JP2011122021A - Composition for sound-absorbing foam and sound-absorbing foam - Google Patents
Composition for sound-absorbing foam and sound-absorbing foam Download PDFInfo
- Publication number
- JP2011122021A JP2011122021A JP2009279453A JP2009279453A JP2011122021A JP 2011122021 A JP2011122021 A JP 2011122021A JP 2009279453 A JP2009279453 A JP 2009279453A JP 2009279453 A JP2009279453 A JP 2009279453A JP 2011122021 A JP2011122021 A JP 2011122021A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl aromatic
- block copolymer
- sound
- composition
- aromatic block
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 121
- 229920001400 block copolymer Polymers 0.000 claims abstract description 79
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000005060 rubber Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 60
- 150000001993 dienes Chemical class 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 description 37
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- 238000004132 cross linking Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
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- 238000006116 polymerization reaction Methods 0.000 description 8
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- 239000000126 substance Substances 0.000 description 5
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
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- 150000001451 organic peroxides Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
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- 238000000691 measurement method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 238000004364 calculation method Methods 0.000 description 2
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- 239000004927 clay Substances 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 239000002667 nucleating agent Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
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Abstract
Description
本発明は、吸音性発泡体用組成物及び吸音性発泡体に関する。 The present invention relates to a sound-absorbing foam composition and a sound-absorbing foam.
従来から、自動車、事務機器、音響機器、家庭用電気製品をはじめとして、各種機器から発生する音を抑制するため、さまざまな吸音性を有する発泡体用組成物が検討されている。 2. Description of the Related Art Conventionally, foam compositions having various sound absorption properties have been studied in order to suppress sound generated from various devices such as automobiles, office equipment, audio equipment, and household electrical appliances.
例えば、有機ポリイソシアネートとポリオールとを発泡剤、触媒等からなるポリウレタンフォーム用組成物が提案されている（例えば、特許文献１参照。）。
また、ポリプロピレンと、ｔａｎδピーク温度が−２０℃以上４０℃以下の範囲にある共役ジエン系重合体と、発泡剤と、架橋剤とからなる組成物が提案されている（例えば、特許文献２参照。）。前記共役ジエン系重合体には、ビニル芳香族ブロック共重合体が含まれ、例えば、スチレン−イソプレン−スチレントリブロック共重合体、スチレン−ブタジエン−スチレントリブロック共重合体、スチレン−エチレン−ブタジエン−スチレンブロック共重合体が挙げられている。
For example, a polyurethane foam composition comprising an organic polyisocyanate and a polyol as a foaming agent, a catalyst and the like has been proposed (see, for example, Patent Document 1).
A composition comprising polypropylene, a conjugated diene polymer having a tan δ peak temperature in the range of −20 ° C. or more and 40 ° C. or less, a foaming agent, and a crosslinking agent has been proposed (see, for example, Patent Document 2). .) The conjugated diene polymer includes a vinyl aromatic block copolymer, for example, a styrene-isoprene-styrene triblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene-ethylene-butadiene- Styrene block copolymers are mentioned.
しかしながら、特許文献１に記載のポリウレタンフォーム用組成物は、耐水性が十分では無く、また、経済性も必ずしも有利ではないという問題を有している。
また、特許文献１、２に記載されている組成物は、いずれも吸音率については、未だ改良の余地がある。
However, the polyurethane foam composition described in Patent Document 1 has problems that water resistance is not sufficient and that economic efficiency is not necessarily advantageous.
In addition, the compositions described in Patent Documents 1 and 2 still have room for improvement in sound absorption coefficient.
そこで本発明においては、優れた吸音率を有する吸音性発泡体用組成物、及び発泡体を提供することを目的とする。 Then, in this invention, it aims at providing the composition for sound-absorbing foams which has the outstanding sound absorption rate, and a foam.
本発明者らは、上記従来技術の課題を解決するため鋭意検討を重ねた結果、熱可塑性樹脂（ａ）及び／又はゴム（ｂ）と、特定のビニル芳香族系ブロック共重合体（ｃ）とを含有する吸音性発泡体用組成物及びこれを用いた吸音性発泡体が、上記従来の課題を解決できることを見出し、本発明を完成するに至った。
すなわち、本発明は、以下の通りである。
As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that the thermoplastic resin (a) and / or rubber (b) and a specific vinyl aromatic block copolymer (c) The present inventors have found that a composition for sound-absorbing foam and a sound-absorbing foam using the same can solve the above conventional problems, and have completed the present invention.
That is, the present invention is as follows.
〔１〕
熱可塑性樹脂（ａ）及び／又はゴム（ｂ）と、
ビニル芳香族系ブロック共重合体（ｃ）と、
を、含有し、
前記ビニル芳香族系ブロック共重合体（ｃ）が、−２０℃以上５０℃以下の範囲にｔａｎδピーク温度を有し、
前記ビニル芳香族系ブロック共重合体（ｃ）のＳＰ値（（Ｊ／ｃｍ3）1/2）が、１７．３以上２０．０以下である吸音性発泡体用組成物。
[1]
A thermoplastic resin (a) and / or rubber (b);
Vinyl aromatic block copolymer (c);
Containing,
The vinyl aromatic block copolymer (c) has a tan δ peak temperature in the range of −20 ° C. or more and 50 ° C. or less,
The composition for sound-absorbing foams in which the SP value ((J / cm 3 ) 1/2 ) of the vinyl aromatic block copolymer (c) is 17.3 or more and 20.0 or less.
〔２〕
前記ビニル芳香族系ブロック共重合体（ｃ）が、水素添加物である前記〔１〕に記載の吸音性発泡体用組成物。
[2]
The composition for sound-absorbing foams according to [1], wherein the vinyl aromatic block copolymer (c) is a hydrogenated product.
〔３〕
前記熱可塑性樹脂（ａ）又はゴム（ｂ）のＳＰ値（（Ｊ／ｃｍ3）1/2）と、
前記ビニル芳香族系ブロック共重合体（ｃ）のＳＰ値（（Ｊ／ｃｍ3）1/2）との差が、０．５（（Ｊ／ｃｍ3）1/2）以上である前記〔１〕又は〔２〕に記載の吸音性発泡体用組成物。
[3]
SP value ((J / cm 3 ) 1/2 ) of the thermoplastic resin (a) or rubber (b),
The difference from the SP value ((J / cm 3 ) 1/2 ) of the vinyl aromatic block copolymer (c) is 0.5 ((J / cm 3 ) 1/2 ) or more [ The composition for sound-absorbing foams according to [1] or [2].
〔４〕
前記ビニル芳香族系ブロック共重合体（ｃ）が、ビニル芳香族単量体と共役ジエン単量体とを主体とする共重合体である前記〔１〕乃至〔３〕のいずれか一に記載の吸音性発泡体用組成物。
[4]
The vinyl aromatic block copolymer (c) according to any one of [1] to [3], wherein the vinyl aromatic block copolymer (c) is a copolymer mainly composed of a vinyl aromatic monomer and a conjugated diene monomer. A sound absorbing foam composition.
〔５〕
前記ビニル芳香族系ブロック共重合体（ｃ）が、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を、１つ以上を含有する前記〔１〕乃至〔４〕のいずれか一に記載の吸音性発泡体用組成物。
[5]
Any one of [1] to [4], wherein the vinyl aromatic block copolymer (c) contains one or more polymer blocks (c1) mainly composed of a vinyl aromatic monomer. The composition for sound-absorbing foams described in 1.
〔６〕
前記ビニル芳香族系ブロック共重合体（ｃ）中の、前記ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）のＳＰ値と、前記（ｃ１）以外のブロックのＳＰ値との差の少なくとも一つが、２．５以下である前記〔１〕乃至〔５〕のいずれか一に記載の吸音性発泡体用組成物。
[6]
Difference between SP value of polymer block (c1) mainly composed of vinyl aromatic monomer and SP value of blocks other than (c1) in vinyl aromatic block copolymer (c) The composition for sound-absorbing foams according to any one of [1] to [5], wherein at least one of is 2.5 or less.
〔７〕
前記ビニル芳香族系ブロック共重合体（ｃ）が、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を１つ以上と、ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック（ｃ２）を１つ以上、含有する前記〔１〕乃至〔６〕のいずれか一に記載の吸音性発泡体用組成物。
[7]
The vinyl aromatic block copolymer (c) is mainly composed of one or more polymer blocks (c1) mainly composed of a vinyl aromatic monomer, and mainly composed of a vinyl aromatic monomer and a conjugated diene monomer. The composition for sound-absorbing foams according to any one of [1] to [6], which contains at least one copolymer block (c2).
〔８〕
前記ビニル芳香族系ブロック共重合体（ｃ）中の、非水素添加の共役ジエン単量体単位が、５質量％〜７０質量％の範囲にある前記〔１〕乃至〔７〕のいずれか一に記載の吸音性発泡体用組成物。
[8]
Any one of [1] to [7], wherein the non-hydrogenated conjugated diene monomer unit in the vinyl aromatic block copolymer (c) is in the range of 5% by mass to 70% by mass. The composition for sound-absorbing foams described in 1.
〔９〕
前記ビニル芳香族系ブロック共重合体（ｃ）が、水素添加物であり、水素添加前におけるビニル芳香族ブロック共重合体中の総共役ジエンの不飽和基のうち、５ｍｏｌ％以上８５ｍｏｌ％以下の範囲が水素添加されている前記〔１〕乃至〔８〕のいずれか一に記載の吸音性発泡体用組成物。
[9]
The vinyl aromatic block copolymer (c) is a hydrogenated product, and the unsaturated group of the total conjugated diene in the vinyl aromatic block copolymer before hydrogenation is 5 mol% or more and 85 mol% or less. The composition for sound-absorbing foams according to any one of [1] to [8], wherein the range is hydrogenated.
〔１０〕
発泡剤及び架橋剤を、さらに含有する前記〔１〕乃至〔９〕のいずれか一に記載の吸音性発泡体用組成物。
[10]
The composition for sound-absorbing foams according to any one of [1] to [9], further including a foaming agent and a crosslinking agent.
〔１１〕
前記〔１〕乃至〔１０〕のいずれか一に記載の吸音性発泡体用組成物を用いて成形した吸音性発泡体。
[11]
A sound-absorbing foam formed by using the composition for sound-absorbing foam according to any one of [1] to [10].
本発明によれば、優れた吸音率を有する吸音性発泡体、及び当該発泡体を得るための吸音性発泡体用組成物が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the sound-absorbing foam which has the outstanding sound absorption rate, and the composition for sound-absorbing foams for obtaining the said foam are obtained.
以下、本発明を実施するための形態（以下、「本実施形態」と言う。）について詳細に説明する。
本発明は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施できる。
Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.
