JP2013204211A - Wallpaper and method for producing the same - Google Patents
Wallpaper and method for producing the same Download PDFInfo
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- JP2013204211A JP2013204211A JP2012076915A JP2012076915A JP2013204211A JP 2013204211 A JP2013204211 A JP 2013204211A JP 2012076915 A JP2012076915 A JP 2012076915A JP 2012076915 A JP2012076915 A JP 2012076915A JP 2013204211 A JP2013204211 A JP 2013204211A
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- resin
- foaming agent
- wallpaper
- foaming
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- 239000004088 foaming agent Substances 0.000 claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 9
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 17
- 238000003475 lamination Methods 0.000 claims description 3
- 238000005187 foaming Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 10
- 238000001125 extrusion Methods 0.000 abstract description 9
- -1 oxybisbenzenesulfonyl Chemical group 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 238000009474 hot melt extrusion Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、繊維質基材に無機充填剤と発泡剤とを含有する樹脂からなる層を積層してなる壁紙およびその製造方法に関するものであり、特には、均一な発泡状態を有する壁紙及びその製造方法に関する。 The present invention relates to a wallpaper obtained by laminating a layer made of a resin containing an inorganic filler and a foaming agent on a fibrous base material, and a method for producing the same. It relates to a manufacturing method.
従来主流であった塩化ビニル樹脂を発泡層とした壁紙は、環境汚染および可塑剤による健康への影響が懸念されて代替材料への移行が進んでいる。塩化ビニル樹脂の利点としては、成形加工性の良さ、難燃性を有すること、低コストであることが挙げられる。現在、代替材料としてはエチレン・酢酸ビニル共重合体樹脂、エチレン・メチルアクリレート共重合体樹脂といったエチレン共重合体等のポリオレフィン系樹脂の使用が考えられており、各種フィラーの添加による難燃性向上、発泡倍率向上によるコストの低減など改良も進められている。 Background Art Conventionally, wallpaper using a vinyl chloride resin foam layer as a mainstream has been moving to an alternative material due to concern about environmental pollution and health effects caused by plasticizers. Advantages of the vinyl chloride resin include good moldability, flame retardancy, and low cost. Currently, the use of polyolefin resins such as ethylene copolymers such as ethylene / vinyl acetate copolymer resins and ethylene / methyl acrylate copolymer resins is considered as an alternative material, and flame retardancy is improved by the addition of various fillers. Improvements such as cost reduction by increasing the expansion ratio are also being promoted.
しかし、ポリオレフィン系樹脂は、発泡適正粘度の温度範囲が狭く生産が安定しないという問題がある。特に発泡剤を含んだ状態で加熱溶融押出し製膜し、その後の工程で加熱発泡させる場合には、加熱溶融押出し工程より発泡工程は高い温度設定に限定されるので、より安定生産を行うことが困難になる。 However, the polyolefin resin has a problem that the temperature range of proper foaming viscosity is narrow and production is not stable. In particular, when a film is formed by heat-melt extrusion in a state containing a foaming agent and is heated and foamed in the subsequent process, the foaming process is limited to a higher temperature setting than the heat-melt extrusion process, so that more stable production can be performed. It becomes difficult.
そこで、加熱溶融押出しによる発泡剤入り樹脂層の製膜後に、電子線等の電離放射線照射架橋により樹脂を改質してから加熱発泡を行う製造法が提案されている。（特許文献１） In view of this, there has been proposed a production method in which after forming a resin layer containing a foaming agent by heat melt extrusion, the resin is modified by ionizing radiation irradiation crosslinking such as an electron beam and then heat foaming is performed. (Patent Document 1)
ところが、電離放射線照射架橋する場合にも樹脂の種類、膜厚、発泡剤の種類、添加量に合わせて所望の発泡倍率になるよう架橋の程度を調整することは容易ではない。また、架橋させるための装置代や製造工程が増えることによるコストアップが問題点として残った。 However, even when ionizing radiation irradiation crosslinking is performed, it is not easy to adjust the degree of crosslinking so as to obtain a desired expansion ratio in accordance with the type of resin, the film thickness, the type of foaming agent, and the amount added. In addition, an increase in cost due to an increase in equipment costs and manufacturing processes for crosslinking remained as a problem.
本発明は前記問題点を解決するためになされたものであり、その課題とするところは、溶融押出し製膜後に架橋による樹脂改質を行わなくても発泡工程にて安定して均一な発泡状態を得る方法を提供することにある。 The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to stably and uniformly foam in the foaming step without performing resin modification by crosslinking after melt extrusion film formation. It is to provide a method of obtaining.
