JP2016221778A - Manufacturing method of foam laminated sheet - Google Patents
Manufacturing method of foam laminated sheet Download PDFInfo
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- JP2016221778A JP2016221778A JP2015109080A JP2015109080A JP2016221778A JP 2016221778 A JP2016221778 A JP 2016221778A JP 2015109080 A JP2015109080 A JP 2015109080A JP 2015109080 A JP2015109080 A JP 2015109080A JP 2016221778 A JP2016221778 A JP 2016221778A
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- superheated steam
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- laminated sheet
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000006260 foam Substances 0.000 title claims abstract description 22
- 239000011342 resin composition Substances 0.000 claims abstract description 147
- 238000004132 cross linking Methods 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 239000004088 foaming agent Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000005187 foaming Methods 0.000 claims description 56
- 238000003475 lamination Methods 0.000 claims description 21
- 229920005672 polyolefin resin Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000002950 deficient Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 145
- 238000005507 spraying Methods 0.000 description 32
- 239000000463 material Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004604 Blowing Agent Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- KINULKKPVJYRON-PVNXHVEDSA-N n-[(e)-[10-[(e)-(4,5-dihydro-1h-imidazol-2-ylhydrazinylidene)methyl]anthracen-9-yl]methylideneamino]-4,5-dihydro-1h-imidazol-2-amine;hydron;dichloride Chemical compound Cl.Cl.N1CCN=C1N\N=C\C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1\C=N\NC1=NCCN1 KINULKKPVJYRON-PVNXHVEDSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 238000012423 maintenance Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Molding Of Porous Articles (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、発泡積層シートの製造方法に関する。 The present invention relates to a method for producing a foam laminate sheet.
発泡壁紙に用いる発泡積層シートとして、従来から、紙基材上に塩化ビニル樹脂からなる発泡樹脂層を形成したものが知られている。しかしながら、近年、環境への配慮から、ハロゲンを含有しない樹脂として、エチレン−酢酸ビニル共重合体を含む樹脂のようなオレフィン系樹脂等が発泡樹脂層に用いられるようになってきている。このような樹脂からなる発泡積層シートは、例えば、エチレン−酢酸ビニル共重合体を含むエマルジョンにマイクロカプセル型発泡剤を添加した発泡樹脂組成物を紙基材に塗布して乾燥させた後、その表面に絵柄模様を印刷し、次いで加熱発泡させ、エンボス版により凹凸模様を形成することにより製造される。また、このような樹脂からなる発泡積層シートは、例えば、エチレン−酢酸ビニル共重合体に熱分解型発泡剤を添加した発泡樹脂組成物を、Ｔダイ押出機を用いて紙基材上に押し出し積層し、表面に絵柄模様を印刷し、次いで加熱発泡させ、エンボス版により凹凸模様を形成することにより製造されることもある。また、このような樹脂からなる発泡積層シートは、例えば、オレフィン系樹脂にガス発生型の発泡剤を添加した発泡樹脂組成物のシートに対し、架橋処理を施し、上記同様の工程を経ることにより製造されることもある。 2. Description of the Related Art Conventionally, a foamed laminated sheet used for foamed wallpaper is known in which a foamed resin layer made of a vinyl chloride resin is formed on a paper substrate. However, in recent years, in consideration of the environment, an olefin resin such as a resin containing an ethylene-vinyl acetate copolymer has been used for a foamed resin layer as a resin containing no halogen. The foamed laminated sheet made of such a resin, for example, after applying a foamed resin composition obtained by adding a microcapsule type foaming agent to an emulsion containing an ethylene-vinyl acetate copolymer on a paper substrate and drying it, It is manufactured by printing a pattern on the surface, then heating and foaming, and forming an uneven pattern with an embossed plate. In addition, the foamed laminated sheet made of such a resin is obtained by, for example, extruding a foamed resin composition obtained by adding a pyrolytic foaming agent to an ethylene-vinyl acetate copolymer onto a paper substrate using a T-die extruder. It is sometimes produced by laminating and printing a pattern on the surface, then heating and foaming, and forming an uneven pattern with an embossed plate. In addition, the foam laminated sheet made of such a resin is obtained by, for example, subjecting a foamed resin composition sheet obtained by adding a gas generating foaming agent to an olefin resin to a cross-linking treatment and performing the same steps as described above. Sometimes manufactured.
ところで、近年、発泡積層シートにおける架橋処理として、シランカップリング反応を用いる水架橋処理が知られつつある。水架橋処理の方法としては、例えば、発泡積層シートを湿潤下で養生する方法、又は、発泡積層シートに対して温水を付与する方法がある。しかしながら、これらの方法では、架橋に時間がかかってしまい、発泡積層シートの生産性を高めることが難しいという問題がある。 By the way, in recent years, a water crosslinking treatment using a silane coupling reaction has been known as a crosslinking treatment in a foamed laminated sheet. As a method of water crosslinking treatment, for example, there is a method of curing a foamed laminated sheet under moisture, or a method of applying warm water to the foamed laminated sheet. However, these methods have a problem that it takes time to crosslink and it is difficult to increase the productivity of the foamed laminated sheet.
そこで、水架橋処理を行う方法として、例えば１００℃を超える過熱水蒸気を用いる方法が考えられる。「過熱水蒸気」とは、飽和蒸気を更に加熱して飽和温度以上の蒸気温度を持たせた水蒸気である。過熱水蒸気を用いることにより、樹脂組成物層に対して熱と同時に水分を与えることができる。しかし、過熱水蒸気を用いる場合、上述した湿潤下で養生する方法等に比べれば架橋に要する時間が短縮されるものの、十分に架橋させるためには依然として時間がかかる。よって、十分且つ迅速に架橋させるため、更なる改善が望まれている。 Therefore, as a method for performing the water crosslinking treatment, for example, a method using superheated steam exceeding 100 ° C. can be considered. “Superheated steam” is steam that has been further heated to have a steam temperature equal to or higher than the saturation temperature. By using superheated steam, moisture can be given to the resin composition layer simultaneously with heat. However, when superheated steam is used, the time required for cross-linking is reduced as compared with the above-described method of curing under wet conditions, but it still takes time to sufficiently cross-link. Therefore, further improvement is desired in order to crosslink sufficiently and rapidly.
