
ートを温水を用いて架橋した後、２４０℃で発泡させ、
第１２表に示す物性を有する発泡体を得た。この発泡体
を表皮材として、ポリ塩化ビニルシートと貼り合わせ、
接着剤を用いて接合して貼り合わせシートを得た。この
貼り合わせシートを直径が５０鴎φ、深さが３０ｍｍの
金型を用いて真空成形し、底部の破壊（発泡体の破壊及
び接合面の界面剥Ｍ）状態を調べて比較した。その結果
を第１−３表に示した。Examples 1 to 10 As shown in Table 1-1, a propylene random copolymer containing 5% by weight of ethylene units, a propylene block copolymer containing 6.5% by weight of ethylene units, ethylene/propylene Rubber (density 0.88□g/cd, M
10.71 g/10 min (at 230'C) Sumitomo Chemical, Nisprene E808), and ethylene-acrylic acid-maleic anhydride terpolymer (comonomer content 32
Weight %, M 17. For each formulation of O1 density 0.95 g/afl Sumitomo Chemical, Bondine AX8390), ditertiary butyl peroxide 100! A blend of 250 parts by weight of vinylmethoxysilane is added to 1.0 parts by weight per 100 parts by weight of the blended polyolefin resin. 1.3゜5 as an antioxidant
-tris(3,5-di-t-butyl-4-hydroxybenzyl)-3-triazine-2,4,6(LH,3H,
0.3 parts by weight of 5H)-)ion was added to 100 parts by weight of the polyolefin resin, and a silyl-modified polyolefin resin was formed using a twin-screw extruder. For 100 parts by weight of the obtained silyl-modified polyolefin resin, the weight loss starting temperature measured by thermogravimetric analysis (TGA) as a blowing agent is 1.
At 80℃, the temperature at which the weight loss rate reaches 1% is 207℃, which is 1
After distributing 133 parts by weight of azodicarbonamide which has thermal decomposition properties that take about 13 minutes to reach an Ml ratio of 1% at 65°C and mixing uniformly, the resin temperature was increased to 160 to 165°C using an extruder. A molded sheet was formed by adjusting the residence time in one machine to about 5 to 6 minutes. After crosslinking the obtained sheet using hot water, it was foamed at 240°C,
A foam having the physical properties shown in Table 12 was obtained. This foam is used as a skin material and is bonded to a polyvinyl chloride sheet.
A bonded sheet was obtained by bonding using an adhesive. This laminated sheet was vacuum-formed using a mold with a diameter of 50 mm and a depth of 30 mm, and the state of destruction at the bottom (destruction of the foam and interfacial peeling of the joint surface) was examined and compared. The results are shown in Table 1-3.
実施例１１〜１日
５重量％のエチレン単位を含有するプロピレンランダム
共重合体４２重量部、６．５重量％のエチレン単位を含
有するプロピレン・ブロック共重合体２８を置部、エチ
レン・プロピレンゴム（密度０、８８ ｇ ／ｃｄ、Ｍ
ｌｏ、７１ｇ／１０分（ａｔ２３０℃）住友化学、ニス
ブレンＥ８０８）２０重量部及びエチレン・アクリル酸
・無水マレイン酸三元共重合体（コ壜ツマー含量３２重
量％、Ｍ Ｉ ７゜０、密度０．９５ｇ／ａｄ住友化学
、ボンダインＡＸ８３９０）１０重量部の配合に、ジタ
ーシャリブチルパーオキサイド、ビニルトリメトキシシ
ランを第２−１表に示す割合で添加し、酸化防止剤とし
て１．３．５−）リス（３，５−ジ−ｔ−ブチル−４−
ヒドロキシベンジル）−８−トリアジン−２，４，６（
１）（，３Ｈ，５Ｈ）−トリオンをポリオレフィン樹脂
混合物１００重量部に対して０．３重量部配合し、２軸
押出機を用いてシリル変成ポリオレフィン樹脂を形成し
た。得られたシリル変成ポリオレフィン樹脂１００重量
部に対し、実施例１〜１０で用いた発泡剤を第２−１表
に示す量を配合して混合した後、押出機を用いて、樹脂
温度が１６０〜１６５℃、機内の滞留時間が５〜６分程
度になるよう調整して成形シートを形成した。得られた
シートを温水を用いて架橋した後、２３０〜２４０℃で
発泡させ、第２−２表に示す物性を有する発泡体を得た
。この発泡体を表皮材として、ポリ塩化ビニルシートと
貼り合わせ、接着剤を用いて接合して貼り合わせシート