本発明は前記課題を解決したものであり、すなわちその請求項１記載の発明は、少なくとも繊維質基材上に無機充填剤と発泡剤とを含有する樹脂からなる層を有する壁紙において、前記樹脂は１９０℃におけるメルトフローレートが５〜１５ｇ／１０分である１種または２種以上のエチレン・α−オレフィン共重合体樹脂と低密度ポリエチレンとの混練樹脂であり、前記発泡剤は分解温度が１４０〜１６０℃のアゾジカルボンアミド系発泡剤とオキシビスベンゼンスルホニルヒドラジド系発泡剤の少なくとも１種を含むものであり、前記樹脂を１００重量部として前記無機充填剤が５０〜１５０重量部、前記発泡剤が１〜９重量部であることを特徴とする壁紙である。 The present invention solves the above-mentioned problem, that is, the invention according to claim 1 is a wallpaper having a layer made of a resin containing an inorganic filler and a foaming agent on at least a fibrous base material. Is a kneaded resin of one or more ethylene / α-olefin copolymer resins having a melt flow rate at 190 ° C. of 5 to 15 g / 10 min and low density polyethylene, and the blowing agent has a decomposition temperature of It contains at least one of an azodicarbonamide-based foaming agent at 140 to 160 ° C. and an oxybisbenzenesulfonylhydrazide-based foaming agent, and the inorganic filler is 50 to 150 parts by weight based on 100 parts by weight of the resin. The wallpaper is characterized in that the agent is 1 to 9 parts by weight.
またその請求項２記載の発明は、前記無機充填剤と発泡剤とを含有する樹脂を加熱溶融して前記繊維質基材上に直接押出し、積層後に架橋による樹脂改質なしに加熱発泡させてなることを特徴とする請求項１記載の壁紙の製造方法である。 In the invention of claim 2, the resin containing the inorganic filler and the foaming agent is heated and melted, extruded directly onto the fibrous base material, and heated and foamed without resin modification by crosslinking after lamination. The wallpaper manufacturing method according to claim 1, wherein:
本発明はその請求項１記載の発明により、樹脂を限定することで低温度域で溶融押出し製膜を可能とし、発泡剤を限定することで当該温度域での分解・発泡を抑えることが可能となる。 According to the first aspect of the present invention, by limiting the resin, it is possible to perform melt extrusion film formation at a low temperature range, and by limiting the foaming agent, it is possible to suppress decomposition / foaming in the temperature range. It becomes.
本発明はその請求項２記載の発明により、溶融押出直接製膜後に加熱発泡させることで、架橋による樹脂改質なしに安定して均一な発泡が可能となる。 According to the invention of the second aspect, the present invention enables stable and uniform foaming without resin modification by crosslinking by heat foaming after melt extrusion direct film formation.
以下、本発明の実施の形態について、図面に基づき詳細に説明する。図１に本発明の壁紙の一実施例の断面の構造を示す。繊維質基材２上に発泡樹脂層１を設けてなる。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the wallpaper of the present invention. A foamed resin layer 1 is provided on a fibrous base material 2.
本発明における発泡樹脂層１に使用されるエチレン・α−オレフィン共重合体樹脂は、エチレンとα−オレフィンの共重合体であるが、α−オレフィンの例としては、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン等が挙げられる。中でもプロピレン、１−ブテンが好適である。これらのα−オレフィンは１種または２種以上をエチレンとの共重合に使用することができる。エチレン・α−オレフィン共重合体樹脂は低温度域で溶融押出し製膜可能であることから発泡剤を発泡させずに製膜するのに適している。 The ethylene / α-olefin copolymer resin used for the foamed resin layer 1 in the present invention is a copolymer of ethylene and α-olefin, and examples of α-olefin include propylene, 1-butene, 1 -Pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and the like. Of these, propylene and 1-butene are preferable. One or more of these α-olefins can be used for copolymerization with ethylene. The ethylene / α-olefin copolymer resin is suitable for forming a film without foaming a foaming agent since it can be melt-extruded to form a film at a low temperature.