〔吸音性発泡体用組成物〕
本実施形態の吸音性発泡体用組成物は、熱可塑性樹脂（ａ）及び／又はゴム（ｂ）と、ビニル芳香族系ブロック共重合体（ｃ）とを含有するものである。
前記ビニル芳香族系ブロック共重合体（ｃ）は、−２０℃以上５０℃以下の範囲にｔａｎδピーク温度を有している。
前記ビニル芳香族系ブロック共重合体（ｃ）の、後述するＳＰ値（（Ｊ／ｃｍ3）1/2）は、１７．３以上２０．０以下である。
[Composition for sound absorbing foam]
The composition for sound-absorbing foams of this embodiment contains a thermoplastic resin (a) and / or rubber (b) and a vinyl aromatic block copolymer (c).
The vinyl aromatic block copolymer (c) has a tan δ peak temperature in the range of −20 ° C. to 50 ° C.
The vinyl aromatic block copolymer (c) has an SP value ((J / cm 3 ) 1/2 ) described later of 17.3 or more and 20.0 or less.
〔熱可塑性樹脂（ａ）〕
熱可塑性樹脂（ａ）は、特に限定はされないが、オレフィン系樹脂、スチレン系樹脂、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリフェニレンエーテル（ＰＰＥ）、ポリフェニレンスルフィド（ＰＰＳ）等の芳香族系樹脂、ナイロン６６、ナイロン６等のポリアミド、メタクリル樹脂、アクリル樹脂、エチレン酢酸ビニル共重合体（ＥＶＡ）、ポリ塩化ビニル系樹脂等が挙げられる。
これらは、一種のみを単独で用いてもよく、二種以上を使用してもよい。
[Thermoplastic resin (a)]
The thermoplastic resin (a) is not particularly limited, but is an olefin resin, a styrene resin, a polyester such as a polycarbonate, polyethylene terephthalate, or polybutylene terephthalate, or an aromatic resin such as polyphenylene ether (PPE) or polyphenylene sulfide (PPS). Resin, polyamide such as nylon 66 and nylon 6, methacrylic resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), polyvinyl chloride resin and the like.
These may be used alone or in combination of two or more.
オレフィン系樹脂としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のホモ重合体、エチレン又はプロピレンとブテン、ヘキセン又はオクテン等とのブロック共重合体又はランダム共重合体、ポリメチルペンテン、ポリ１−ブテン、プロピレン・１−ブテン共重合体、塩素化ポリオレフィン、エチレン・メタクリル酸及びそのエステル共重合体、スチレン・アクリル酸及びそのエステル共重合体、エチレン・プロピレン共重合体（ＥＰＲ）等を挙げることができる。 Examples of the olefin resin include homopolymers such as polyethylene (PE) and polypropylene (PP), block copolymers or random copolymers of ethylene or propylene and butene, hexene or octene, polymethylpentene, poly 1-butene, propylene / 1-butene copolymer, chlorinated polyolefin, ethylene / methacrylic acid and its ester copolymer, styrene / acrylic acid and its ester copolymer, ethylene / propylene copolymer (EPR), etc. Can be mentioned.
高い耐薬品性や耐熱性の観点から、上記の中でも、結晶性を有する熱可塑性樹脂が好ましい。
また、経済性の観点から、ポリプロピレン、プロピレンを含むブロック共重合体又はランダム共重合体などのプロピレン系樹脂や、高圧法低密度ポリエチレン、低圧法低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、メタロセン触媒を使用して重合されたポリエチレン系樹脂、あるいはエチレン酢酸ビニル共重合体が好ましい。
Among the above, from the viewpoint of high chemical resistance and heat resistance, a thermoplastic resin having crystallinity is preferable.
Also, from the viewpoint of economy, propylene resins such as polypropylene, propylene-containing block copolymers or random copolymers, high pressure method low density polyethylene, low pressure method low density polyethylene, medium density polyethylene, high density polyethylene, metallocene A polyethylene resin polymerized using a catalyst or an ethylene vinyl acetate copolymer is preferred.
〔ゴム（ｂ）〕
ゴム（ｂ）は、特に限定されないが、例えば、天然ゴム、アクリルゴム（ＡＣＭ）、ニトリルゴム（ＮＢＲ）、イソプレンゴム（ＩＲ）、ウレタンゴム（Ｕ）、エチレンプロピレンゴム（ＥＰＭ、ＥＰＤＭ）、エピクロルヒドリンゴム（ＣＯ、ＥＣＯ）、クロロプレンゴム（ＣＲ）、シリコーンゴム（Ｑ）、ブロックを有さないスチレン・ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、フッ素ゴム（ＦＫＭ）等を挙げることができる。
経済性の観点から、天然ゴム、イソプレンゴム（ＩＲ）、エチレンプロピレンゴム（ＥＰＭ、ＥＰＤＭ）、ブロックを有さないスチレン・ブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）が好ましい。
[Rubber (b)]
The rubber (b) is not particularly limited. For example, natural rubber, acrylic rubber (ACM), nitrile rubber (NBR), isoprene rubber (IR), urethane rubber (U), ethylene propylene rubber (EPM, EPDM), epichlorohydrin. Examples thereof include rubber (CO, ECO), chloroprene rubber (CR), silicone rubber (Q), styrene / butadiene rubber (SBR) having no block, butadiene rubber (BR), and fluorine rubber (FKM).
From the viewpoint of economy, natural rubber, isoprene rubber (IR), ethylene propylene rubber (EPM, EPDM), styrene-butadiene rubber (SBR) and butadiene rubber (BR) having no block are preferable.
上述した各種熱可塑性樹脂（ａ）、ゴム（ｂ）の中においては、優れた経済性及び高い吸音性を実現できる観点から、分子中にエチレン構造を有するものが好ましい。
また、熱可塑性樹脂（ａ）及び／又はゴム（ｂ）の組み合わせの中では、経済性の観点から、熱可塑性樹脂が多い方が好ましく、（ａ）熱可塑性樹脂のみがより好ましい。
Among the various thermoplastic resins (a) and rubbers (b) described above, those having an ethylene structure in the molecule are preferable from the viewpoint of realizing excellent economic efficiency and high sound absorption.
Moreover, in the combination of a thermoplastic resin (a) and / or rubber | gum (b), the direction with much thermoplastic resin is preferable from a viewpoint of economical efficiency, and only (a) thermoplastic resin is more preferable.
〔ビニル芳香族系ブロック共重合体（ｃ）〕
ビニル芳香族系ブロック共重合体（ｃ）とは、ビニル芳香族単量体単位を有する共重合体を指す。
なお、本明細書において、共重合体を構成する各単量体単位の命名は、該単量体単位が由来する単量体の命名に従う。
例えば、「ビニル芳香族単量体単位」とは、単量体であるビニル芳香族化合物を重合した結果生ずる、重合体の構成単位を意味し、その構造は、置換ビニル基に由来する置換エチレン基の二つの炭素が結合部位となっている分子構造である。
また、「共役ジエン単量体単位」とは、単量体である共役ジエンを重合した結果生ずる、重合体の構成単位を意味し、その構造は、共役ジエン単量体に由来するオレフィンの二つの炭素が結合部位となっている分子構造である。
また、「主体とする」とは、含有量が６０質量％以上であることを意味し、８０質量％以上が好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
なお、ビニル芳香族系ブロック共重合体（ｃ）は、水素添加物であることが好ましい。
[Vinyl aromatic block copolymer (c)]
The vinyl aromatic block copolymer (c) refers to a copolymer having a vinyl aromatic monomer unit.
In the present specification, the naming of each monomer unit constituting the copolymer follows the naming of the monomer from which the monomer unit is derived.
For example, “vinyl aromatic monomer unit” means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is substituted ethylene derived from a substituted vinyl group. It is a molecular structure in which the two carbons of the group are binding sites.
The term “conjugated diene monomer unit” means a structural unit of a polymer produced as a result of polymerizing a monomer, conjugated diene, and its structure is the same as that of an olefin derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.
Further, “mainly” means that the content is 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. Further preferred.
The vinyl aromatic block copolymer (c) is preferably a hydrogenated product.
前記ビニル芳香族系ブロック共重合体（ｃ）は、本実施形態の発泡体用組成物を用いて成形した発泡体において高い吸音率を得る観点から、−２０℃以上５０℃以下の範囲にｔａｎδピーク温度を有するものとする。
ｔａｎδピーク温度は、−１０℃以上４０℃以下の範囲が好ましく、０℃以上３０℃以下の範囲がより好ましく、１０℃以上３０℃未満がさらに好ましい。
ｔａｎδピーク温度は、後述する実施例に示す粘弾性測定より得られる値である。
The vinyl aromatic block copolymer (c) is tan δ in the range of −20 ° C. or more and 50 ° C. or less from the viewpoint of obtaining a high sound absorption coefficient in the foam molded using the foam composition of the present embodiment. It shall have a peak temperature.
The tan δ peak temperature is preferably in the range of −10 ° C. to 40 ° C., more preferably in the range of 0 ° C. to 30 ° C., and even more preferably in the range of 10 ° C. to less than 30 ° C.
The tan δ peak temperature is a value obtained from the viscoelasticity measurement shown in the examples described later.
前記ビニル芳香族系ブロック共重合体（ｃ）は、本実施形態の発泡体用組成物を用いて成形した発泡体において高い吸音率を得る観点から、ＳＰ値（（Ｊ／ｃｍ3）1/2）が、１７．３以上２０．０以下の範囲であることが必須である。ＳＰ値（（Ｊ／ｃｍ3）1/2）は、１８．０以上１９．３以下が好ましく、１８．２以上１９．０以下がより好ましく、１８．５以上１８．８以下がさらに好ましい。 The vinyl aromatic block copolymer (c) has an SP value ((J / cm 3 ) 1 / from the viewpoint of obtaining a high sound absorption coefficient in a foam molded using the foam composition of the present embodiment. 2 ) is in the range of 17.3 or more and 20.0 or less. The SP value ((J / cm 3 ) 1/2 ) is preferably from 18.0 to 19.3, more preferably from 18.2 to 19.0, and even more preferably from 18.5 to 18.8.
前記ＳＰ値は、ビニルポリマーのモル体積、凝集エネルギーを、Ｂｉｃｅｒａｎｏ（文献：Ｊ．Ｂｉｃｅｒａｎｏ，Ｐｒｅｄｉｃｔｉｏｎ ｏｆ Ｐｏｌｙｍｅｒ Ｐｒｏｐｅｒｔｉｅｓ，３ｒｄ，Ｍａｒｃｅｌ Ｄｅｋｋｅｒ，２００２）の方法で計算し、Ｖａｎ Ｋｒｅｖｅｌｅｎ法に準拠し求めることができる。
結晶性の有無は無視する。また、ブロック共重合体が、ミクロ相分離していても無視する。
計算方法は、Ｊｏｚｅｆ.Ｂｉｃｅｒａｎｏ：ＰＲＥＤＩＣＴＩＯＮ ＯＦ ＰＯＬＹＭＥＲ ＰＲＯＰＥＲＴＩＥＳ, Ｍａｒｃｅｌ Ｄｅｋｋｅｒ,ＡＭＥＲＩＣＡ（２００２）のｐ．６１５の１７．８から１７．１０式に示される方法を使用できる。
The SP value can be calculated according to the Van Krebelen method by calculating the molar volume and cohesive energy of the vinyl polymer by the method of Bicerano (reference: J. Bicerano, Prediction of Polymer Properties, 3rd, Marcel Dekker, 2002). it can.