を得た。Example 11 - 42 parts by weight of a propylene random copolymer containing 5% by weight of ethylene units per day, 28 parts by weight of a propylene block copolymer containing 6.5% by weight of ethylene units, ethylene-propylene rubber (density 0, 88 g/cd, M
lo, 71 g/10 minutes (at 230°C) Sumitomo Chemical, Nisbrene E808) 20 parts by weight and ethylene/acrylic acid/maleic anhydride terpolymer (bottle content 32% by weight, M I 7°0, density 0) Ditert-butyl peroxide and vinyltrimethoxysilane were added in the proportions shown in Table 2-1 to 10 parts by weight of .95g/ad Sumitomo Chemical, Bondine AX8390) to form an antioxidant of 1.3.5- ) Lis(3,5-di-t-butyl-4-
hydroxybenzyl)-8-triazine-2,4,6(
1) 0.3 parts by weight of (,3H,5H)-trione was blended with 100 parts by weight of the polyolefin resin mixture, and a silyl-modified polyolefin resin was formed using a twin-screw extruder. 100 parts by weight of the obtained silyl-modified polyolefin resin was mixed with the blowing agent used in Examples 1 to 10 in the amount shown in Table 2-1. Using an extruder, the resin temperature was increased to 160%. A molded sheet was formed at ~165° C. and the residence time in the machine was adjusted to about 5 to 6 minutes. After crosslinking the obtained sheet using hot water, it was foamed at 230 to 240°C to obtain a foam having the physical properties shown in Table 2-2. This foam was used as a skin material and was bonded to a polyvinyl chloride sheet, and bonded using an adhesive to obtain a bonded sheet.
この貼り合わせシートを直径が５０ｍｍφ、深さが３０
ｍｍの金型を用いて真空成形し、底部の破壊（発泡体の
破壊及び接合面の剥Ｂ）状態を調べて比較した。その結
果を第２−３表に示した。This laminated sheet has a diameter of 50 mmφ and a depth of 30 mm.
Vacuum forming was performed using a mm mold, and the state of destruction at the bottom (destruction of the foam and peeling of the joint surface B) was examined and compared. The results are shown in Table 2-3.
比較例１〜１０
実施例１〜１０に示した各配合についてシリル変成ポリ
オレフィン樹脂１００重量部に対し、発泡剤として熱重
量分析（ＴＧＡ）法で測定される減量開始温度が１６５
℃で、減量１％に達する温度が１９５℃であり、１６５
℃における減量率１％に達する時間が約６分である熱分
解特性を有するアブジカルボンアミドを１３重量部配合
し、均一に混合した後、押出機を用いて、樹脂温度が１
６０〜１６５℃１機内の滞留時間が５〜６分程度になる
よう調整して成形シートを形成した。得られた成形シー
トを温水を用いて架橋した後２４０℃で発泡させた。第
３−１表にシリル変成ポリオレフィン樹脂の配合と成形
シートの密度を示し、第３−２表に発泡品の特性を示し
た。この発泡体を表皮材とちえ、ポリ塩化ビニルシート
と貼り合わせ、接着剤を用いて接合して貼り合わせシー
トを得た。この貼り合わせシートを直径が５０ｍｍφ、
深さが３０ｍｍの金型を用いて真空成形し、底部の破壊
（発泡体の破壊及び接合面の界面剥離）状態を調べて比
較した。その結果を第３−３表に示した。なお本発明比
較例において、シート成形特発泡剤の分解によりシート
成形品の密度が０．８０〜０．８５ｇ／ｃｔｌ？となり
、押出時のロングラン性も実施例に比較して大巾にダウ
ンする傾向があり作業性の面で問題である。Comparative Examples 1 to 10 For each formulation shown in Examples 1 to 10, the weight loss initiation temperature measured by thermogravimetric analysis (TGA) as a blowing agent was 165% for 100 parts by weight of the silyl-modified polyolefin resin.
℃, the temperature at which 1% weight loss is reached is 195℃, and 165℃.
13 parts by weight of abdicarbonamide, which has a thermal decomposition property that takes about 6 minutes to reach a weight loss rate of 1% at °C, is mixed uniformly, and then an extruder is used to increase the resin temperature to 1%.