発泡樹脂層１に使用される低密度ポリエチレン樹脂は発泡時の溶融張力を調整する目的で使用する。低密度ポリエチレン樹脂であれば特に規定するところではないが、ラジカル触媒を用いエチレンを高圧下で重合したいわゆる高圧法ポリエチレンがエチレンの重合過程でポリエチレン主鎖に沿って適度な分岐を生じるという点において好適である。 The low density polyethylene resin used for the foamed resin layer 1 is used for the purpose of adjusting the melt tension at the time of foaming. Although it is not particularly specified as long as it is a low density polyethylene resin, a so-called high pressure polyethylene obtained by polymerizing ethylene under a high pressure using a radical catalyst causes appropriate branching along the polyethylene main chain during the polymerization of ethylene. Is preferred.
前記エチレン・α−オレフィン共重合体樹脂と前記低密度ポリエチレン樹脂に無機充填剤および発泡剤を混練して溶融押出し製膜することになるが、前記エチレン・α−オレフィン共重合体樹脂と前記低密度ポリエチレン樹脂は混練状態で１９０℃におけるメルトフローレートが５〜１５ｇ／１０分になる組み合わせを選択した。５未満の場合、溶融押出し製膜時のせん断による発熱量が大きいため発泡し易くなり、１５より大きいと発泡工程で樹脂の溶融張力が不足して、破泡し易い、発泡セル凝集による不均一な発泡状態になり易いといった問題がある。 The ethylene / α-olefin copolymer resin and the low-density polyethylene resin are kneaded with an inorganic filler and a foaming agent to be melt-extruded to form the ethylene / α-olefin copolymer resin and the low-density polyethylene resin. As the density polyethylene resin, a combination in which the melt flow rate at 190 ° C. in a kneaded state was 5 to 15 g / 10 minutes was selected. If it is less than 5, the amount of heat generated by shearing during melt extrusion film formation is large, so foaming is likely to occur. If it is greater than 15, the resin has insufficient melt tension in the foaming process, and foaming tends to break, resulting in unevenness due to foam cell aggregation. There is a problem that it is easy to become a foaming state.
発泡樹脂層１に使用される無機充填剤としては、炭酸カルシウム、硫酸バリウム、酸化チタン、水酸化マグネシウム、クレー、タルク、マイカ、シリカ、アルミナ、ケイソウ土、ケイ砂等が使用できる。着色や隠蔽性、難燃性を考慮して選択を行い、複数の併用も可能である。ただし、無機充填剤の添加量は発泡状態、コスト、難燃性に影響をおよぼし、安価な無機充填剤を多量に添加して増量効果でコストを抑えることは可能であるが、過多な状態では発泡が低倍率に留まる。また少量過ぎる場合は発泡セルが凝集する傾向にあり均一な発泡状態を生成しにくいという不具合とともに、特に難燃性に寄与する無機充填剤が少量であると難燃性が不十分になるという不具合が生じるので、添加量としては樹脂分を１００重量部とした場合５０〜１５０重量部が好適である。 As the inorganic filler used for the foamed resin layer 1, calcium carbonate, barium sulfate, titanium oxide, magnesium hydroxide, clay, talc, mica, silica, alumina, diatomaceous earth, silica sand, and the like can be used. Selection is made in consideration of coloring, hiding properties, and flame retardancy, and multiple combinations are possible. However, the amount of inorganic filler added affects the foaming state, cost, and flame retardancy, and it is possible to add a large amount of inexpensive inorganic filler to reduce the cost due to the increase effect. Foaming remains at a low magnification. In addition, if the amount is too small, the foamed cells tend to agglomerate and it is difficult to produce a uniform foamed state, and in particular, if the amount of the inorganic filler that contributes to flame retardancy is small, the flame retardancy becomes insufficient. Therefore, the addition amount is preferably 50 to 150 parts by weight when the resin content is 100 parts by weight.