Ignore the presence or absence of crystallinity. Further, even if the block copolymer is microphase-separated, it is ignored.
The calculation method is described in p. Of Joseph. Bicerano: PREDICTION OF POLYMER PROPERIES, Marcel Dekker, AMERICA (2002). The method shown in equations 17.8 to 17.10 of 615 can be used.
具体的に、前記ビニル芳香族系ブロック共重合体のＳＰ値の計算方法は、ビニル芳香族系ブロック共重合体（ｃ）を構成する各々のビニルポリマーのモル体積、凝集エネルギーを、Ｂｉｃｅｒａｎｏ（文献：Ｊ．Ｂｉｃｅｒａｎｏ，Ｐｒｅｄｉｃｔｉｏｎ ｏｆ Ｐｏｌｙｍｅｒ Ｐｒｏｐｅｒｔｉｅｓ，３ｒｄ，ＭａｒｃｅｌＤｅｋｋｅｒ，２００２）の方法で計算する。
凝集エネルギーに関しては、Ｖａｎ Ｋｒｅｖｅｌｅｎ法に準拠し計算した値を用いる。
次に、Ｊｏｚｅｆ.Ｂｉｃｅｒａｎｏ：ＰＲＥＤＩＣＴＩＯＮ ＯＦ ＰＯＬＹＭＥＲ ＰＲＯＰＥＲＴＩＥＳ, Ｍａｒｃｅｌ Ｄｅｋｋｅｒ,ＡＭＥＲＩＣＡ（２００２）の、ｐ．６１５の１７．８から１７．１０式に示される方法で、任意の組成の共重合体のＳＰ値を求めることができる。
なお、結晶性やブロック共重合体等のミクロ相分離構造は無視する。
Specifically, the SP value of the vinyl aromatic block copolymer is calculated by calculating the molar volume and cohesive energy of each vinyl polymer constituting the vinyl aromatic block copolymer (c) by Bicerano (reference) : J. Bicerano, Prediction of Polymer Properties, 3rd, Marcel Dekker, 2002).
For the cohesive energy, a value calculated in accordance with the Van Krevelen method is used.
Next, p. Of Jozef. Bicerano: PREDICTION OF POLYMER PROPERIES, Marcel Dekker, AMERICA (2002), p. The SP value of a copolymer having an arbitrary composition can be obtained by the method represented by the formulas 17.8 to 17.10.
Note that microphase separation structures such as crystallinity and block copolymers are ignored.
前記ビニル芳香族系ブロック共重合体（ｃ）を構成する各ビニルポリマーの凝集エネルギーＥ（Ｊ／ｍｏｌ）／モル体積Ｖ（１０-6ｍ3／ｍｏｌ）例示する。
ポリスチレン：３６９３２／９７．０、１，２−ポリブタジエン：１６４５０／５８．３、１，４−ポリブタジエン：１８５７９／５９．１、１,２−ポリブチレン：１７５２７／６５．６、水素添加１,４−ポリブタジエン：１８１４６／６４．４、１，４−ポリイソプレン：２２６４４／７６．６、１，２−ポリイソプレン：１９４０７／７５．３、３,４−ポリイソプレン：２０９０８／８２．２、ポリエチレン：９０７３／３２．２である。
例えば、スチレン／１，４−ブタジエンの等モルの共重合体の場合のＳＰ値の計算方法を以下に示す。
Ｅ＝３６９３２×０．５＋１８５７９×０．５＝２７７５５（Ｊ／ｍｏｌ）
Ｖ＝９７．０×０．５＋５９．１×０．５＝７８．１（ｍ3／ｍｏｌ）
ＳＰ値＝（２７７５５／７８．１）1/2７５５／＝１８．６（（Ｊ／ｃｍ3）1/2）
Examples of the cohesive energy E (J / mol) / molar volume V (10 −6 m 3 / mol) of each vinyl polymer constituting the vinyl aromatic block copolymer (c) are given below.
Polystyrene: 36932 / 97.0, 1,2-polybutadiene: 16450 / 58.3, 1,4-polybutadiene: 18579 / 59.1, 1,2-polybutylene: 17527 / 65.6, hydrogenated 1,4- Polybutadiene: 18146 / 64.4, 1,4-polyisoprene: 22644 / 76.6, 1,2-polyisoprene: 19407 / 75.3, 3,4-polyisoprene: 20908 / 82.2, polyethylene: 9073 /32.2.
For example, the calculation method of SP value in the case of equimolar copolymer of styrene / 1,4-butadiene is shown below.
E = 36932 × 0.5 + 18579 × 0.5 = 27755 (J / mol)
V = 97.0 × 0.5 + 59.1 × 0.5 = 78.1 (m 3 / mol)
SP value = (27755 / 78.1) 1/2 755 / = 18.6 ((J / cm 3 ) 1/2 )
本実施形態の発泡体組成物を用いて成形した発泡体において、より高い吸音率を得る観点から、前記熱可塑性樹脂（ａ）又はゴム（ｂ）のＳＰ値（（Ｊ／ｃｍ3）1/2）と、前記ビニル芳香族系ブロック共重合体（ｃ）のＳＰ値（（Ｊ／ｃｍ3）1/2）との差が、０．５（（Ｊ／ｃｍ3）1/2）以上であることが好ましく、１．０以上であることがより好ましく、１．５以上であることがさらに好ましい。 In the foam molded using the foam composition of the present embodiment, the SP value of the thermoplastic resin (a) or rubber (b) ((J / cm 3 ) 1 / 2 ) and the SP value ((J / cm 3 ) 1/2 ) of the vinyl aromatic block copolymer (c) is 0.5 ((J / cm 3 ) 1/2 ) or more Preferably, it is 1.0 or more, more preferably 1.5 or more.
前記ビニル芳香族系ブロック共重合体（ｃ）は、経済性や、本実施形態の発泡体組成物を用いて成形した発泡体において、より高い吸音率を得る観点から、ビニル芳香族単量体単位と共役ジエン単量体単位とを主体とする共重合体であることが好ましい。
ビニル芳香族単量体とは、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼン、１，１−ジフェニルエチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノエチルスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノエチルスチレン等のビニル芳香族化合物が挙げられる。
これらは一種のみを用いてもよく、二種以上を併用してもよい。
上記ビニル芳香族単量体の中では、経済性の観点からスチレンが好ましい。
The vinyl aromatic block copolymer (c) is a vinyl aromatic monomer from the viewpoint of economic efficiency and obtaining a higher sound absorption coefficient in a foam molded using the foam composition of the present embodiment. It is preferably a copolymer mainly composed of units and conjugated diene monomer units.
Examples of the vinyl aromatic monomer include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, and N, N-diethyl. And vinyl aromatic compounds such as -p-aminoethylstyrene.
These may use only 1 type and may use 2 or more types together.
Among the vinyl aromatic monomers, styrene is preferable from the viewpoint of economy.
上記共役ジエン単量体を構成する「共役ジエン」は、１対の共役二重結合を有するジオレフィンである。
例えば、１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン等が挙げられ、１，３−ブタジエン、イソプレンが好ましい。
これらの共役ジエンは、一種のみを用いてもよく、二種以上を併用してもよい。
また、本実施形態の発泡体組成物を用いて成形した発泡体において、優れた機械強度を得る観点から、１，３−ブタジエンを主体とするものであることがより好ましい。
さらに、共役ジエン中の１，３−ブタジエン含有量が８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
The “conjugated diene” constituting the conjugated diene monomer is a diolefin having a pair of conjugated double bonds.
For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1 1,3-hexadiene and the like, and 1,3-butadiene and isoprene are preferred.
These conjugated dienes may be used alone or in combination of two or more.
Moreover, in the foam shape | molded using the foam composition of this embodiment, it is more preferable that it is what mainly has 1, 3- butadiene from a viewpoint of obtaining the outstanding mechanical strength.
Furthermore, the 1,3-butadiene content in the conjugated diene is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
前記ビニル芳香族系ブロック共重合体（ｃ）は、当該共重合体の製造容易性、及び本実施形態の発泡体組成物の機械的強度の観点から、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を、１つ以上含有するものであることが好ましい。
前記ビニル芳香族系ブロック共重合体（ｃ）中の、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）の量は、本実施形態の発泡体組成物の機械的強度の観点や、前記共重合体（ｃ）の製造容易性の観点から、５質量％以上が好ましく、本実施形態の発泡体組成物を用いて成形した発泡体において高い吸音率を得る観点から５０質量％以下が好ましく、１０質量％以上３０質量％以下の範囲がより好ましく、１３質量％以上２５質量％以下がさらに好ましい。
なお、前記ビニル芳香族系ブロック共重合体（ｃ）中の、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）の量は、後述する実施例に示す方法で求めることができる。
The vinyl aromatic block copolymer (c) is mainly composed of a vinyl aromatic monomer from the viewpoint of ease of production of the copolymer and the mechanical strength of the foam composition of the present embodiment. It is preferable to contain one or more polymer blocks (c1).
The amount of the polymer block (c1) mainly composed of a vinyl aromatic monomer in the vinyl aromatic block copolymer (c) is determined in view of the mechanical strength of the foam composition of the present embodiment. From the viewpoint of ease of production of the copolymer (c), 5% by mass or more is preferable, and from the viewpoint of obtaining a high sound absorption coefficient in the foam molded using the foam composition of the present embodiment, 50% by mass or less. Is preferable, the range of 10% by mass to 30% by mass is more preferable, and the range of 13% by mass to 25% by mass is more preferable.
In addition, the amount of the polymer block (c1) mainly composed of the vinyl aromatic monomer in the vinyl aromatic block copolymer (c) can be determined by the method shown in the examples described later.
また、本実施形態の発泡体用組成物を用いて成形した発泡体において高い吸音率を得る観点から、前記ビニル芳香族系ブロック共重合体（ｃ）中の、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）と、（ｃ１）以外のブロックのＳＰ値との差の少なくとも一つが、０．２以上２．５以下の範囲であることが好ましく、０．４以上２．０以下の範囲であることがより好ましく、０．６以上１．５以下の範囲であることがさらに好ましい。
前記ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）以外のブロックの分子量は、少なくとも３０００以上である。
Further, from the viewpoint of obtaining a high sound absorption coefficient in the foam molded using the foam composition of the present embodiment, the vinyl aromatic block copolymer (c) is mainly composed of the vinyl aromatic monomer. Preferably, at least one of the differences between the polymer block (c1) and the SP value of blocks other than (c1) is in the range of 0.2 to 2.5, and 0.4 to 2.0. The following range is more preferable, and the range of 0.6 to 1.5 is more preferable.