一方、十分且つ迅速に架橋させるためには、樹脂組成物層に供給する過熱水蒸気の温度を上げることが考えられる。しかし、過熱水蒸気の温度が高くなり過ぎると、樹脂組成物層に含まれる発泡剤の一部が高温となり架橋処理の段階で発泡し、架橋後の発泡処理によって生成される発泡積層シートの表面が荒れてしまうおそれがある。表面が荒れた発泡積層シートは、印刷に適さず、結果的に生産効率の著しい低下を招き、大量生産等の実情に見合わない。よって、単に過熱水蒸気の温度を上げるだけでは、生産性を高めることが難しい。 On the other hand, in order to crosslink sufficiently and rapidly, it is conceivable to raise the temperature of superheated steam supplied to the resin composition layer. However, if the temperature of the superheated steam becomes too high, a part of the foaming agent contained in the resin composition layer becomes high temperature and foams at the stage of crosslinking treatment, and the surface of the foamed laminated sheet generated by the foaming treatment after crosslinking is There is a risk of getting rough. A foam laminated sheet having a rough surface is not suitable for printing, and as a result, the production efficiency is remarkably lowered, which is not suitable for the actual situation such as mass production. Therefore, it is difficult to increase productivity simply by raising the temperature of superheated steam.
以上のことから、従来は、十分且つ迅速に架橋させると、発泡積層シートの表面に形成不良を生じやすく、生産性を高めることが難しいという問題が生じていた。 From the above, conventionally, there has been a problem that, when sufficiently and rapidly crosslinked, formation defects are likely to occur on the surface of the foamed laminated sheet and it is difficult to increase productivity.
本発明は、上記実情に鑑みてなされたものであり、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シートの製造方法を提供することを目的とする。 This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of the foaming lamination sheet which can be bridge | crosslinked sufficiently and rapidly and does not produce a formation defect on the surface easily.
上記課題を解決するため、本発明に係る発泡積層シートの製造方法は、基材と該基材上に形成される発泡樹脂層とを備える発泡積層シートの製造方法であって、発泡剤及びシラン架橋性樹脂層を含有する樹脂組成物層に対し、樹脂組成物層の温度が発泡剤の分解温度に対して＋６５℃を超えない温度となるように過熱水蒸気を供給する工程を含み、過熱水蒸気を供給する工程において、過熱水蒸気を１５ｋｇ/時間以上且つ１００ｋｇ/時間以下の噴霧蒸気量となるように樹脂組成物層に対して供給することにより、樹脂組成物層に含まれるシラン架橋性樹脂層を過熱水蒸気により架橋し、架橋後の樹脂組成物層を形成することを特徴とする。 In order to solve the above problems, a method for producing a foamed laminated sheet according to the present invention is a method for producing a foamed laminated sheet comprising a base material and a foamed resin layer formed on the base material. Including a step of supplying superheated steam to the resin composition layer containing the crosslinkable resin layer so that the temperature of the resin composition layer does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent. The silane crosslinkable resin layer contained in the resin composition layer by supplying superheated steam to the resin composition layer so that the amount of sprayed steam is 15 kg / hour or more and 100 kg / hour or less. Is crosslinked with superheated steam to form a crosslinked resin composition layer.
本発明に係る発泡積層シートの製造方法では、過熱水蒸気が１５ｋｇ/時間以上且つ１００ｋｇ/時間以下の噴霧蒸気量となるように樹脂組成物層に供給されることによって、樹脂組成物層に含まれるシラン架橋性樹脂層を十分且つ迅速に架橋させることができる。また、樹脂組成物層の温度が発泡剤の分解温度に対して＋６５℃を超えない温度となるように過熱水蒸気が供給されるため、架橋処理の際の過熱水蒸気の温度が高くなり過ぎず、樹脂組成物層に含まれる発泡剤の一部が高温となり架橋処理の段階で発泡する可能性が低減される。これにより、架橋後の発泡処理によって生成される発泡積層シートの表面の荒れを生じ難くすることができる。以上より、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シートの製造方法を提供することができる。 In the method for producing a foamed laminated sheet according to the present invention, superheated steam is contained in the resin composition layer by being supplied to the resin composition layer so that the amount of sprayed steam is 15 kg / hour or more and 100 kg / hour or less. The silane crosslinkable resin layer can be sufficiently and rapidly crosslinked. Further, since the superheated steam is supplied so that the temperature of the resin composition layer does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent, the temperature of the superheated steam during the crosslinking treatment does not become too high, A part of the foaming agent contained in the resin composition layer becomes high temperature, and the possibility of foaming at the stage of crosslinking treatment is reduced. Thereby, it can be made difficult to produce the surface roughness of the foaming laminated sheet produced | generated by the foaming process after bridge | crosslinking. From the above, it is possible to provide a method for producing a foamed laminated sheet that can be sufficiently and rapidly crosslinked and that is less likely to form defects on the surface.
樹脂組成物層は、ポリオレフィン樹脂を含んでいてもよい。この場合、例えば過熱水蒸気を用いて基材と樹脂組成物層とのラミネート処理を行う際、当該処理をより容易に行うことができる。 The resin composition layer may contain a polyolefin resin. In this case, for example, when performing the lamination process of a base material and a resin composition layer using superheated steam, the said process can be performed more easily.
過熱水蒸気を供給する工程では、過熱水蒸気を樹脂組成物層の幅方向の略全体にわたって供給してもよい。この場合、樹脂組成物層の幅方向の略全体にわたって、過熱水蒸気による架橋処理をより十分に行うことができる。 In the step of supplying superheated steam, the superheated steam may be supplied over substantially the entire width of the resin composition layer. In this case, the crosslinking treatment with superheated steam can be performed more fully over substantially the entire width of the resin composition layer.
過熱水蒸気を供給する工程では、樹脂組成物層に対して過熱水蒸気を直接噴霧してもよい。過熱水蒸気は、基材側から樹脂組成物層に噴霧してもよいが、樹脂組成物層に対して直接噴霧することにより、熱の伝達がより確実に行われるため、架橋処理をより十分且つ迅速に行うことができる。 In the step of supplying superheated steam, superheated steam may be directly sprayed on the resin composition layer. The superheated steam may be sprayed onto the resin composition layer from the base material side. However, by directly spraying the resin composition layer on the resin composition layer, heat transfer is more reliably performed. Can be done quickly.