A molded sheet was formed by adjusting the residence time in one machine at 60 to 165° C. to about 5 to 6 minutes. The obtained molded sheet was crosslinked using warm water and then foamed at 240°C. Table 3-1 shows the formulation of the silyl-modified polyolefin resin and the density of the molded sheet, and Table 3-2 shows the characteristics of the foamed product. This foam was used as a skin material, and it was bonded to a polyvinyl chloride sheet and bonded using an adhesive to obtain a bonded sheet. This laminated sheet has a diameter of 50mmφ,
Vacuum forming was performed using a mold with a depth of 30 mm, and the state of destruction at the bottom (destruction of the foam and interfacial peeling of the bonded surface) was examined and compared. The results are shown in Table 3-3. In addition, in the comparative example of the present invention, the density of the sheet molded product was 0.80 to 0.85 g/ctl due to decomposition of the special foaming agent for sheet molding. Therefore, the long run performance during extrusion also tends to be significantly lower than that of the examples, which is a problem in terms of workability.
第３−３表
比較例１１〜１５
第４−１表に示すように、５重量％のエチレン単位を含
有するプロピレンランダム共重合体、６゜５重量％のエ
チレン単位を含有するプロピレンブロック共重合体、エ
チレン・プロピレンゴム（密度０．８８ｇ／ｃ＋＋１．
Ｍ１０．７１ｇ／１０分（ａむ２３０℃））及びエチレ
ン・アクリル酸・無水マレイン酸三元共重合体（コモノ
マー含量３２重量％、Ｍ ｌ ７． Ｏ１密度０−９５
ｇ ／ｃ＋ｆｌ）の各配合について、ジターシャリブ
チルパーオキサイド１００重量部に対しビニルメトキシ
シラン２５０重世部の割合でブレンドしたものを上記配
合ポリオレフィン樹脂１００重量部に対して１，０重量
部添加する。酸化防止剤として１．−３．５−１−リス
（３，５−ジーむ−ブチルー４−ヒドロキシベンジル）
−Ｓ−トリアジン−２，４，６−（ＬＨ，３Ｈ，５Ｈ）
−トリオンをポリオレフィン樹脂配合物１００重量部に
対し、０．３重量部配合し、２軸押用機を用いてシリル
変成ポリオレフィン樹脂混合物を形成した。Table 3-3 Comparative Examples 11 to 15 As shown in Table 4-1, propylene random copolymer containing 5% by weight of ethylene units, propylene block copolymer containing 6.5% by weight of ethylene units. Combined, ethylene propylene rubber (density 0.88 g/c++1.
M10.71g/10min (am 230°C)) and ethylene-acrylic acid-maleic anhydride terpolymer (comonomer content 32% by weight, Ml 7.O1 density 0-95
For each formulation (g / c + fl), 1.0 parts by weight of a blend of 100 parts by weight of ditertiary butyl peroxide and 250 parts by weight of vinylmethoxysilane is added to 100 parts by weight of the above blended polyolefin resin. . As an antioxidant 1. -3.5-1-lis(3,5-dimu-butyl-4-hydroxybenzyl)
-S-triazine-2,4,6-(LH,3H,5H)
-0.3 parts by weight of trione was added to 100 parts by weight of the polyolefin resin mixture, and a silyl-modified polyolefin resin mixture was formed using a twin-screw extrusion machine.
得られたシリル変成ポリオレフィン樹脂１００重量部に
対し、発泡剤として熱重量分析（ＴＧＡ）法で測定され
る減量開始温度が１８０℃で、減量率１％に達する温度
が２０７℃であり、１６５℃における減量率１％に達す
る時間が約１３分である熱分解特性を有するアゾジカル
ボンアミドを１３重量部配合し、均一に混合した後、押
出機を用いて、樹脂温度が１６０〜１６５℃１機内の滞
留時間が５〜６分程度になるよう調整して成形シートを
形成した。得られたシートを温水を用いて架橋した後、
２４０℃で発泡させ、第４−２表に示す物性を有する発
泡体を得た。With respect to 100 parts by weight of the obtained silyl-modified polyolefin resin, the temperature at which weight loss starts as measured by thermogravimetric analysis (TGA) as a blowing agent is 180°C, the temperature at which the weight loss rate reaches 1% is 207°C, and 165°C. 13 parts by weight of azodicarbonamide, which has a thermal decomposition property that takes about 13 minutes to reach a weight loss rate of 1%, is mixed uniformly, and then an extruder is used to increase the resin temperature to 160-165℃ in one machine. A molded sheet was formed by adjusting the residence time of about 5 to 6 minutes. After crosslinking the obtained sheet using hot water,
It was foamed at 240°C to obtain a foam having the physical properties shown in Table 4-2.