The molecular weight of blocks other than the polymer block (c1) mainly composed of the vinyl aromatic monomer is at least 3000 or more.
前記ビニル芳香族系ブロック共重合体（ｃ）の製造容易性の観点から、当該ビニル芳香族系ブロック共重合体（ｃ）が、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を１つ以上と、ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック（ｃ２）を、１つ以上含有することが好ましい。なお、ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック（ｃ２）は、水素添加しても、しなくてもよい。 From the viewpoint of ease of production of the vinyl aromatic block copolymer (c), the vinyl aromatic block copolymer (c) is a polymer block (c1) mainly composed of a vinyl aromatic monomer. It is preferable to contain at least one copolymer block (c2) mainly composed of a vinyl aromatic monomer and a conjugated diene monomer. The copolymer block (c2) mainly composed of a vinyl aromatic monomer and a conjugated diene monomer may or may not be hydrogenated.
ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック（ｃ２）中の、ビニル芳香族単量体単位の含有量は、本実施形態の発泡体用組成物を用いて成形した発泡体において高い吸音性を得る観点から、３５質量％以上８５質量％以下の範囲が好ましく、４０質量％以上８０質量％の範囲がより好ましく、５０質量％以上７５質量％以下の範囲がさらに好ましく、５５質量％以上７０質量％以下の範囲がさらにより好ましい。 The content of the vinyl aromatic monomer unit in the copolymer block (c2) mainly composed of the vinyl aromatic monomer and the conjugated diene monomer is determined using the foam composition of the present embodiment. From the viewpoint of obtaining high sound absorption in the molded foam, a range of 35% by mass to 85% by mass is preferable, a range of 40% by mass to 80% by mass is more preferable, and a range of 50% by mass to 75% by mass is preferable. More preferably, the range of 55% by mass or more and 70% by mass or less is even more preferable.
前記ビニル芳香族系ブロック共重合体（ｃ）中に、前記ブロック（ｃ１）、（ｃ２）が、それぞれ２つ以上あるときは、各ブロックは同一であっても異なっていてもよい。
また、必要に応じて、共役ジエン単量体を主体とする重合体ブロックを含有してもよい。
前記ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）、ビニル芳香族単量体と共役ジエン単量体を主体とする共役ジエン単量体を主体とする共重合体ブロック（ｃ２）中のビニル芳香族単量体単位の分布は、上述したビニル芳香族化合物含有量の範囲であれば限定されず、均一に分布していても、テーパー状、階段状、凸状、あるいは凹状に分布していてもよい。
また、重合体ブロック中には、結晶部が存在していてもよい。
各共重合体ブロック中には、ビニル芳香族化合物含有量の異なるセグメントが複数個共存していてもよい。
各共重合体ブロック中のビニル結合量に分布があってもよい。
When the vinyl aromatic block copolymer (c) has two or more blocks (c1) and (c2), each block may be the same or different.
Moreover, you may contain the polymer block which has a conjugated diene monomer as a main component as needed.
Polymer block (c1) mainly composed of vinyl aromatic monomer, copolymer block (c2) mainly composed of conjugated diene monomer mainly composed of vinyl aromatic monomer and conjugated diene monomer The distribution of the vinyl aromatic monomer unit is not limited as long as it is within the range of the vinyl aromatic compound content described above, and may be tapered, stepped, convex, or concave, evenly distributed. It may be distributed.
In addition, a crystal part may be present in the polymer block.
In each copolymer block, a plurality of segments having different vinyl aromatic compound contents may coexist.
There may be a distribution in the amount of vinyl bonds in each copolymer block.
前記ビニル芳香族系ブロック共重合体（ｃ）のブロック構造としては、例えば、（（ｃ１）−（ｃ２））ｎ、（ｃ１）−（（ｃ２）−（ｃ１））ｎ、（ｃ１）−（ｃ３）−（ｃ２）−（ｃ１）、（ｃ１）−（ｃ３）−（ｃ２）−（ｃ３）−（ｃ１）の構造（カップリング重合や逐次重合のどちらでもよい。）が挙げられる。
ここで、ｎは、１〜３の整数、ｃ３は、共役ジエンを主体とする重合体ブロック（水素添加してもよい。）である。
特に、（ｃ１）−（ｃ２）−（ｃ１）、（ｃ１）−（ｃ３）−（ｃ２）−（ｃ１）の構造がより好ましい。
Examples of the block structure of the vinyl aromatic block copolymer (c) include ((c1)-(c2)) n, (c1)-((c2)-(c1)) n, and (c1)- (C3)-(c2)-(c1), (c1)-(c3)-(c2)-(c3)-(c1) structures (either coupling polymerization or sequential polymerization may be used).
Here, n is an integer of 1 to 3, and c3 is a polymer block mainly composed of conjugated diene (may be hydrogenated).
In particular, the structures of (c1)-(c2)-(c1) and (c1)-(c3)-(c2)-(c1) are more preferable.
前記ビニル芳香族系ブロック系共重合体（ｃ）の総共役ジエン単量体単位中のビニル結合量（水素添加物の場合は、水素添加前の総共役ジエン単量体単位中のビニル結合量）は、当該共重合体（ｃ）の製造容易性の観点から、５ｍｏｌ％以上５０ｍｏｌ％以下の範囲が好ましく、１０ｍｏｌ％以上４０ｍｏｌ％以下の範囲がより好ましく、１５ｍｏｌ％以上３５ｍｏｌ％以下の範囲がさらに好ましい。
ビニル結合量とは、水素添加前の共役ジエンの１，２−結合、３，４−結合及び１，４−結合の結合様式で組み込まれているうち、１，２−結合及び３，４−結合で組み込まれているものの割合とする。
架橋用組成物の場合、機械強度の観点から、前記ビニル芳香族ブロック共重合体（ｃ）中の、非水素添加の共役ジエン単量体単位が５質量％から７０質量％の範囲にあることが好ましい。
また、吸音性発泡体用組成物の高い耐光性や機械的物性の観点から、水素添加前における、前記共重合体（ｃ）中の、総共役ジエンの不飽和基のうち、５ｍｏｌ％以上８５ｍｏｌ％以下の範囲を水素添加することが好ましく、１０ｍｏｌ％以上７５ｍｏｌ％以下の範囲がより好ましく、２０ｍｏｌ％以上６０ｍｏｌ％以下がさらに好ましい。
Vinyl bond amount in the total conjugated diene monomer unit of the vinyl aromatic block copolymer (c) (in the case of hydrogenated product, vinyl bond amount in the total conjugated diene monomer unit before hydrogenation) ) Is preferably in the range of 5 mol% or more and 50 mol% or less, more preferably in the range of 10 mol% or more and 40 mol% or less, and in the range of 15 mol% or more and 35 mol% or less from the viewpoint of ease of production of the copolymer (c). Further preferred.
The amount of vinyl bonds refers to the 1,2-bond, 3,4-bond, and 1,4-bond linkage modes of the conjugated diene before hydrogenation. It is the ratio of what is incorporated in the bond.
In the case of the crosslinking composition, from the viewpoint of mechanical strength, the non-hydrogenated conjugated diene monomer unit in the vinyl aromatic block copolymer (c) is in the range of 5% by mass to 70% by mass. Is preferred.
Further, from the viewpoint of high light resistance and mechanical properties of the sound-absorbing foam composition, 5 mol% or more and 85 mol of unsaturated groups of the total conjugated diene in the copolymer (c) before hydrogenation. % Or less is preferably hydrogenated, more preferably 10 mol% or more and 75 mol% or less, and even more preferably 20 mol% or more and 60 mol% or less.
〔ビニル芳香族系ブロック共重合体（ｃ）の製造方法〕
ビニル芳香族系ブロック共重合体（ｃ）の重合方法としては、特に限定されないが、配位重合、アニオン重合またはカチオン重合などの重合方法が挙げられる。構造の制御の容易さの点で、アニオン重合が好ましい。
アニオン重合のビニル芳香族系ブロック共重合体の製造方法としては、公知の方法を適用でき、例えば、特公昭３６−１９２８６号公報、特公昭４３−１７９７９号公報、特公昭４６−３２４１５号公報、特公昭４９−３６９５７号公報、特公昭４８−２４２３号公報、特公昭４８−４１０６号公報、特公昭５６−２８９２５号公報、特開昭５９−１６６５１８号公報、特開昭６０−１８６５７７号公報等に記載された方法が挙げられる。
また、ビニル芳香族系ブロック共重合体（ｃ）は、アニオン重合系で、逐次重合やカップリング重合等を行うことにより製造できる。
カップリング重合を行うときのカップリング剤としては、四塩化ケイ素、四塩化スズ、エポキシ化大豆油、ポリハロゲン化炭化水素化合物、カルボン酸エステル化合物、ポリビニル化合物、ビスフェノール型エポキシ化合物、アルコキシシラン化合物、ハロゲン化シラン化合物、エステル系化合物等が挙げられる。
[Method for Producing Vinyl Aromatic Block Copolymer (c)]
The polymerization method of the vinyl aromatic block copolymer (c) is not particularly limited, and examples thereof include a polymerization method such as coordination polymerization, anionic polymerization, or cationic polymerization. Anionic polymerization is preferable from the viewpoint of easy control of the structure.
As a method for producing an anionic polymerization vinyl aromatic block copolymer, a known method can be applied, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, JP-B-56-28925, JP-A-59-166518, JP-A-60-186777, etc. Can be mentioned.
Further, the vinyl aromatic block copolymer (c) can be produced by an anionic polymerization system by performing sequential polymerization, coupling polymerization or the like.
As a coupling agent when performing coupling polymerization, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, polyhalogenated hydrocarbon compound, carboxylic acid ester compound, polyvinyl compound, bisphenol type epoxy compound, alkoxysilane compound, Examples include halogenated silane compounds and ester compounds.