架橋後の樹脂組成物層に含まれる発泡剤を加熱発泡させて樹脂組成物層から発泡樹脂層を得る工程を更に含んでもよい。この場合、基材上に発泡樹脂層が形成された発泡積層シートを確実に得ることができる。 You may further include the process of heat-foaming the foaming agent contained in the resin composition layer after bridge | crosslinking, and obtaining a foamed resin layer from a resin composition layer. In this case, a foamed laminated sheet in which a foamed resin layer is formed on the substrate can be reliably obtained.
本発明によれば、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シートの製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, while being able to bridge | crosslink sufficiently and rapidly, the manufacturing method of the foaming lamination sheet which does not produce a formation defect on the surface easily is provided.
以下、図面を参照しつつ、本発明の一実施形態に係る発泡積層シートの製造方法について詳細に説明する。なお、説明において、同一要素又は同一機能を有する要素には、同一符号を用いることとし、重複する説明は省略する。 Hereinafter, the manufacturing method of the foaming lamination sheet which concerns on one Embodiment of this invention is demonstrated in detail, referring drawings. In the description, the same reference numerals are used for the same elements or elements having the same function, and redundant description is omitted.
まず、図１を参照して、本発明の一実施形態に係る製造方法によって製造される発泡積層シートについて説明する。図１は、本発明の一実施形態に係る製造方法で製造される発泡積層シートの例を示す断面図であり、（ａ）は発泡前、（ｂ）は発泡後の断面形状を示す。図１（ａ）に示すように、発泡前の積層シート１は、紙基材３と、発泡剤を含有する樹脂組成物層５とを備えている。 First, with reference to FIG. 1, the foam lamination sheet manufactured by the manufacturing method which concerns on one Embodiment of this invention is demonstrated. Drawing 1 is a sectional view showing an example of a foam lamination sheet manufactured with a manufacturing method concerning one embodiment of the present invention, (a) shows before foaming and (b) shows a section shape after foaming. As shown to Fig.1 (a), the lamination sheet 1 before foaming is provided with the paper base material 3 and the resin composition layer 5 containing a foaming agent.
樹脂組成物層５は、紙基材３上に重ね合わされてラミネート処理され、且つ、架橋処理された状態で、紙基材３上に形成されている。積層シート１は、含有する発泡剤が所定の発泡倍率で発泡し、図１（ｂ）に示すように、発泡後の発泡樹脂層５ａを含む発泡積層シート１ａとなる。なお、発泡積層シート１ａは、表面に凹凸模様を有していてもよい。このような発泡積層シート１ａは、例えば発泡壁紙として用いられる。 The resin composition layer 5 is formed on the paper base material 3 in a state where the resin composition layer 5 is superposed on the paper base material 3, laminated, and crosslinked. The laminated sheet 1 becomes a foamed laminated sheet 1a including a foamed resin layer 5a after foaming, as shown in FIG. In addition, the foaming lamination sheet 1a may have an uneven | corrugated pattern on the surface. Such a foam laminated sheet 1a is used as foam wallpaper, for example.
紙基材３は、例えば壁紙用裏打紙などの通常使用されている紙材を用いることができるが、特に限定されない。紙基材３としては、好ましくは、スルファミン酸グアニジンやリン酸グアニジンなどの水溶性難燃剤を含浸させたパルプ主体の難燃紙、又は、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウムなどの無機質剤を混抄した無機質紙等を用いることができ、その坪量としては５０〜３００ｇ／ｍ２、好ましくは６０〜１６０ｇ／ｍ２である。 The paper base 3 may be a commonly used paper material such as wallpaper backing paper, but is not particularly limited. The paper base 3 is preferably a pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanidine sulfamate or guanidine phosphate, or an inorganic agent such as magnesium carbonate, aluminum hydroxide or magnesium hydroxide. Can be used, and the basis weight is 50 to 300 g / m 2 , preferably 60 to 160 g / m 2 .
また、紙基材３の表面のうち樹脂組成物層５を設ける側の接着面には、例えば、コロナ放電処理、プラズマ処理、又はオゾン処理等の易接着処理を施してもよい。また、紙基材３の接着面には、アクリル−ブチル共重合体、イソシアネートとポリオールからなるポリウレタン等を塗布した易接着処理層（図示しない）を設けるようにしてもよい。なお、紙基材３に代えて、例えば樹脂等からなる基材を用いてもよい。 Moreover, the adhesion surface on the side where the resin composition layer 5 is provided on the surface of the paper base 3 may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, or ozone treatment. Moreover, you may make it provide the easily bonding process layer (not shown) which apply | coated the polyurethane which consists of an acryl-butyl copolymer, isocyanate, and a polyol etc. in the adhesive surface of the paper base material 3. FIG. Instead of the paper substrate 3, a substrate made of resin or the like may be used.
樹脂組成物層５は、例えば発泡樹脂層５ａを形成するための層であり、無機充填剤と発泡剤と樹脂とを含む樹脂組成物を用いて形成することができる。樹脂としては、無極性の非ハロゲン系熱可塑性樹脂が好ましい。非ハロゲン系熱可塑性樹脂としては、エチレン単独重合体、又は、エチレンと他のオレフィンモノマーとの共重合体を挙げることができる。非ハロゲン系熱可塑性樹脂を用いることで、エチレン−メタクリル酸メチル共重合樹脂、エチレン−メタクリル酸共重合樹脂、エチレン−アクリル酸共重合樹脂、エチレン−酢酸ビニル共重合樹脂、及びアイオノマー樹脂などの極性樹脂を使用した場合と比較して、フィラーを増量した場合の粘度上昇が抑えられる為、高品質の壁紙を安定して生産することができる。 The resin composition layer 5 is a layer for forming the foamed resin layer 5a, for example, and can be formed using a resin composition containing an inorganic filler, a foaming agent, and a resin. The resin is preferably a nonpolar non-halogen thermoplastic resin. Examples of non-halogen thermoplastic resins include ethylene homopolymers and copolymers of ethylene and other olefin monomers. By using non-halogen thermoplastic resins, polarities such as ethylene-methyl methacrylate copolymer resins, ethylene-methacrylic acid copolymer resins, ethylene-acrylic acid copolymer resins, ethylene-vinyl acetate copolymer resins, and ionomer resins Compared to the case of using a resin, the increase in viscosity when the amount of filler is increased is suppressed, so that high-quality wallpaper can be stably produced.