尚、エチレンプロピレンゴム及びエチレン・アクリル酸
・無水マレイン酸三元共重合体の配合量の合計が６５重
量部以上になると発泡時にフクレ等が発生し、外観の良
好な成形品が得られなかった。この発泡体を表皮材とし
て、ポリ塩化ビニルシートと貼り合わせ、接着剤を用い
て接合して貼り合わせシートを得た。この貼り合わせシ
ートを直径が５０ｍｍφ、深さが３０＋ｎｍの金型を用
いて真空成形し、底部の破壊（発泡体の破壊及び接合面
の剥＃）状態を調べて比較した。その結果を第４３表に
示した。Furthermore, if the total amount of the ethylene propylene rubber and the ethylene/acrylic acid/maleic anhydride ternary copolymer exceeded 65 parts by weight, blistering occurred during foaming, and a molded product with a good appearance could not be obtained. . This foam was used as a skin material and was bonded to a polyvinyl chloride sheet, and bonded using an adhesive to obtain a bonded sheet. This laminated sheet was vacuum-formed using a mold with a diameter of 50 mm and a depth of 30+ nm, and the state of destruction at the bottom (destruction of the foam and peeling of the joint surface) was examined and compared. The results are shown in Table 43.
第２−３表
の口」Ｉコタ〕０＼り）く５゜
〔発明の効果〕
本発明により得られたポリオレフィン系樹脂発泡体は、
耐熱性、成形性、ゴム弾性に優れ、且つ均一微細な気泡
構造を有し、その表面に凹凸が極めて少なく、そのため
表皮材との接着、接合が容易で優れた成形性を示す。し
たがってその成形加工中及び成形によって得られた成形
製品における架橋発泡体と表皮材との剥離や破壊がなく
、実用性に優れたものである。更に基材（プラスチック
成形品等）との接着、接合が前処理なしで真空成形、圧
縮成形等において可能であり、大巾に生産性が向上する
。またシート成形時に発泡剤を一部分解させる必要がな
く、したがってロングラン性に優れ、製造面でも有効で
ある。したがって多くの用途において優れた成形性、品
質特性を有し、自動車の内装材（ドアパネル、インスト
ルメントパネル）、体育マット等柔らかい感触、ゴム弾
性を要求される用途など広く適用できる。[Effects of the Invention] The polyolefin resin foam obtained by the present invention has the following properties:
It has excellent heat resistance, moldability, and rubber elasticity, and has a uniform and fine cell structure, with extremely few irregularities on its surface, making it easy to adhere and bond with the skin material, and exhibits excellent moldability. Therefore, there is no peeling or destruction of the crosslinked foam and the skin material during the molding process or in the molded product obtained by the molding, and it is highly practical. Furthermore, adhesion and bonding with base materials (plastic molded products, etc.) can be performed by vacuum forming, compression molding, etc. without any pretreatment, and productivity is greatly improved. In addition, there is no need to partially decompose the blowing agent during sheet molding, so it has excellent long-run properties and is effective in terms of production. Therefore, it has excellent moldability and quality characteristics in many applications, and can be widely applied to applications that require a soft feel and rubber elasticity, such as automobile interior materials (door panels, instrument panels) and sports mats.