ビニル芳香族系ブロック共重合体を水素添加し、ビニル芳香族系ブロック共重合体（ｃ）を得る際の、水素添加を行う方法としては、水素添加触媒の存在下で、水素を供給し、不飽和部を水素添加する方法が挙げられる。
水素添加触媒としては、特に限定はされるものではなく、従来公知の（１）Ｎｉ、Ｐｔ、Ｐｄ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等に担持させた担持型不均一系水素添加触媒、（２）Ｎｉ、Ｃｏ、Ｆｅ、Ｃｒ等の有機酸塩またはアセチルアセトン塩等の遷移金属塩と有機アルミニウム等の還元剤とを用いる、いわゆるチーグラー型水素添加触媒、（３）Ｔｉ、Ｒｕ、Ｒｈ、Ｚｒ等の有機金属化合物等のいわゆる有機金属錯体等の均一系水素添加触媒が挙げられる。
ビニル芳香族系ブロック共重合体（ｃ）の重量平均分子量は、機械強度の観点から、５万以上が好ましく、発泡体用組成物において良好な加工性を得る観点から、４０万以下の範囲が好ましく、６万以上３０万以下の範囲がより好ましく、８万以上２０万以下の範囲がさらに好ましく、１０万以上１５万以下の範囲がさらにより好ましい。
ビニル芳香族系ブロック共重合体（ｃ）の重量平均分子量は、後述する実施例に記載された方法により測定できる。
As a method of performing hydrogenation when hydrogenating a vinyl aromatic block copolymer to obtain a vinyl aromatic block copolymer (c), hydrogen is supplied in the presence of a hydrogenation catalyst, The method of hydrogenating an unsaturated part is mentioned.
The hydrogenation catalyst is not particularly limited, and the conventionally known (1) supported heterogeneous system in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A hydrogenation catalyst, (2) a so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Examples thereof include homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Ru, Rh and Zr.
The weight average molecular weight of the vinyl aromatic block copolymer (c) is preferably 50,000 or more from the viewpoint of mechanical strength, and from the viewpoint of obtaining good workability in the foam composition, a range of 400,000 or less. Preferably, the range of 60,000 to 300,000 is more preferable, the range of 80,000 to 200,000 is more preferable, and the range of 100,000 to 150,000 is even more preferable.
The weight average molecular weight of the vinyl aromatic block copolymer (c) can be measured by the method described in Examples described later.
本実施形態の発泡体用組成物中の、ビニル芳香族ブロック共重合体（ｃ）の含有量は、高い吸音性を得る観点から、１０質量％以上であることが好ましく、経済性の観点から９０質量％以下の範囲が好ましく、１５質量％以上７５質量％以下の範囲がより好ましく、２０質量％以上５０質量％以下の範囲がさらに好ましい。 The content of the vinyl aromatic block copolymer (c) in the foam composition of the present embodiment is preferably 10% by mass or more from the viewpoint of obtaining high sound absorption, and from the viewpoint of economy. The range of 90% by mass or less is preferable, the range of 15% by mass to 75% by mass is more preferable, and the range of 20% by mass to 50% by mass is more preferable.
〔発泡体用組成物、発泡体〕
本実施形態の発泡体用組成物は、前記熱可塑性樹脂（ａ）、ゴム（ｂ）、前記ビニル芳香族系ブロック共重合体（ｃ）、発泡剤、及び架橋剤を含有する。
これらを、例えば、加圧ニーダー及びロールオープンミル等を用いて、混練することにより発泡体用組成物が得られる。
[Composition for foam, foam]
The foam composition of this embodiment contains the thermoplastic resin (a), rubber (b), the vinyl aromatic block copolymer (c), a foaming agent, and a crosslinking agent.
These are knead | mixed using a pressure kneader, a roll open mill, etc., for example, and the composition for foams is obtained.
上記発泡体用組成物を発泡することにより発泡体が得られる。
発泡体用組成物の発泡方法としては、特に限定されるものではなく、化学的方法、物理的方法等が適用でき、各々、無機系発泡剤、有機系発泡剤等の化学的発泡剤、物理発泡剤等の発泡剤の添加等により、発泡体用組成物の内部に気泡を分布させて、発泡体が得られる。
また、樹脂からなる外殻と、内包される膨張剤とを有する熱膨張性微小球を発泡剤として用いてもよい。
A foam is obtained by foaming the composition for foam.
The foaming method of the foam composition is not particularly limited, and a chemical method, a physical method, or the like can be applied, and a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, By adding a foaming agent such as a foaming agent, bubbles are distributed inside the foam composition to obtain a foam.
Moreover, you may use the thermally expansible microsphere which has the outer shell which consists of resin, and the expansion | swelling agent included as a foaming agent.
無機系発泡剤としては、例えば、炭酸水素ナトリウム、炭酸水素アンモニウム、塩化アンモニウム、炭酸アンモニウム等の無機化合物が挙げられる。
また、無機系発泡剤に、発泡速度を改良するため弱酸性化合物を併用してもよい。
弱酸性化合物としては、シュウ酸、マロン酸、クエン酸、乳酸等の有機酸、ホウ酸等の無機酸、及びクエン酸モノソーダ、酸性酒石酸カリウム等の酸性塩が挙げられる。
有機系発泡剤としては、例えば、アゾジカルボンアミド、アゾビスホルムアミド、アゾビスイソブチロニトリル、アゾジカルボン酸バリウム、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ’−ジニトロソ−Ｎ，Ｎ’−ジメチルテレフタルアミド、ベンゼンスルホニルヒドラジド、ｐ−トルエンスルホニルヒドラジド、ｐ，ｐ’−オキシビスベンゼンスルホニルヒドラジド、ｐ−トルエンスルホニルセミカルバジド等が挙げられる。
物理的発泡剤としては、例えば、ペンタン、ブタン、ヘキサン等の炭化水素、塩化メチル、塩化メチレン等のハロゲン化炭化水素、窒素、空気等のガス、トリクロロフルオロメタン、ジクロロジフルオロメタン、トリクロロトリフルオロエタン、クロロジフルオロエタン、ハイドロフルオロカーボン等のフッ素化炭化水素等が挙げられる。
上述した発泡剤は、単独で用いてもよく、組み合わせて使用してもよい。
発泡剤の配合量は、発泡用組成物中の０．１〜２０質量％の範囲が好ましく、０．３〜１５質量％の範囲がより好ましく、０．５〜８質量％の範囲がさらに好ましい。
これらの発泡剤の助剤として尿素を主成分とした化合物、酸化亜鉛、酸化鉛等の金属酸化物、サリチル酸、ステアリン酸等を主成分とする化合物、即ち高級脂肪酸あるいは高級脂肪酸の金属化合物を添加してもよい。
Examples of the inorganic foaming agent include inorganic compounds such as sodium hydrogen carbonate, ammonium hydrogen carbonate, ammonium chloride, and ammonium carbonate.
In addition, a weak acidic compound may be used in combination with the inorganic foaming agent in order to improve the foaming speed.
Examples of the weakly acidic compound include organic acids such as oxalic acid, malonic acid, citric acid, and lactic acid, inorganic acids such as boric acid, and acidic salts such as monosodium citrate and acidic potassium tartrate.
Examples of the organic foaming agent include azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, N, N′-dinitroso-N, N. Examples include '-dimethyl terephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p'-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide and the like.
Examples of physical blowing agents include hydrocarbons such as pentane, butane and hexane, halogenated hydrocarbons such as methyl chloride and methylene chloride, gases such as nitrogen and air, trichlorofluoromethane, dichlorodifluoromethane, and trichlorotrifluoroethane. Fluorinated hydrocarbons such as chlorodifluoroethane and hydrofluorocarbon.
The above-mentioned foaming agents may be used alone or in combination.
The blending amount of the foaming agent is preferably in the range of 0.1 to 20% by mass in the foaming composition, more preferably in the range of 0.3 to 15% by mass, and still more preferably in the range of 0.5 to 8% by mass. .
As an auxiliary agent for these foaming agents, compounds containing urea as the main component, metal oxides such as zinc oxide and lead oxide, compounds containing salicylic acid and stearic acid as the main component, that is, higher fatty acids or higher fatty acid metal compounds are added. May be.
本実施形態における発泡体の比重は任意であるが、０．０３〜０．４の範囲が好ましい。 Although the specific gravity of the foam in this embodiment is arbitrary, the range of 0.03-0.4 is preferable.
本実施形態の発泡体は、より高い機械強度を得る観点から、架橋発泡体とすることが好ましい。
架橋体の製造方法は、特に制限されるものではなく、架橋剤により架橋する方法、紫外線架橋法、電子線架橋法、熱架橋法等の公知の方法を用いることができる。特に、架橋剤により、架橋する方法が好ましい。
架橋剤としては、例えば、有機過酸化物及びアゾ化合物などのラジカル発生剤、オキシム化合物、ニトロソ化合物、ポリアミン化合物、硫黄、硫黄化合物が使用される。硫黄含有化合物には、一塩化硫黄、二塩化硫黄、ジスルフィド化合物、高分子多硫化合物などが含まれる。
有機過酸化物としては、例えば、ジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルペルオキシ）バレレート、ベンゾイルペルオキシド、ｐ−クロロベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ｔｅｒｔ−ブチルペルオキシベンゾエート、ｔｅｒｔ−ブチルペルオキシベンゾエート、ｔｅｒｔ−ブチルペルオキシイソプロピルカーボネート、ジアセチルペルオキシド、ラウロイルペルオキシド、ｔｅｒｔ−ブチルクミルペルオキシド等が挙げられる。
なお、架橋剤としての有機過酸化物は、使用される樹脂や、架橋時における温度によって最適な材料を用いる。
架橋時における温度は、好ましくは８０以上２００℃以下、より好ましくは１００以上１８０℃以下である。
架橋剤の含有量は、高い機械強度を得る観点から、発泡体用組成物中において、０．０１質量％以上とすることが好ましく、経済性の観点から１０質量％以下とすることが好ましく、これらの観点から０．１質量％以上３質量％以下とすることがより好ましい。
The foam of this embodiment is preferably a cross-linked foam from the viewpoint of obtaining higher mechanical strength.
The production method of the crosslinked product is not particularly limited, and a known method such as a method of crosslinking with a crosslinking agent, an ultraviolet crosslinking method, an electron beam crosslinking method, a thermal crosslinking method, or the like can be used. Particularly preferred is a method of crosslinking with a crosslinking agent.
As the crosslinking agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds are used. Sulfur-containing compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like.
Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5- Di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate DOO, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.
In addition, the organic peroxide as a crosslinking agent uses an optimal material by the resin used and the temperature at the time of bridge | crosslinking.
The temperature at the time of crosslinking is preferably 80 or more and 200 ° C. or less, more preferably 100 or more and 180 ° C. or less.
The content of the crosslinking agent is preferably 0.01% by mass or more in the foam composition from the viewpoint of obtaining high mechanical strength, and preferably 10% by mass or less from the viewpoint of economy. From these viewpoints, the content is more preferably 0.1% by mass or more and 3% by mass or less.