樹脂組成物層５を形成するための上記樹脂組成物は、更に、シラン架橋性樹脂を含有している。含有されるシラン架橋性樹脂としては、従来公知のシラン架橋性樹脂、特にシラン架橋性ポリオレフィン系樹脂が好適に使用可能である。シラン架橋性ポリオレフィン系樹脂としては、母体としてのポリオレフィン系重合体に加水分解性シリル基を主として側鎖に導入した樹脂を用いることができる。例えば、低密度ポリエチレン系、高密度ポリエチレン系、エチレン酢酸ビニル共重合体系、ポリプロピレン系等のシラン架橋性ポリオレフィン系樹脂を用いることができる。架橋は、置換シリル基の加水分解により行われる。なお、このシリル基が末端に位置するポリオレフィン系樹脂が含まれていてもよい。 The resin composition for forming the resin composition layer 5 further contains a silane crosslinkable resin. As the silane crosslinkable resin to be contained, conventionally known silane crosslinkable resins, in particular, silane crosslinkable polyolefin resins can be suitably used. As the silane crosslinkable polyolefin resin, a resin in which a hydrolyzable silyl group is mainly introduced into a side chain in a polyolefin polymer as a base can be used. For example, silane crosslinkable polyolefin resins such as low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, and polypropylene can be used. Crosslinking is performed by hydrolysis of substituted silyl groups. In addition, the polyolefin resin which this silyl group is located in the terminal may be contained.
このシラン架橋性ポリオレフィン系樹脂は、ポリオレフィン系樹脂のモノマーとエチレン性不飽和シラン化合物を容器中でランダム共重合させる方法、又は、ポリオレフィン系樹脂の溶融物に過酸化物を用いてエチレン性不飽和シラン化合物をグラフト共重合する方法により得ることができる。ここで、母体のポリオレフィン系樹脂としては前記と同様の樹脂をいずれも使用することができる。更に、母体のポリオレフィン系樹脂は、一種を単独で又は二種以上を組み合わせて用いることができる。また、両樹脂の混合又は分散が許容される程度であれば上記ポリオレフィン系樹脂とは異なる樹脂を併用してもよい。混合又は分散の程度は、使用する押出機の種類により大差があり、また適宜の相溶化剤も使用できるので、組み合わせ樹脂は一概に区分はできないが、同種の樹脂であることが好ましい。以上で説明した樹脂組成物層５の樹脂組成物としては、三菱化学株式会社製の「リンクロン」などが例示される。 This silane crosslinkable polyolefin resin is a method of randomly copolymerizing a polyolefin resin monomer and an ethylenically unsaturated silane compound in a container, or using a peroxide in the polyolefin resin melt. It can be obtained by a method of graft copolymerizing a silane compound. Here, as the base polyolefin-based resin, any of the same resins as described above can be used. Further, the base polyolefin resin can be used alone or in combination of two or more. In addition, a resin different from the polyolefin resin may be used in combination as long as mixing or dispersion of both resins is allowed. The degree of mixing or dispersion varies greatly depending on the type of extruder used, and an appropriate compatibilizer can be used. Therefore, the combined resins cannot be generally classified, but the same type of resins are preferable. Examples of the resin composition of the resin composition layer 5 described above include “Linkron” manufactured by Mitsubishi Chemical Corporation.
また、樹脂組成物層５には、必要に応じて顔料等を添加して着色してもよい。顔料添加による着色は透明であってもよいし、半透明であってもよいし、不透明であってもよい。顔料としては、例えば、二酸化チタン、酸化鉄、カーボンブラック等の無機顔料やアニリンブラック、フタロシアニンブルー等の有機顔料を用いることができる。樹脂組成物層５に添加される顔料の添加量としては、樹脂成分１００重量部に対して、５〜５０重量部、好ましくは１０〜３０重量部である。また、樹脂組成物層５に、難燃剤、セル調整剤、安定剤、又は滑剤等の周知の添加剤を添加してもよい。 The resin composition layer 5 may be colored by adding a pigment or the like as necessary. The coloring by adding the pigment may be transparent, translucent, or opaque. Examples of the pigment include inorganic pigments such as titanium dioxide, iron oxide, and carbon black, and organic pigments such as aniline black and phthalocyanine blue. The amount of the pigment added to the resin composition layer 5 is 5 to 50 parts by weight, preferably 10 to 30 parts by weight with respect to 100 parts by weight of the resin component. Moreover, you may add well-known additives, such as a flame retardant, a cell regulator, a stabilizer, or a lubricant, to the resin composition layer 5.
続いて、図２を参照して、上述した積層シート１に対して架橋処理を行う方法について説明する。図２は、本発明の一実施形態に係る樹脂組成物層５の架橋処理方法を説明するための図である。なお、ラミネート処理に関しては、過熱水蒸気で架橋処理を行いつつラミネート処理も行ってもよく、架橋前の樹脂組成物層５に架橋処理を施した後に、別途、樹脂組成物層５を紙基材３上にラミネート等により積層するようにしてもよい。 Then, with reference to FIG. 2, the method to perform the bridge | crosslinking process with respect to the laminated sheet 1 mentioned above is demonstrated. FIG. 2 is a diagram for explaining a crosslinking treatment method for the resin composition layer 5 according to an embodiment of the present invention. Regarding the laminating process, the laminating process may be performed while performing the cross-linking process with superheated steam. After the cross-linking process is performed on the resin composition layer 5 before cross-linking, the resin composition layer 5 is separately attached to the paper base material. 3 may be laminated by lamination or the like.