発泡樹脂層１に使用される発泡剤としては、アゾジカルボンアミド系発泡剤とオキシビスベンゼンスルホニルヒドラジド系発泡剤の少なくとも１種を含むもので分解温度が１４０〜１６０℃であるものを使用する。１４０℃未満のものを使用した場合、前述の少なくとも１種または２種以上のエチレン・α−オレフィン共重合体樹脂と低密度ポリエチレン樹脂の混合樹脂を加熱溶融押出し製膜する工程で発泡剤が分解し発泡してしまう。また、１６０℃より高いものを使用した場合、製膜工程での発泡は抑制できるが加熱発泡工程の温度条件を高温にしなければならず、製膜されていた樹脂層の溶融張力が低下し過ぎて、発泡ガスにより生じた発泡セルが凝集して大きくなり過ぎて強度が保てなかったり、凝集状態によってセルの大きさが均一でなかったり、樹脂内に発泡ガスが溜まらずに多量に外部に放出されて発泡不足になってしまう。また発泡剤の発生ガス量に関しては、前記樹脂に対してはガス抜けやセル凝集の問題と高発泡倍率確保の兼ね合いで１００〜２００ｍｌ／ｇのものが好適である。添加量としては樹脂分を１００重量部とした場合１〜９重量部が好適である。 As the foaming agent used for the foamed resin layer 1, a foaming agent containing at least one of an azodicarbonamide-based foaming agent and an oxybisbenzenesulfonylhydrazide-based foaming agent and having a decomposition temperature of 140 to 160 ° C. is used. When the one below 140 ° C. is used, the foaming agent is decomposed in the process of heating, melt-extrusion and film formation of the above-mentioned mixed resin of at least one or two or more ethylene / α-olefin copolymer resins and low density polyethylene resins. And foam. In addition, when a temperature higher than 160 ° C. is used, foaming in the film forming process can be suppressed, but the temperature condition of the heating foaming process has to be increased, and the melt tension of the resin layer that has been formed is too low. The foamed cells generated by the foaming gas are aggregated and become too large to maintain strength, the size of the cells is not uniform due to the aggregated state, or the foamed gas does not accumulate in the resin and a large amount of It will be released and become insufficiently foamed. Regarding the amount of gas generated by the foaming agent, a resin having a gas content of 100 to 200 ml / g is suitable for the resin in view of outgassing and cell aggregation problems and securing a high expansion ratio. The addition amount is preferably 1 to 9 parts by weight when the resin content is 100 parts by weight.
繊維質基材２に関しては特に限定されるものではないが、天然パルプや合成パルプから抄造した紙、それらに無機物を混ぜて混抄した紙、織布、不織布等壁紙の用途に応じて適宜選定可能である。 Although it does not specifically limit regarding the fiber base material 2, it can select suitably according to the use of wallpaper, such as paper made from natural pulp and synthetic pulp, paper mixed with them, and woven fabric, nonwoven fabric, etc. It is.
また、繊維質基材２上に加熱溶融された発泡樹脂層１の樹脂を直接押し出して積層することにより繊維質基材と発泡樹脂層の間に接着層が不要である。溶融張力が低い樹脂状態で発泡させた場合、発泡時には発泡樹脂層の表面から多少の発泡ガス抜けが発生し、基材側からも基材が繊維質であることから同様にガス抜けが発生している。しかし接着層を設けた場合は接着層側にガスが溜まり易く、発泡セルが凝集し易いため均一な発泡状態を得ることが困難である。そのため接着層が不要な加熱溶融押出しラミネート方式で繊維質基材と発泡樹脂層の積層を行う。 Moreover, the adhesive layer is unnecessary between the fibrous base material and the foamed resin layer by directly extruding and laminating the resin of the foamed resin layer 1 heated and melted on the fibrous base material 2. When foaming is performed in a resin state having a low melt tension, some foaming gas escapes from the surface of the foamed resin layer during foaming, and outgassing also occurs from the base material side because the base material is fibrous. ing. However, when the adhesive layer is provided, it is difficult to obtain a uniform foamed state because gas tends to accumulate on the adhesive layer side and the foamed cells tend to aggregate. Therefore, the fibrous base material and the foamed resin layer are laminated by a hot melt extrusion laminating method that does not require an adhesive layer.
発泡樹脂層１のエチレン・α−オレフィン共重合体樹脂として三井化学株式会社製の「タフマーＡ−２００８５Ｓ」と「タフマーＡ−１０８５Ｓ」を、低密度ポリエチレンとして住友化学株式会社製の「スミカセンＧ８０１」を使用した。重量比が、「タフマーＡ−２００８５Ｓ」／「タフマーＡ−１０８５Ｓ」／「スミカセンＧ８０１」＝４０／２０／４０になるよう配合し、更に全体の重量を１００重量部とした時に、無機充填剤として石原産業株式会社製の酸化チタン「ＣＲ−６０」を１５重量部と備北粉化工業株式会社の炭酸カルシウム「ソフトン１０００」を５０重量部、発泡剤として永和化成工業株式会社のアゾジカルボンアミド系発泡剤「ビニホールＳＥ＃３０」５重量部を添加して混練した。 “Tuffmer A-20085S” and “Tuffmer A-1085S” manufactured by Mitsui Chemicals, Inc. as the ethylene / α-olefin copolymer resin of the foamed resin layer 1, and “Sumikasen G801” manufactured by Sumitomo Chemical Co., Ltd. as the low density polyethylene. It was used. When blended so that the weight ratio is “Toughmer A-20085S” / “Toughmer A-1085S” / “Sumikasen G801” = 40/20/40, and the total weight is 100 parts by weight, 15 parts by weight of titanium oxide “CR-60” manufactured by Ishihara Sangyo Co., Ltd. and 50 parts by weight of calcium carbonate “Softon 1000” from Bihoku Flour Industry Co., Ltd. 5 parts by weight of the agent “Vinihol SE # 30” was added and kneaded.