架橋剤として上述した有機過酸化物を使用する際には、架橋助剤として、硫黄、ｐ−キノンジオキシム、ｐ，ｐ’−ジベンゾイルキノンジオキシム、Ｎ−メチル−Ｎ，４−ジニトロソアニリン、ニトロソベンゼン、ジフェニルグアニジン、トリメチロールプロパン−Ｎ，Ｎ’−ｍ−フェニレンジマレイミド等のペルオキシ架橋助剤、ジビニルベンゼン、トリアリルイソシアヌレート、トリアリルシアヌレート；エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、ノナンジオールジメタクリレート、トリメチロールプロパントリメタクリレート、アリルメタクリレート等の多官能性メタクリレートモノマー；ビニルブチラート、ビニルステアレート等の多官能性ビニルモノマー等を併用してもよい。
その他の架橋助剤として、亜鉛華、ステアリン酸などを必要に応じた量で使用できる。
When the above-described organic peroxide is used as a crosslinking agent, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitroso is used as a crosslinking aid. Peroxy crosslinking aids such as aniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N′-m-phenylenedimaleimide, divinylbenzene, triallyl isocyanurate, triallyl cyanurate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate Polyfunctional methacrylate monomers such as polyethylene glycol dimethacrylate, nonanediol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate; polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate Mer, etc. may be used in combination.
As other crosslinking aids, zinc white, stearic acid and the like can be used in an amount as required.
本実施形態の発泡体において、発泡性の改良（造核剤）の改良を図り、高い曲げ弾性率、耐衝撃性を得る観点から、無機充填剤を併用してもよい。
無機充填剤としては、例えば、シリカ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、硫酸カルシウム、硫酸バリウム、カーボンブラック、ガラス繊維、ガラスビーズ、ガラスバルーン、ガラスフレーク、グラファイト、酸化チタン、チタン酸カリウムウイスカー、カーボンファイバー、アルミナ、カオリンクレー、ケイ酸、ケイ酸カルシウム、石英、マイカ、タルク、クレー、ジルコニア、チタン酸カリウム、アルミナ、金属粒子等が挙げられる。
In the foam of this embodiment, an inorganic filler may be used in combination from the viewpoint of improving foamability (nucleating agent) and obtaining high flexural modulus and impact resistance.
Examples of the inorganic filler include silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloon, glass flake, graphite, titanium oxide, Examples include potassium titanate whiskers, carbon fibers, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, metal particles, and the like.
本実施形態の発泡体用組成物及び発泡体には、要求性能に応じて、その他の添加剤を併用してもよい。
例えば、難燃剤、安定剤、着色剤、紫外線吸収剤、顔料、酸化防止剤、帯電防止剤、分散剤、流れ増強剤、ステアリン酸金属塩といった離型剤、シリコーンオイル、鉱物油系軟化剤、合成樹脂系軟化剤、銅害防止剤、架橋剤、核剤等が挙げられるが、これらに限定されるものではない。
Other additives may be used in combination with the foam composition and foam of the present embodiment according to the required performance.
For example, flame retardants, stabilizers, colorants, UV absorbers, pigments, antioxidants, antistatic agents, dispersants, flow enhancers, mold release agents such as metal stearates, silicone oils, mineral oil softeners, Examples include, but are not limited to, synthetic resin softeners, copper damage inhibitors, crosslinking agents, and nucleating agents.
本実施形態の発泡体は、より高い吸音率を得るために、連続気泡を有する発泡体にしてもよい。
連続気泡を有する発泡体を得る方法としては、上述した熱可塑性樹脂（ａ）及び／又はゴム（ｂ）、及びビニル芳香族系ブロック共重合体（ｃ）に、発泡剤及び架橋剤を添加混練し、得られた発泡体用組成物を加熱発泡させて発泡体を形成させ、次いで機械的変形を加えて気泡を連通化させる方法であれば、従来公知の方法が適用でき、特に限定されない。
このような方法のうち、特に、特公昭６２−１９２９４号公報及び特公平１−４４４９９号公報に記載されているように、発泡体用組成物を所望の形状に加熱成形した後、気密でない金型中で常圧下にて加熱して、架橋剤及び発泡剤を同時進行的に分解させて気泡体を形成させ、次いで機械的変形を加えて気泡を連通化させる方法等が挙げられる。
この発泡・架橋工程例としては、例えば、発泡体用組成物を所望の断面形状、寸法を有する気密でない、すなわち密閉されていない金型に入れ、当該金型中に入れ、金型の金属板を外部から加熱することによって、上記組成物を間接的に加熱せしめる方法が挙げられる。
また、発泡体用組成物シートの両面に、それぞれに電子線を照射して架橋させ、得られた架橋された発泡体用組成物シートを熱風式発泡炉に通して加熱し、発泡させる方法も挙げられる。
上述のようにして得られた気泡体（いわゆる独立気泡体）を、例えば、等速二本ロール等により圧縮変形を加えることによって気泡膜が破壊され、気泡が連通化されて連続気泡体が得られる。このとき、等速二本ロールの表面に無数の小さい針を設けるか、又は等速二本ロールの前及び／又は後に無数の針を設けたロールを配置して、気泡体の表面に無数の小孔を開けることによって、気泡の連通化を促進させることができる。
なお、発泡体用組成物をエマルジョン化させて、泡立て器などを用いて樹脂組成物中に空気を混合させることにより、発泡エマルジョンとして用いてもよい。
The foam of this embodiment may be a foam having open cells in order to obtain a higher sound absorption coefficient.
As a method of obtaining a foam having open cells, a foaming agent and a cross-linking agent are added to the thermoplastic resin (a) and / or rubber (b) and vinyl aromatic block copolymer (c) described above and kneaded. Any conventionally known method can be applied as long as the foam composition is heated and foamed to form a foam, and then mechanically deformed to make the bubbles communicate with each other. The method is not particularly limited.
Among such methods, in particular, as described in Japanese Patent Publication No. 62-19294 and Japanese Patent Publication No. 1-444499, after the foam composition is heat-molded into a desired shape, gold which is not airtight is used. Examples include a method of heating under normal pressure in a mold to simultaneously decompose the cross-linking agent and the foaming agent to form bubbles, and then mechanically deform to make the bubbles communicate.
As an example of the foaming / crosslinking process, for example, the foam composition is placed in a non-airtight mold having a desired cross-sectional shape and dimensions, that is, not sealed, and placed in the mold, and the metal plate of the mold The method of heating the said composition indirectly by heating from the outside is mentioned.
Also, there is a method in which both surfaces of the foam composition sheet are crosslinked by irradiating with an electron beam, and the resulting crosslinked foam composition sheet is heated through a hot-air foaming furnace for foaming. Can be mentioned.
For example, by applying compressive deformation to the foam obtained as described above (so-called closed-cell foam) with, for example, a constant-speed two-roll, the foam film is broken, and the foam is connected to obtain an open-cell foam. It is done. At this time, an infinite number of small needles are provided on the surface of the constant-velocity two-roll, or a roll provided with an infinite number of needles is arranged before and / or after the constant-speed two-roll, and an infinite number of surfaces are provided on the surface of the bubble body. By opening the small holes, the communication of the bubbles can be promoted.
In addition, you may use as a foaming emulsion by emulsifying the composition for foams and mixing air in a resin composition using a whisk.
本実施形態の発泡体は、他の例えば繊維シート等のシートを積層して用いてもよい。 The foam of this embodiment may be used by laminating other sheets such as fiber sheets.
〔用途〕
本実施形態の発泡体用組成物、及び発泡体は、事務機器、音響機器、家庭用電気製品をはじめとして、各種機器の内外装材、自動車用の内外装材、あるいは住居の床や内装材等に利用できる。
[Use]
The foam composition and foam of the present embodiment include office equipment, acoustic equipment, household electrical appliances, various equipment interior and exterior materials, automotive interior and exterior materials, residential floors and interior materials, and the like. Available to:
以下、本発明の実施例と比較例を挙げて具体的に説明するが、本発明は下記の例に限定されるものではない。
実施例及び比較例に用いた評価法、及び測定方法を下記に示す。
Hereinafter, although an example and a comparative example of the present invention are given and explained concretely, the present invention is not limited to the following examples.
Evaluation methods and measurement methods used in Examples and Comparative Examples are shown below.
〔Ｉ．（ｃ）の組成、及び構造評価〕
（Ｉ−１）スチレン含有量、共役ジエンのビニル結合量、共役ジエンに基づく二重結合の水素添加率
ポリマー中のスチレン単位、ブタジエンの１，４−結合単位、及び１，２−結合単位、エチレン単位、あるいはブチレン単位量は、核磁気共鳴スペクトル解析（ＮＭＲ）により下記の条件で測定した。
測定機器：ＪＮＭ−ＬＡ４００（ＪＥＯＬ製）
溶媒：重水素化クロロホルム
測定サンプル：ポリマーを水素添加する前後の抜き取り品
サンプル濃度：５０ｍｇ／ｍｌ
観測周波数：４００ＭＨｚ
化学シフト基準：ＴＭＳ（テトラメチルシラン）
パルスディレイ：２．９０４秒
スキャン回数：６４回
パルス幅：４５°
測定温度：２６℃
[I. (C) Composition and Structure Evaluation]
(I-1) Styrene content, vinyl bond amount of conjugated diene, hydrogenation rate of double bond based on conjugated diene, styrene unit in polymer, 1,4-bond unit of butadiene, and 1,2-bond unit, The amount of ethylene units or butylene units was measured under the following conditions by nuclear magnetic resonance spectrum analysis (NMR).
Measuring instrument: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Sample: Sample taken before and after hydrogenation of polymer Sample concentration: 50 mg / ml
Observation frequency: 400 MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C
（Ｉ−２）ビニル芳香族系ブロック共重合体（ｃ）中の、ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）の含有量
Ｉ．Ｍ．Ｋｏｌｔｈｏｆｆ，ｅｔ ａｌ．，Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．，１９４６，Ｖｏｌ．１，ｐ．４２９に記載の四酸化オスミウム酸法で測定した。
測定サンプル：下記〔ＩＩＩ．〕で作製するビニル芳香族系ブロック共重合体（ｃ）が、水素添加される前段階における抜き取り品。
ポリマー分解用溶液：オスミウム酸０．１ｇを第３級ブタノール１２５ｍＬに溶解した溶液。
(I-2) Content of polymer block (c1) mainly composed of vinyl aromatic monomer in vinyl aromatic block copolymer (c) M.M. Kolthoff, et al. , J .; Polym. Sci. , 1946, Vol. 1, p. 429, and measured by the osmium tetroxide method.
Measurement sample: [III. The vinyl aromatic block copolymer (c) prepared in the above step is a product extracted before hydrogenation.
Polymer decomposition solution: a solution in which 0.1 g of osmic acid was dissolved in 125 mL of tertiary butanol.
（Ｉ−３）数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）
下記の条件で、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
ポリスチレン（ＰＳ）換算分子量で求めた。
測定装置：ＨＬＣ−８２２０（ＴＯＳＯＨ社製、商品名）
カラム：ＴＳＫｇｅｌＧＭＨＸＬ ＳｕｐｅｒＨ５０００：１本、ＳｕｐｅｒＨ４０００：２本（ＴＯＳＯＨ社製、商品名）
溶媒：テトラヒドロフラン
温度：４０℃
検量線用サンプル：市販（ＴＯＳＯＨ社製）の標準ポリスチレン、１０点測定
(I-3) Number average molecular weight (Mn), weight average molecular weight (Mw)
It measured by gel permeation chromatography (GPC) on the following conditions.