まず、この架橋処理方法に用いる架橋処理装置１０について、図２を参照しながら説明する。図２に示すように、本実施形態に係る架橋処理装置１０は、積層シート１を構成する架橋前の樹脂組成物層５に対して過熱水蒸気Ｖを噴霧することができる噴霧ノズル１２を複数備えている。各噴霧ノズル１２は、図示下方に向かって放射状に過熱水蒸気Ｖを噴霧するように構成されており、各噴霧ノズル１２からの過熱水蒸気Ｖが積層シート１の幅方向全体にかかるように各噴霧ノズル１２間の位置及び高さが設定されている。 First, the crosslinking treatment apparatus 10 used for this crosslinking treatment method will be described with reference to FIG. As shown in FIG. 2, the crosslinking treatment apparatus 10 according to the present embodiment includes a plurality of spray nozzles 12 that can spray superheated steam V onto the resin composition layer 5 before crosslinking that constitutes the laminated sheet 1. ing. Each spray nozzle 12 is configured to spray the superheated steam V radially downward in the figure, and each spray nozzle 12 so that the superheated steam V from each spray nozzle 12 is applied to the entire width direction of the laminated sheet 1. The position and height between 12 are set.
各噴霧ノズル１２は、その噴霧先端と樹脂組成物層５（積層シート１）との距離が５ｍｍ以上２００ｍｍ以下となるように、樹脂組成物層５に近接してその上方に配置されていることが好ましい。なお、架橋処理装置１０では、それぞれの噴霧ノズル１２に温度勾配をつけて、装置全体としてより厳密な温度調整を行うようにしてもよいし、特に温度勾配をつけなくてもよい。また、複数の噴霧ノズル１２を用いた場合、各ノズルの構造を簡素化できるため、設備のメンテナンスを容易に行うことができる。また、各噴霧ノズル１２としては、樹脂組成物層５の幅方向と同一又はそれよりも長いスリットを有するスリットノズルを用いて、スリットから過熱水蒸気Ｖを押し出すようにしてもよい。スリットノズルの場合、噴霧ノズル１２を樹脂組成物層５に近づけたとしても樹脂組成物層５全体に過熱水蒸気を確実に噴霧することができるため、噴霧ノズル１２を樹脂組成物層５により簡単に近づけることができる。 Each spray nozzle 12 is disposed close to and above the resin composition layer 5 so that the distance between the spray tip and the resin composition layer 5 (laminated sheet 1) is 5 mm or more and 200 mm or less. Is preferred. In the cross-linking apparatus 10, a temperature gradient may be applied to each spray nozzle 12 so that more precise temperature adjustment may be performed as the entire apparatus, or a temperature gradient may not be particularly applied. Further, when a plurality of spray nozzles 12 are used, the structure of each nozzle can be simplified, so that maintenance of the equipment can be easily performed. Moreover, as each spray nozzle 12, you may make it extrude the superheated steam V from a slit using the slit nozzle which has a slit the same as that of the width direction of the resin composition layer 5, or longer than it. In the case of the slit nozzle, even when the spray nozzle 12 is brought close to the resin composition layer 5, the superheated steam can be reliably sprayed on the entire resin composition layer 5. You can get closer.
また、架橋処理装置１０は、熱効率を向上させるため、各噴霧ノズル１２と過熱水蒸気Ｖが積層シート１上に噴霧される噴霧領域とを覆うボックス１４を備えている。ボックス１４の容積は、例えば０．０１ｍ３〜２ｍ３である。ボックス１４の容積に応じて、架橋処理を行う樹脂組成物層５（積層シート１）の横幅を異ならせてもよい。例えば、ボックス１４の容積が０．０１ｍ３である場合には、積層シート１の横幅を１０ｃｍとし、ボックス１４の容積が２ｍ３である場合には、積層シート１の横幅を３０ｃｍとしてもよい。積層シート１は、ボックス１４の一方に設けられた開口の入口１４ａからボックス１４内に挿入され、ボックス１４の他方に設けられた開口の出口１４ｂから出るように搬送される。積層シート１は、噴霧ノズル１２側に樹脂組成物層５が位置するように配置されている。すなわち、樹脂組成物層５に対して過熱水蒸気Ｖが直接噴霧されている。なお、紙基材３の場合には水蒸気が透過するため、紙基材３を噴霧ノズル１２側に配置してもよい。 Moreover, the crosslinking processing apparatus 10 is provided with the box 14 which covers each spray nozzle 12 and the spray area | region where the superheated steam V is sprayed on the lamination sheet 1 in order to improve thermal efficiency. The volume of box 14 is, for example, 0.01 m 3 to 2 m 3. Depending on the volume of the box 14, the width of the resin composition layer 5 (laminated sheet 1) to be crosslinked may be varied. For example, when the volume of the box 14 is 0.01 m 3 , the lateral width of the laminated sheet 1 may be 10 cm, and when the volume of the box 14 is 2 m 3 , the lateral width of the laminated sheet 1 may be 30 cm. The laminated sheet 1 is inserted into the box 14 from an inlet 14 a of an opening provided in one of the boxes 14 and conveyed so as to exit from an outlet 14 b of an opening provided in the other of the boxes 14. The laminated sheet 1 is disposed so that the resin composition layer 5 is positioned on the spray nozzle 12 side. That is, the superheated steam V is directly sprayed on the resin composition layer 5. In addition, in the case of the paper base material 3, since water vapor permeates, the paper base material 3 may be disposed on the spray nozzle 12 side.
このような構成を備えた架橋処理装置１０内に積層シート１が挿入され、図示矢印方向に搬送されると、この積層シート１の樹脂組成物層５に対して、噴霧ノズル１２から過熱水蒸気Ｖが噴霧される。このとき、１５ｋｇ/時間以上で且つ１００ｋｇ/時間以下の噴霧蒸気量の過熱水蒸気Ｖが樹脂組成物層５に対して供給されるように、噴霧ノズル１２から過熱水蒸気Ｖが噴霧される。これにより、樹脂組成物層５に含まれるシラン架橋性樹脂層が過熱水蒸気により架橋し、架橋後の樹脂組成物層５が形成される。なお、過熱水蒸気Ｖが噴霧される樹脂組成物層５（積層シート１）の横幅は例えば３０ｃｍであるが、適宜、変更可能であり、噴霧蒸気量も積層シート１の横幅に比例して変更可能である。 When the laminated sheet 1 is inserted into the cross-linking apparatus 10 having such a configuration and conveyed in the direction of the arrow in the figure, the superheated steam V is applied from the spray nozzle 12 to the resin composition layer 5 of the laminated sheet 1. Is sprayed. At this time, the superheated steam V is sprayed from the spray nozzle 12 so that the superheated steam V having a spray vapor amount of 15 kg / hour or more and 100 kg / hour or less is supplied to the resin composition layer 5. Thereby, the silane crosslinkable resin layer contained in the resin composition layer 5 is crosslinked by superheated steam, and the resin composition layer 5 after crosslinking is formed. The lateral width of the resin composition layer 5 (laminated sheet 1) to which the superheated steam V is sprayed is, for example, 30 cm, but can be changed as appropriate, and the amount of spray vapor can also be changed in proportion to the lateral width of the laminated sheet 1. It is.