なお、前記樹脂の１９０℃におけるメルトフローレートは、「タフマーＡ−２００８５Ｓ」が１８ｇ／１０分、「タフマーＡ−１０８５Ｓ」が１．２ｇ／１０分、「スミカセンＧ８０１」が２０ｇ／１０分であり、３種の前記配合比樹脂のメルトフローレートは１１ｇ／１０分である。また、発泡剤である「ビニホールＳＥ＃３０」の分解温度は１４２℃である。 The melt flow rate of the resin at 190 ° C. is 18 g / 10 minutes for “Tuffmer A-20085S”, 1.2 g / 10 minutes for “Tuffmer A-1085S”, and 20 g / 10 minutes for “Sumikasen G801”. The melt flow rate of the three kinds of the above-mentioned blending ratio resins is 11 g / 10 minutes. The decomposition temperature of “Vinole SE # 30”, which is a foaming agent, is 142 ° C.
繊維質基材２として株式会社興人製の坪量６５ｇの紙である「ＷＫ−６６５ＩＨＴ」を使用し、その上に前記配合樹脂を１３０℃になるよう加熱溶融して直接押出すと同時に圧をかけて紙に密着させて積層した。その後１７０℃の雰囲気温度のオーブンに投入し１２０秒間静置して発泡させた後オーブンから取り出して常温静置して冷却し、本発明の壁紙を作成した。前記加温条件下でシート温度としては１６５〜１６８℃まで加温されていた。 “WK-665IHT”, a paper with a basis weight of 65 g manufactured by Kojin Co., Ltd., is used as the fibrous base material 2, and the above compounded resin is heated and melted to 130 ° C. and extruded directly at the same time. And stuck to the paper for lamination. Thereafter, it was put into an oven at an ambient temperature of 170 ° C. and left to stand for 120 seconds to foam, and then taken out from the oven and left to cool at room temperature to prepare the wallpaper of the present invention. The sheet temperature was heated to 165 to 168 ° C. under the heating condition.
実施例１の「タフマーＡ−２００８５Ｓ」をエチレン・α−オレフィン共重合体樹脂「タフマーＡ−４０８５Ｓ」に替えて配合比を、「タフマーＡ−４０８５Ｓ」／「タフマー１０８５Ｓ」／「スミカセンＧ８０１」＝５０／２０／３０に変更した以外は実施例１と同様にして本発明の壁紙を作成した。前記配合の混練樹脂の１９０℃におけるメルトフローレートは５ｇ／１０分である。 “Tuffmer A-20085S” in Example 1 was replaced with ethylene / α-olefin copolymer resin “Tuffmer A-4085S”, and the mixing ratio was “Tuffmer A-4085S” / “Toughmer 1085S” / “Sumikasen G801” = A wallpaper of the present invention was prepared in the same manner as in Example 1 except that it was changed to 50/20/30. The kneaded resin having the above blend has a melt flow rate at 190 ° C. of 5 g / 10 min.
実施例１の発泡剤添加量を３重量部とした以外は実施例１と同様にして本発明の壁紙を作成した。 A wallpaper of the present invention was prepared in the same manner as in Example 1 except that the amount of foaming agent added in Example 1 was 3 parts by weight.
＜比較例１＞
実施例１の「タフマーＡ−２００８５Ｓ」を「タフマーＡ−３５０７０Ｓ」に替えて配合比を、「タフマーＡ−３５０７０Ｓ」／「タフマー１０８５Ｓ」／「スミカセンＧ８０１」＝６０／２０／２０に変更した以外は実施例１と同様にして壁紙を作成した。前記配合の混練樹脂の１９０℃におけるメルトフローレートは１６ｇ／１０分である。
<Comparative Example 1>
Except for changing “Tuffmer A-20085S” in Example 1 to “Tuffmer A-3570S” and changing the blending ratio to “Toughmer A-3570S” / “Toughmer 1085S” / “Sumikasen G801” = 60/20/20 Prepared a wallpaper in the same manner as in Example 1. The kneaded resin having the above blend has a melt flow rate of 16 g / 10 min at 190 ° C.