The molecular weight was calculated in terms of polystyrene (PS).
Measuring device: HLC-8220 (trade name, manufactured by TOSOH)
Column: TSKgelGMHXL SuperH5000: 1 and SuperH4000: 2 (trade name, manufactured by TOSOH)
Solvent: Tetrahydrofuran Temperature: 40 ° C
Calibration curve sample: commercially available standard polystyrene (manufactured by TOSOH), 10-point measurement
（Ｉ−４）ｔａｎδピーク温度
ｔａｎδピーク温度は、動的粘弾性測定（１Ｈｚ）により得た。
具体的には、動的粘弾性データは、試料を、幅１０ｍｍ、長さ３５ｍｍのサイズにカットし、装置ＡＲＥＳ（ティーエイインスツルメントー株式会社製、商品名）の捻りタイプのジオメトリーに試料をセットし、実効測定長さは２５ｍｍ、ひずみ０．５％、周波数１Ｈｚ、−６０℃から１００℃まで、昇温速度３℃／分の条件で測定した。
ピーク温度は、ＲＳＩ Ｏｒｃｈｅｓｔｒａｔｏｒ（ティーエイインスツルメントー株式会社製、商品名）の自動測定より求めた。
(I-4) tan δ peak temperature The tan δ peak temperature was obtained by dynamic viscoelasticity measurement (1 Hz).
Specifically, the dynamic viscoelasticity data is obtained by cutting the sample into a size of 10 mm in width and 35 mm in length, and applying the sample to the torsion type geometry of the device ARES (trade name, manufactured by TI Instrument Co., Ltd.). The effective measurement length was 25 mm, the strain was 0.5%, the frequency was 1 Hz, and the temperature was measured from −60 ° C. to 100 ° C. under the temperature increase rate of 3 ° C./min.
The peak temperature was determined by automatic measurement of RSI Orchestrator (trade name, manufactured by TI Instrument Co., Ltd.).
〔ＩＩ．水素添加触媒の調製〕
下記ＩＩＩの、ビニル芳香族系ブロック共重合体（ｃ−１）を製造する際に行う水素添加反応に用いた水素添加触媒は、下記の方法で調製した。
窒素置換した反応容器に、乾燥、精製したシクロヘキサン１リットルを仕込み、ビス（シクロペンタジエニル）チタニウムジクロリド１００ミリモルを添加し、十分に攪拌しながらトリメチルアルミニウム２００ミリモルを含むｎ−ヘキサン溶液を添加して、室温にて約３日間反応させた。
[II. Preparation of hydrogenation catalyst)
The hydrogenation catalyst used for the hydrogenation reaction performed when producing the vinyl aromatic block copolymer (c-1) of III below was prepared by the following method.
Charge 1 liter of dry and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (cyclopentadienyl) titanium dichloride, and add an n-hexane solution containing 200 mmol of trimethylaluminum while stirring thoroughly. For about 3 days at room temperature.
〔ＩＩＩ．ビニル芳香族系ブロック共重合体：（ｃ−１）、（ｃ−２）の調製〕
（ｃ−１）
攪拌装置及びジャケットを備えた槽型反応器（内容積：１０リットル）に、シクロヘキサン２００質量部を仕込み、温度７０℃に調整した。
その後、ｎ−ブチルリチウムを０．０７質量部、反応器の底部から添加した。
次に、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンを０．１０質量部、添加した。
その後、スチレンを７．５質量部、約１０分間で供給した。
供給停止後、１５分間、反応器内温度を７０℃に維持し、反応させた。
次に、シクロヘキサンで２４質量％に希釈したブタジエン３４質量部と、スチレン５１質量部とを、６０分間かけて一定速度で連続的に反応器に供給した。
供給停止後、１５分間反応器内温度を７０℃に維持し、その後に、シクロヘキサンで２４質量％に希釈したスチレンを７．５質量部、約１０分で供給した。
その間の反応器内温度を７０〜８０℃になるように調整した。
供給停止後、１０分間反応器内温度を７０℃に調整しながら反応させた。
その後、メタノールを０．０３質量部添加した。
次に、上記〔ＩＩ〕で調製した水素添加触媒を添加し、水素圧０．７ＭＰａ、温度６５℃で水素添加反応を１時間行った。
反応終了後、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを添加し、ビニル芳香族ブロック共重合体（ｃ−１）を得た。
このビニル芳香族ブロック共重合体（ｃ−１）は、ビニル芳香族単量体を主体とする重合体ブロックの含有量が１５質量％、１，４−ブタジエン単位が１６質量％、水素添加１，４−ブタジエン単位が７質量％、水素添加１，２−ブタジエン単位が１１質量％であった。
また、共役ジエン中の不飽和基の水素添加率は５０ｍｏｌ％、重量平均分子量は１３万であった。
さらに、ｔａｎδピーク温度は２０℃であった。
またさらに、このビニル芳香族ブロック共重合体（ｃ−１）のＳＰ値は、１８．６１（（Ｊ／ｃｍ3）1/2）、ｃ１（ビニル芳香族単量体を主体とする重合体ブロック）のＳＰ値は、１９．５１（（Ｊ／ｃｍ3）1/2）、ｃ２（ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック）のＳＰ値は、１８．４５（（Ｊ／ｃｍ3）1/2）であった。
[III. Vinyl aromatic block copolymer: Preparation of (c-1) and (c-2)]
(C-1)
A tank reactor (internal volume: 10 liters) equipped with a stirrer and a jacket was charged with 200 parts by mass of cyclohexane and adjusted to a temperature of 70 ° C.
Thereafter, 0.07 parts by mass of n-butyllithium was added from the bottom of the reactor.
Next, 0.10 parts by mass of N, N, N ′, N′-tetramethylethylenediamine was added.
Thereafter, 7.5 parts by mass of styrene was supplied in about 10 minutes.
After stopping the supply, the reaction was carried out while maintaining the temperature in the reactor at 70 ° C. for 15 minutes.
Next, 34 parts by mass of butadiene diluted to 24% by mass with cyclohexane and 51 parts by mass of styrene were continuously fed to the reactor at a constant rate over 60 minutes.
After stopping the supply, the temperature in the reactor was maintained at 70 ° C. for 15 minutes, and then 7.5 parts by mass of styrene diluted to 24% by mass with cyclohexane was supplied in about 10 minutes.
During that time, the temperature in the reactor was adjusted to 70 to 80 ° C.
After stopping the supply, the reaction was carried out for 10 minutes while adjusting the temperature in the reactor to 70 ° C.
Thereafter, 0.03 parts by mass of methanol was added.
Next, the hydrogenation catalyst prepared in [II] above was added, and a hydrogenation reaction was performed for 1 hour at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.
After completion of the reaction, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to obtain a vinyl aromatic block copolymer (c-1).
This vinyl aromatic block copolymer (c-1) has a content of polymer block mainly composed of vinyl aromatic monomer of 15% by mass, 1,4-butadiene unit of 16% by mass, hydrogenation 1 , 4-butadiene unit was 7% by mass, and hydrogenated 1,2-butadiene unit was 11% by mass.
The hydrogenation rate of unsaturated groups in the conjugated diene was 50 mol%, and the weight average molecular weight was 130,000.
Furthermore, the tan δ peak temperature was 20 ° C.
Further, the SP value of this vinyl aromatic block copolymer (c-1) is 18.61 ((J / cm 3 ) 1/2 ), c1 (polymer mainly composed of vinyl aromatic monomer). The SP value of the block) is 19.51 ((J / cm 3 ) 1/2 ), and the SP value of c2 (a copolymer block mainly composed of a vinyl aromatic monomer and a conjugated diene monomer) is It was 18.45 ((J / cm 3 ) 1/2 ).
（ｃ−２）
攪拌装置及びジャケットを備えた槽型反応器（内容積：１０リットル）に、シクロヘキサン２００質量部を仕込み、温度５０℃に調整した。
その後、ｎ−ブチルリチウムを０．０９質量部、反応器の底部から添加した。
次に、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンを０．２６質量部、添加した。
その後、スチレンを１０質量部、約１０分間で供給した。
供給停止後、１５分間反応器内温度を５０℃に維持し、反応させた。
次に、シクロヘキサンで２４質量％に希釈したイソプレン８０質量部を、７０分間かけて一定速度で連続的に反応器に供給した。
供給停止後、１５分間反応器内温度を５０℃に維持した後に、シクロヘキサンで２４質量％に希釈したスチレンを１０質量部、約１０分で供給した。なお、その間の反応器内温度を５０℃になるように調整した。
供給停止後、１５分間反応器内温度を５０℃に調整しながら反応させた。
その後、メタノールを０．０４質量部添加した。
その後、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを添加し、ビニル芳香族ブロック共重合体（ｃ−２）を得た。
このビニル芳香族系ブロック共重合体（ｃ−２）は、ビニル芳香族単量体を主体とする重合体ブロックの含有量が２０質量％、１，４−イソプレン単位が２４質量％、３，４−イソプレン単位が４８質量％、１，２−イソプレン単位が８質量％、重量平均分子量は１０万であった。
ｔａｎδピーク温度は１７℃であった。
またさらに、このビニル芳香族ブロック共重合体（ｃ−２）のＳＰ値は１７．０９（（Ｊ／ｃｍ3）1/2）であった。
ｃ１のＳＰ値は、１９．５１（（Ｊ／ｃｍ3）1/2）、イソプレンブロックのＳＰ値は、１６．５９（（Ｊ／ｃｍ3）1/2）であった。
(C-2)
A tank reactor (internal volume: 10 liters) equipped with a stirrer and a jacket was charged with 200 parts by mass of cyclohexane and adjusted to a temperature of 50 ° C.
Thereafter, 0.09 parts by mass of n-butyllithium was added from the bottom of the reactor.
Next, 0.26 parts by mass of N, N, N ′, N′-tetramethylethylenediamine was added.
Thereafter, 10 parts by mass of styrene was supplied in about 10 minutes.
After stopping the supply, the temperature inside the reactor was maintained at 50 ° C. for 15 minutes to carry out the reaction.
Next, 80 parts by mass of isoprene diluted to 24% by mass with cyclohexane was continuously supplied to the reactor at a constant rate over 70 minutes.
After the supply was stopped, the reactor internal temperature was maintained at 50 ° C. for 15 minutes, and then 10 parts by mass of styrene diluted to 24% by mass with cyclohexane was supplied in about 10 minutes. The reactor internal temperature was adjusted to 50 ° C.