ここで、噴霧ノズル１２から噴霧される「過熱水蒸気」とは、飽和蒸気を更に加熱して飽和温度以上の蒸気温度を持たせた水蒸気であり、熱効率が良い。従来、架橋処理を十分且つ迅速に行うためには、樹脂組成物層５に対して供給する過熱水蒸気Ｖの温度を上げることが第一に考えられていた。しかしながら、単に過熱水蒸気Ｖの温度を上げるだけでは発泡後の積層シートのシート表面が荒れてしまうことがある。そこで、本発明者等は、更に検討を加え、樹脂組成物層５に対して供給する過熱水蒸気Ｖの温度が高温にならないように抑えつつ、蒸気量を変化（増加）させて架橋処理を行う実験を行った結果、次のことを見出した。 Here, the “superheated steam” sprayed from the spray nozzle 12 is steam obtained by further heating the saturated steam to have a steam temperature equal to or higher than the saturation temperature, and has high thermal efficiency. Conventionally, in order to perform the crosslinking treatment sufficiently and quickly, it was first considered to raise the temperature of the superheated steam V supplied to the resin composition layer 5. However, simply raising the temperature of the superheated steam V may roughen the sheet surface of the laminated sheet after foaming. Therefore, the present inventors further study and perform the crosslinking treatment by changing (increasing) the amount of steam while suppressing the temperature of the superheated steam V supplied to the resin composition layer 5 from becoming high. As a result of the experiment, the following was found.
すなわち、本発明者等は、一般的に横幅が３０ｃｍである積層シートに対し、過熱水蒸気Ｖの蒸気量が１５ｋｇ/時間以上で且つ１００ｋｇ/時間以下という十分且つ適切な範囲で噴霧した場合、過熱水蒸気Ｖの温度が高過ぎない所定の温度であっても、樹脂組成物層５に含まれるシラン架橋性樹脂層を十分且つ迅速に架橋させることができることを見出した。ここで、過熱水蒸気Ｖの温度とは、噴霧ノズル１２から噴霧された直後の温度を意味し、装置誤差がない場合、装置での設定温度に相当する。 That is, the present inventors generally overheated a laminated sheet having a width of 30 cm when the amount of superheated steam V is sprayed in a sufficient and appropriate range of 15 kg / hour or more and 100 kg / hour or less. It has been found that the silane crosslinkable resin layer contained in the resin composition layer 5 can be sufficiently and rapidly crosslinked even at a predetermined temperature at which the temperature of the water vapor V is not too high. Here, the temperature of the superheated steam V means a temperature immediately after spraying from the spray nozzle 12 and corresponds to a set temperature in the apparatus when there is no apparatus error.
所定の温度とは、例えば、少なくとも架橋処理を行うために必要な架橋温度以上であって、且つ、樹脂組成物層５の温度が発泡剤の分解温度に対して＋６５℃を超えない温度である。架橋温度は、例えば１３０〜１４０℃程度である。発泡剤の分解温度とは、樹脂組成物層５に含まれる発泡剤が分解又は気化しガスを発生し始める温度、すなわち発泡開始温度である。分解温度は、樹脂組成物層５に含まれる発泡剤の種類、又は発泡助剤等に応じて異なる。例えば、樹脂組成物層５に含まれる発泡剤がＡＤＣＡ（アゾジカルボン酸アミド）であり発泡助剤を入れていない場合には、分解温度は１９０±１０℃程度である。樹脂組成物層５に含まれる発泡剤がＡＤＣＡ（アゾジカルボン酸アミド）であり発泡助剤を入れている場合には、分解温度が１４０〜１５０℃付近にまで低下する。よって、発泡剤の分解温度とは、発泡助剤を入れていない場合には発泡剤そのものの分解温度をいい、発泡助剤を入れている場合には発泡剤そのものの分解温度ではなく、発泡助剤により低下した分解温度をいう。例えば架橋温度が１３０℃であり、且つ、分解温度が１４０℃である場合には、所定の温度は、１３０℃以上であり、且つ、２０５℃とならない温度となる。 The predetermined temperature is, for example, a temperature that is at least equal to or higher than the crosslinking temperature necessary for performing the crosslinking treatment, and the temperature of the resin composition layer 5 does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent. . The crosslinking temperature is, for example, about 130 to 140 ° C. The decomposition temperature of the foaming agent is a temperature at which the foaming agent contained in the resin composition layer 5 starts to decompose or vaporize to generate gas, that is, a foaming start temperature. The decomposition temperature varies depending on the type of foaming agent contained in the resin composition layer 5 or the foaming aid. For example, when the foaming agent contained in the resin composition layer 5 is ADCA (azodicarboxylic amide) and no foaming aid is added, the decomposition temperature is about 190 ± 10 ° C. When the foaming agent contained in the resin composition layer 5 is ADCA (azodicarboxylic acid amide) and a foaming aid is added, the decomposition temperature decreases to around 140 to 150 ° C. Therefore, the decomposition temperature of the foaming agent refers to the decomposition temperature of the foaming agent itself when no foaming aid is added, and when the foaming aid is included, it is not the decomposition temperature of the foaming agent itself but the foaming aid itself. The decomposition temperature lowered by the agent. For example, when the crosslinking temperature is 130 ° C. and the decomposition temperature is 140 ° C., the predetermined temperature is 130 ° C. or higher and does not become 205 ° C.