＜比較例２＞
実施例１の「タフマーＡ−２００８５Ｓ」を「タフマーＡ−４０８５Ｓ」に替えて配合比を、「タフマーＡ−４０８５Ｓ」／「タフマー１０８５Ｓ」／「スミカセンＧ８０１」＝６０／２０／２０に変更した以外は実施例１と同様にして壁紙を作成した。前記配合の混練樹脂の１９０℃におけるメルトフローレートは４ｇ／１０分である。
<Comparative example 2>
Except for changing “Tuffmer A-4085S” in Example 1 to “Tuffmer A-4085S” and changing the blending ratio to “Toughmer A-4085S” / “Toughmer 1085S” / “Sumikasen G801” = 60/20/20 Prepared a wallpaper in the same manner as in Example 1. The kneaded resin having the above blend has a melt flow rate at 190 ° C. of 4 g / 10 min.
＜比較例３＞
実施例１の発泡剤添加量を１０重量部とした以外は実施例１と同様にして壁紙を作成した。
<Comparative Example 3>
A wallpaper was prepared in the same manner as in Example 1 except that the amount of foaming agent added in Example 1 was 10 parts by weight.
＜比較例４＞
実施例１の発泡剤添加量を０重量部とした以外は実施例１と同様にして壁紙を作成した。
<Comparative example 4>
A wallpaper was prepared in the same manner as in Example 1 except that the amount of foaming agent added in Example 1 was changed to 0 part by weight.
＜比較例５＞
実施例１の発泡剤を永和化成工業株式会社のアゾジカルボンアミド系発泡剤「ビニホールＤＷ＃６」に変更し、５部添加とした以外は実施例１と同様にして壁紙を作製した。「ビニホールＤＷ＃６」は分解温度が１６５℃である。
<Comparative Example 5>
A wallpaper was prepared in the same manner as in Example 1 except that the foaming agent of Example 1 was changed to the azodicarbonamide-based foaming agent “Vinhole DW # 6” of Eiwa Kasei Kogyo Co., Ltd. and 5 parts were added. “Vinihole DW # 6” has a decomposition temperature of 165 ° C.
＜性能比較＞
以上のように作製した実施例１、２、３および比較例１、２、３、４、５の壁紙の発泡状態を目視にて観察して評価した。結果を表１に示す。
<Performance comparison>
The foamed states of the wallpaper of Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4, 5 produced as described above were visually observed and evaluated. The results are shown in Table 1.
本発明により、加熱溶融押出し樹脂層と繊維質基材とを積層してなる壁紙で、特には、積層後に加熱発泡させて均一な発泡状態を有する壁紙を得ることが可能となった。 According to the present invention, it is possible to obtain a wallpaper having a uniform foamed state by laminating by heating after laminating, with a wallpaper obtained by laminating a heat-melt extruded resin layer and a fibrous base material.
１…発泡樹脂層
２…繊維質基材
DESCRIPTION OF SYMBOLS 1 ... Foamed resin layer 2 ... Fiber base material
Claims (2)
前記樹脂は１９０℃におけるメルトフローレートが５〜１５ｇ／１０分である１種または２種以上のエチレン・α−オレフィン共重合体樹脂と低密度ポリエチレンとの混練樹脂であり、
前記発泡剤は分解温度が１４０〜１６０℃のアゾジカルボンアミド系発泡剤とオキシビスベンゼンスルホニルヒドラジド系発泡剤の少なくとも１種を含むものであり、
前記樹脂を１００重量部として前記無機充填剤が５０〜１５０重量部、前記発泡剤が１〜９重量部であることを特徴とする壁紙。 In a wallpaper having a layer made of a resin containing an inorganic filler and a foaming agent on at least a fibrous base material,
The resin is a kneaded resin of one or more ethylene / α-olefin copolymer resins having a melt flow rate at 190 ° C. of 5 to 15 g / 10 min and low-density polyethylene,
The foaming agent contains at least one of an azodicarbonamide-based foaming agent having a decomposition temperature of 140 to 160 ° C. and an oxybisbenzenesulfonylhydrazide-based foaming agent,
A wallpaper comprising 100 parts by weight of the resin, 50 to 150 parts by weight of the inorganic filler, and 1 to 9 parts by weight of the foaming agent.
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