After stopping the supply, the reaction was carried out for 15 minutes while adjusting the temperature in the reactor to 50 ° C.
Thereafter, 0.04 parts by mass of methanol was added.
Thereafter, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to obtain a vinyl aromatic block copolymer (c-2).
In this vinyl aromatic block copolymer (c-2), the content of the polymer block mainly composed of a vinyl aromatic monomer is 20% by mass, the 1,4-isoprene unit is 24% by mass, 3, The 4-isoprene unit was 48 mass%, the 1,2-isoprene unit was 8 mass%, and the weight average molecular weight was 100,000.
The tan δ peak temperature was 17 ° C.
Furthermore, the SP value of this vinyl aromatic block copolymer (c-2) was 17.09 ((J / cm 3 ) 1/2 ).
The SP value of c1 was 19.51 ((J / cm 3 ) 1/2 ), and the SP value of the isoprene block was 16.59 ((J / cm 3 ) 1/2 ).
〔実施例１、２〕、〔比較例１、２〕
〔ＩＶ．発泡体の製造〕
下記表１に示す第１工程の配合成分を、下記表１に示す割合に従い、加圧ニーダーを用いて、設定温度１２０℃で、１０分混合を行った。
その後に、ロールオープンミルを用いて、第１工程の混練物と、第２工程の各配合成分とを、設定温度１１０℃で、５分混合した。
次に、圧縮成形機を用いて、上記の混練物を、温度１６０℃、圧力１５０ｋｇｆ／ｃｍ2で１５分間圧縮成形した。
その後、圧力を開放して重合体組成物の架橋発泡体を得た。
得られた架橋発泡体の上面と下面をスライスし、厚み５ｍｍ発泡体を得た。
下記表１中、第１工程で用いた材料（ａ）：ＬＤＰＥ、第２工程で用いたジクミルパーオキサイド、発泡剤の具体的な材料名を下記に示す。
ＬＤＰＥ：ノバテックＹＦ３０（日本ポリエチレン株製、商品名、ＭＦＲ（ＪＩＳ−Ｋ６９２２−２：１．１ｇ／１０分）
発泡剤 ：ＦＥ７８８（永和化成工業製、商品名、ＡＤＣＡ系）
ＤＣＰ ：ジクミルパーオキサイド
[Examples 1 and 2], [Comparative Examples 1 and 2]
[IV. Production of foam)
The blending components of the first step shown in Table 1 below were mixed for 10 minutes at a set temperature of 120 ° C. using a pressure kneader according to the ratio shown in Table 1 below.
Then, the kneaded material of the 1st process and each compounding component of the 2nd process were mixed for 5 minutes at the preset temperature of 110 degreeC using the roll open mill.
Next, the above kneaded material was compression molded at a temperature of 160 ° C. and a pressure of 150 kgf / cm 2 for 15 minutes using a compression molding machine.
Thereafter, the pressure was released to obtain a crosslinked foamed polymer composition.
The top and bottom surfaces of the obtained crosslinked foam were sliced to obtain a foam having a thickness of 5 mm.
In Table 1 below, specific materials of the material (a) used in the first step: LDPE, dicumyl peroxide used in the second step, and the foaming agent are shown below.
LDPE: Novatec YF30 (Nippon Polyethylene Co., Ltd., trade name, MFR (JIS-K6922-2: 1.1 g / 10 min)
Foaming agent: FE788 (manufactured by Eiwa Chemical Industries, trade name, ADCA series)
DCP: Dicumyl peroxide
〔Ｖ．吸音率の測定方法〕
上記〔ＶＩ．発泡体の製造〕により得られた発泡体を、トムソン刃でＡ管、Ｂ管用の形に打ち抜き、自動垂直入射吸音管（ＴＹＰＥ１００４１Ａ）で吸音率の測定を行った。
測定方法は、ＪＩＳ Ａ１４０５「管内法による建築材料の垂直入射吸音率測定法」に従って行った。
Ａ管法は、１００〜１２５０Ｈｚの範囲で測定を行い、得られた結果より、吸音率の最大値を読みとった。
吸音率は大きい方が好ましい。
[V. (Measurement method of sound absorption coefficient)
[VI. The foam obtained by [Production of Foam] was punched into shapes for A and B tubes with a Thomson blade, and the sound absorption coefficient was measured with an automatic normal incidence sound absorbing tube (TYPE10041A).
The measuring method was performed according to JIS A1405 “Measurement method of normal incidence sound absorption coefficient of building material by pipe method”.
In the A tube method, measurement was performed in the range of 100 to 1250 Hz, and the maximum value of the sound absorption coefficient was read from the obtained result.
A higher sound absorption rate is preferred.
実施例１、２においては、いずれも優れた吸音率を有する発泡体が得られた。 In Examples 1 and 2, foams having an excellent sound absorption rate were obtained.
本発明の発泡体用組成物は、事務機器、音響機器、家庭用電気製品をはじめとして、各種機器の内外装材、自動車用の内外装材、住居の床や内装材等として、産業上の利用可能性がある。 The foam composition of the present invention is used industrially as an interior / exterior material for various devices, such as office equipment, audio equipment, and household electrical appliances, interior / exterior materials for automobiles, floors and interior materials for houses, etc. there is a possibility.
Claims (11)
ビニル芳香族系ブロック共重合体（ｃ）と、
を、含有し、
前記ビニル芳香族系ブロック共重合体（ｃ）が、−２０℃以上５０℃以下の範囲にｔａｎδピーク温度を有し、
前記ビニル芳香族系ブロック共重合体（ｃ）のＳＰ値（（Ｊ／ｃｍ3）1/2）が、１７．３以上２０．０以下である吸音性発泡体用組成物。 A thermoplastic resin (a) and / or rubber (b);
Vinyl aromatic block copolymer (c);
Containing,
The vinyl aromatic block copolymer (c) has a tan δ peak temperature in the range of −20 ° C. or more and 50 ° C. or less,
The composition for sound-absorbing foams in which the SP value ((J / cm 3 ) 1/2 ) of the vinyl aromatic block copolymer (c) is 17.3 or more and 20.0 or less.
前記ビニル芳香族系ブロック共重合体（ｃ）のＳＰ値（（Ｊ／ｃｍ3）1/2）との差が、０．５（（Ｊ／ｃｍ3）1/2）以上である請求項１又は２に記載の吸音性発泡体用組成物。 SP value ((J / cm 3 ) 1/2 ) of the thermoplastic resin (a) or rubber (b),
The difference from the SP value ((J / cm 3 ) 1/2 ) of the vinyl aromatic block copolymer (c) is 0.5 ((J / cm 3 ) 1/2 ) or more. The composition for sound-absorbing foams according to 1 or 2.
ビニル芳香族単量体と共役ジエン単量体とを主体とする共重合体である請求項１乃至３のいずれか一項に記載の吸音性発泡体用組成物。 The vinyl aromatic block copolymer (c) is
The composition for sound-absorbing foams according to any one of claims 1 to 3, which is a copolymer mainly composed of a vinyl aromatic monomer and a conjugated diene monomer.
ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を、１つ以上を含有する請求項１乃至４のいずれか一項に記載の吸音性発泡体用組成物。 The vinyl aromatic block copolymer (c) is
The composition for sound-absorbing foams as described in any one of Claims 1 thru | or 4 which contains one or more polymer blocks (c1) which have a vinyl aromatic monomer as a main component.
前記ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）のＳＰ値と、
前記（ｃ１）以外のブロックのＳＰ値との差の少なくとも一つが、
２．５以下である請求項１乃至５のいずれか一項に記載の吸音性発泡体用組成物。 In the vinyl aromatic block copolymer (c),
SP value of the polymer block (c1) mainly composed of the vinyl aromatic monomer;
At least one of the differences from the SP values of the blocks other than (c1) is as follows:
It is 2.5 or less, The composition for sound-absorbing foams as described in any one of Claims 1 thru | or 5.
ビニル芳香族単量体を主体とする重合体ブロック（ｃ１）を１つ以上と、
ビニル芳香族単量体と共役ジエン単量体を主体とする共重合体ブロック（ｃ２）を１つ以上、含有する請求項１乃至６のいずれか一項に記載の吸音性発泡体用組成物。 The vinyl aromatic block copolymer (c) is
One or more polymer blocks (c1) mainly composed of vinyl aromatic monomers;
The composition for sound-absorbing foams according to any one of claims 1 to 6, comprising at least one copolymer block (c2) mainly composed of a vinyl aromatic monomer and a conjugated diene monomer. .
水素添加前におけるビニル芳香族ブロック共重合体中の総共役ジエンの不飽和基のうち、５ｍｏｌ％以上８５ｍｏｌ％以下の範囲が水素添加されている請求項１乃至８のいずれか一項に記載の吸音性発泡体用組成物。 The vinyl aromatic block copolymer (c) is a hydrogenated product,
The range of 5 mol% or more and 85 mol% or less is hydrogenated among the unsaturated groups of the total conjugated diene in the vinyl aromatic block copolymer before hydrogenation. A composition for sound absorbing foam.
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| JP2009279453A JP2011122021A (en) | 2009-12-09 | 2009-12-09 | Composition for sound-absorbing foam and sound-absorbing foam |
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| JP2009279453A JP2011122021A (en) | 2009-12-09 | 2009-12-09 | Composition for sound-absorbing foam and sound-absorbing foam |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014181336A (en) * | 2013-03-21 | 2014-09-29 | Sumitomo Rubber Ind Ltd | Conductive rubber composition, transfer roller and image formation apparatus |
| WO2020022451A1 (en) * | 2018-07-27 | 2020-01-30 | 株式会社大阪ソーダ | Sound-absorbing material composition |
| CN113912957A (en) * | 2021-11-15 | 2022-01-11 | 新昌中国计量大学企业创新研究院有限公司 | Sound absorption material and preparation method thereof |
-
2009
- 2009-12-09 JP JP2009279453A patent/JP2011122021A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014181336A (en) * | 2013-03-21 | 2014-09-29 | Sumitomo Rubber Ind Ltd | Conductive rubber composition, transfer roller and image formation apparatus |
| US9583232B2 (en) | 2013-03-21 | 2017-02-28 | Sumitomo Rubber Industries, Ltd. | Electrically conductive rubber composition, transfer roller, and image forming apparatus |
| WO2020022451A1 (en) * | 2018-07-27 | 2020-01-30 | 株式会社大阪ソーダ | Sound-absorbing material composition |
| JPWO2020022451A1 (en) * | 2018-07-27 | 2021-08-19 | 株式会社大阪ソーダ | Composition for sound absorbing material |
| JP7287396B2 (en) | 2018-07-27 | 2023-06-06 | 株式会社大阪ソーダ | Composition for sound absorbing material |
| CN113912957A (en) * | 2021-11-15 | 2022-01-11 | 新昌中国计量大学企业创新研究院有限公司 | Sound absorption material and preparation method thereof |
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