所定の温度は、噴霧ノズル１２から過熱水蒸気Ｖが供給されることで樹脂組成物層５の温度が上昇しても、当該樹脂組成物層５の温度が分解温度に対して＋６５℃を超えない温度となるように設定される。また、所定の温度は、当該樹脂組成物層５の温度が分解温度に対して＋３０℃を超えない温度に設定されていてもよい。また、所定の温度は、当該樹脂組成物層５の温度が分解温度を超えないように設定されていてもよい。なお、所定の温度は、例えば噴霧ノズル１２と樹脂組成物層５との間の距離等に応じて異なる値に設定されてもよい。また、所定の温度は、過熱水蒸気Ｖが供給される時間に応じて異なる値に設定されてもよい。 Even if the temperature of the resin composition layer 5 is increased by supplying the superheated steam V from the spray nozzle 12, the temperature of the resin composition layer 5 does not exceed + 65 ° C. with respect to the decomposition temperature. The temperature is set. The predetermined temperature may be set to a temperature at which the temperature of the resin composition layer 5 does not exceed + 30 ° C. with respect to the decomposition temperature. The predetermined temperature may be set so that the temperature of the resin composition layer 5 does not exceed the decomposition temperature. The predetermined temperature may be set to a different value depending on, for example, the distance between the spray nozzle 12 and the resin composition layer 5. Further, the predetermined temperature may be set to a different value according to the time during which the superheated steam V is supplied.
このように、樹脂組成物層５に供給される過熱水蒸気Ｖの量が上記適切な範囲にある場合、過熱水蒸気Ｖの温度を、樹脂組成物層５の温度が発泡剤の分解温度に対して＋６５℃を超えない温度となるように設定できる。このため、樹脂組成物層５に含まれる発泡剤の一部が高温となり架橋処理の段階で発泡してしまう可能性を低減することができる。 Thus, when the amount of the superheated steam V supplied to the resin composition layer 5 is in the appropriate range, the temperature of the superheated steam V is set so that the temperature of the resin composition layer 5 is higher than the decomposition temperature of the blowing agent. The temperature can be set so as not to exceed + 65 ° C. For this reason, a part of foaming agent contained in the resin composition layer 5 becomes high temperature, and possibility that it will foam at the stage of a crosslinking process can be reduced.
上述した架橋処理が行われた積層シート１に対して、所定の発泡処理を施すことで、図１（ｂ）に示すような発泡積層シート１ａが得られる。すなわち、架橋後の樹脂組成物層５に含まれる発泡剤を加熱発泡させて樹脂組成物層５から発泡樹脂層５ａを得ることにより、発泡積層シート１ａが得られる。上述したように、樹脂組成物層５に含まれる発泡剤の一部が架橋処理の段階で発泡してしまう可能性が低減されるので、架橋後の発泡処理により得られる発泡積層シート１ａの表面の荒れが生じ難くなる。なお、この発泡積層シート１ａの表面に対し、凹凸模様等を更に付与する処理を行ってもよい。 A foamed laminated sheet 1a as shown in FIG. 1 (b) is obtained by subjecting the laminated sheet 1 subjected to the above-described crosslinking treatment to a predetermined foaming treatment. That is, the foamed laminated sheet 1a is obtained by heating and foaming the foaming agent contained in the resin composition layer 5 after crosslinking to obtain the foamed resin layer 5a from the resin composition layer 5. As described above, since the possibility that a part of the foaming agent contained in the resin composition layer 5 is foamed at the stage of the crosslinking treatment is reduced, the surface of the foamed laminated sheet 1a obtained by the foaming treatment after the crosslinking Roughness is unlikely to occur. In addition, you may perform the process which further provides an uneven | corrugated pattern etc. with respect to the surface of this foaming lamination sheet 1a.
以上、本実施形態に係る発泡積層シート１ａの製造方法では、過熱水蒸気Ｖが１５ｋｇ/時間以上且つ１００ｋｇ/時間以下の噴霧蒸気量となるように樹脂組成物層５に供給されることによって、樹脂組成物層５に含まれるシラン架橋性樹脂層を十分且つ迅速に架橋させることができる。また、樹脂組成物層５の温度が分解温度に対して＋６５℃を超えない温度となるように過熱水蒸気が供給されるため、架橋処理の際の過熱水蒸気の温度が高くなり過ぎず、樹脂組成物に含まれる発泡剤の一部が高温となり架橋処理の段階で発泡する可能性が低減される。これにより、架橋後の発泡処理によって生成される発泡積層シート１ａの表面の荒れを生じ難くすることが可能となる。以上より、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シート１ａの製造方法を提供することができる。 As mentioned above, in the manufacturing method of the foaming lamination sheet 1a which concerns on this embodiment, resin is supplied to the resin composition layer 5 so that the superheated steam V may be the amount of spray vapor | steam of 15 kg / hour or more and 100 kg / hour or less. The silane crosslinkable resin layer contained in the composition layer 5 can be sufficiently and rapidly crosslinked. Further, since the superheated steam is supplied so that the temperature of the resin composition layer 5 does not exceed + 65 ° C. with respect to the decomposition temperature, the temperature of the superheated steam during the crosslinking treatment does not become too high, and the resin composition Part of the foaming agent contained in the product becomes high temperature, and the possibility of foaming at the stage of crosslinking treatment is reduced. Thereby, it becomes possible to make it hard to produce the rough surface of the foaming lamination sheet 1a produced | generated by the foaming process after bridge | crosslinking. From the above, it is possible to provide a method for producing a foamed laminated sheet 1a that can be sufficiently and rapidly crosslinked and that is less prone to formation defects on the surface.
本実施形態に係る発泡積層シート１ａの製造方法では、樹脂組成物層５が、ポリオレフィン樹脂を含んでいてもよい。この場合、例えば過熱水蒸気Ｖを用いて紙基材３と樹脂組成物層５とのラミネート処理を行う際、当該処理をより容易に行うことができる。 In the manufacturing method of the foam lamination sheet 1a which concerns on this embodiment, the resin composition layer 5 may contain polyolefin resin. In this case, for example, when the lamination process of the paper base material 3 and the resin composition layer 5 is performed using the superheated steam V, the process can be performed more easily.