Claims (1)
ピレンランダム共重合体１００〜２０重量部、０．１〜
１５重量％のエチレン単位を含有するプロピレンブロッ
ク共重合体０〜８０重量部を配合したポリプロピレン樹
脂９０〜４０重量部に対し、エチレンプロピレンゴム５
〜４０重量部及びエチレン・アクリル酸エステル・無水
マレイン酸三元共重合体５〜２０重量部を配合し、次い
で有機過酸化物及び有機シラン化合物を配合し、必要に
応じて酸化防止剤を配合してシリル変成ポリオレフィン
樹脂を形成し、次いでシリル変成ポリオレフィン樹脂に
対し、熱重量分析（ＴＧＡ）法で測定される減量開始温
度が１６０℃以上であり、減量率１％に達する温度が１
８０℃以上であり、１６５℃における減量率１％に達す
る時間が８分以上である熱分解性能を有するアゾジカル
ボンアミドを発泡剤として配合し、得られた配合物をみ
かけ密度が０．９０ｇ／ｃｍ＾３以上になるように押出
成形してシートを形成し、このシートをシリル変成ポリ
オレフィン樹脂の軟化温度以下で水分の存在下で架橋し
た後、前記発泡剤の分解温度以上の温度に加熱して発泡
せしめることを特徴とする架橋ポリオレフィン系樹脂発
泡体の製造方法。1, 100-20 parts by weight of propylene random copolymer containing 0.1-15% by weight of ethylene units, 0.1-20 parts by weight
5 parts by weight of ethylene propylene rubber to 90 to 40 parts by weight of a polypropylene resin blended with 0 to 80 parts by weight of a propylene block copolymer containing 15% by weight of ethylene units.
~40 parts by weight and 5 to 20 parts by weight of ethylene/acrylic acid ester/maleic anhydride terpolymer are blended, then an organic peroxide and an organic silane compound are blended, and an antioxidant is blended if necessary. to form a silyl-modified polyolefin resin, and then the silyl-modified polyolefin resin has a weight loss initiation temperature of 160°C or higher measured by thermogravimetric analysis (TGA) and a temperature at which a weight loss rate of 1% is reached at 1%.
Azodicarbonamide, which has thermal decomposition performance at 80°C or higher and takes 8 minutes or more to reach a weight loss rate of 1% at 165°C, is blended as a foaming agent, and the resulting blend has an apparent density of 0.90g/ A sheet is formed by extrusion molding to a size of cm^3 or more, and this sheet is crosslinked in the presence of moisture at a temperature below the softening temperature of the silyl-modified polyolefin resin, and then heated to a temperature above the decomposition temperature of the blowing agent. 1. A method for producing a crosslinked polyolefin resin foam, which comprises foaming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1262508A JPH03124743A (en) | 1989-10-06 | 1989-10-06 | Preparation of crosslinked polyolefin resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1262508A JPH03124743A (en) | 1989-10-06 | 1989-10-06 | Preparation of crosslinked polyolefin resin foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03124743A true JPH03124743A (en) | 1991-05-28 |
Family
ID=17376777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1262508A Pending JPH03124743A (en) | 1989-10-06 | 1989-10-06 | Preparation of crosslinked polyolefin resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03124743A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0733558A1 (en) * | 1995-03-21 | 1996-09-25 | Rapid S.A. | Sealing plug for an opening and process for manufacturing same |
| EP0938510A4 (en) * | 1996-11-15 | 1999-11-24 | Sentinel Products Corp | Silane-grafted materials for solid and foam applications |
| WO2009089698A1 (en) * | 2008-01-15 | 2009-07-23 | Quanzhou Gongyuan Textile Co., Ltd | Degradable environment-friendly type polypropylene (pp) foam plastic and preparation method thereof |
| US20210395477A1 (en) * | 2018-09-28 | 2021-12-23 | Sekisui Chemical Co., Ltd. | Foamed polyolefin-based-resin sheet |
-
1989
- 1989-10-06 JP JP1262508A patent/JPH03124743A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0733558A1 (en) * | 1995-03-21 | 1996-09-25 | Rapid S.A. | Sealing plug for an opening and process for manufacturing same |
| FR2731984A1 (en) * | 1995-03-21 | 1996-09-27 | Rapid Sa | CLOSURE CAP OF ANY OPENING AND METHOD OF MANUFACTURING THE SAME |
| EP0938510A4 (en) * | 1996-11-15 | 1999-11-24 | Sentinel Products Corp | Silane-grafted materials for solid and foam applications |
| WO2009089698A1 (en) * | 2008-01-15 | 2009-07-23 | Quanzhou Gongyuan Textile Co., Ltd | Degradable environment-friendly type polypropylene (pp) foam plastic and preparation method thereof |
| US20210395477A1 (en) * | 2018-09-28 | 2021-12-23 | Sekisui Chemical Co., Ltd. | Foamed polyolefin-based-resin sheet |
| US12060470B2 (en) * | 2018-09-28 | 2024-08-13 | Sekisui Chemical Co., Ltd. | Foamed polyolefin-based-resin sheet |
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