本実施形態に係る発泡積層シート１ａの製造方法では、過熱水蒸気Ｖを供給する工程において、樹脂組成物層５の幅方向の略全体にわたって過熱水蒸気Ｖが噴霧される。よって、樹脂組成物層５の幅方向の略全体にわたって、過熱水蒸気Ｖによる架橋処理をより十分に行うことができる。 In the manufacturing method of the foaming laminated sheet 1a which concerns on this embodiment, in the process of supplying the superheated steam V, the superheated steam V is sprayed over substantially the whole width direction of the resin composition layer 5. Therefore, the crosslinking treatment with the superheated steam V can be more sufficiently performed over substantially the entire width of the resin composition layer 5.
本実施形態に係る発泡積層シート１ａの製造方法では、過熱水蒸気Ｖを樹脂組成物層５に供給する工程において、樹脂組成物層５に対して過熱水蒸気Ｖが直接噴霧される。過熱水蒸気Ｖは、紙基材３側から樹脂組成物層５に噴霧してもよいが、樹脂組成物層５に対して直接噴霧することにより、熱の伝達がより確実に行われるため、架橋処理をより十分且つ迅速に行うことができる。 In the method for producing the foamed laminated sheet 1 a according to this embodiment, in the step of supplying the superheated steam V to the resin composition layer 5, the superheated steam V is directly sprayed on the resin composition layer 5. The superheated steam V may be sprayed onto the resin composition layer 5 from the paper substrate 3 side, but since heat transfer is more reliably performed by spraying directly on the resin composition layer 5, crosslinking is performed. Processing can be performed more sufficiently and quickly.
本実施形態に係る発泡積層シート１ａの製造方法では、架橋後の樹脂組成物層５に含まれる発泡剤を加熱発泡させて樹脂組成物層５から発泡樹脂層５ａを得る工程を更に含んでいる。よって、紙基材３上に発泡樹脂層５ａが形成された発泡積層シート１ａを確実に得ることができる。 In the manufacturing method of the foaming lamination sheet 1a which concerns on this embodiment, the process of heat-foaming the foaming agent contained in the resin composition layer 5 after bridge | crosslinking and obtaining the foaming resin layer 5a from the resin composition layer 5 is further included. . Therefore, the foamed laminated sheet 1a in which the foamed resin layer 5a is formed on the paper substrate 3 can be obtained reliably.
本発明は、上記実施形態に限定されるものではなく、種々の変形を適用できる。例えば、上記実施形態では、紙基材３上に重ね合わされた樹脂組成物層５に対して過熱水蒸気Ｖを供給する例を示したが、基材も樹脂から構成するようにし、樹脂基材上に重ね合わされた樹脂組成物層５に過熱水蒸気Ｖを供給してもよい。 The present invention is not limited to the above embodiment, and various modifications can be applied. For example, in the above-described embodiment, an example in which the superheated steam V is supplied to the resin composition layer 5 superimposed on the paper base 3 has been described. The superheated steam V may be supplied to the resin composition layer 5 superposed on the substrate.
以下、本発明の実施例について説明するが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
まず、コートハンガータイプのマニュホールドを有するＴダイと、スクリュー径（Ｄ）６５ｍｍ、Ｌ／Ｄ（スクリュー長をスクリュー径で割ったもの）＝３２であるバリアタイプスクリューとを用いて、押出し厚み１００μｍで単層の樹脂シートとして押出し製膜した。押出し条件は、シリンダーからダイにわたる全てのゾーンで設定温度を１２０℃にした。押出しに使用した材料は、以下の表１に示す配合にて行い、樹脂組成物層５とした。表１に示すように、樹脂組成物層５に含まれる発泡剤そのものの分解温度（発泡開始温度）は約１８０℃であるが、発泡助剤を入れることにより、樹脂組成物層５に含まれる発泡剤の分解温度は約１４０℃付近となっている。なお、本実施例では、樹脂組成物層５のみをまずシート状に作製した。樹脂組成物層５（積層シート１）の横幅は３０ｃｍであった。 First, using a T-die having a coat hanger type manifold and a barrier type screw having a screw diameter (D) of 65 mm and L / D (screw length divided by screw diameter) = 32, an extrusion thickness of 100 μm To form a single layer resin sheet by extrusion. Extrusion conditions were such that the set temperature was 120 ° C. in all zones from the cylinder to the die. The material used for the extrusion was prepared according to the formulation shown in Table 1 below to obtain a resin composition layer 5. As shown in Table 1, although the decomposition temperature (foaming start temperature) of the foaming agent itself contained in the resin composition layer 5 is about 180 ° C., it is contained in the resin composition layer 5 by adding a foaming aid. The decomposition temperature of the foaming agent is about 140 ° C. In this example, only the resin composition layer 5 was first formed into a sheet shape. The lateral width of the resin composition layer 5 (laminated sheet 1) was 30 cm.
続いて、図２に示す架橋処理装置１０を用いて、樹脂組成物層５に対して所定の蒸気量で過熱水蒸気Ｖを供給して架橋処理を行った。架橋処理装置１０のボックス１４の容積は０．０２７ｍ３であった。同じ容積のボックス１４において、過熱水蒸気の蒸気量を、１５ｋｇ／時間、及び６０ｋｇ／時間と変えて、過熱水蒸気Ｖの供給を行い、架橋処理を行った。 Subsequently, the crosslinking treatment apparatus 10 illustrated in FIG. 2 was used to perform crosslinking treatment by supplying superheated steam V with a predetermined amount of steam to the resin composition layer 5. The volume of the box 14 of the crosslinking apparatus 10 was 0.027 m 3 . In the box 14 having the same volume, the amount of superheated steam was changed to 15 kg / hour and 60 kg / hour, the superheated steam V was supplied, and the crosslinking treatment was performed.
各蒸気量での過熱水蒸気Ｖの供給は、過熱水蒸気Ｖの水蒸気温度を１７０℃、２００℃、及び２４０℃の３つの温度帯域毎に行った。本実施例において、過熱水蒸気Ｖの水蒸気温度とは、噴霧ノズル１２から噴霧された直後の水蒸気温度と略同じ設定温度である。また、各蒸気量及び各水蒸気温度での過熱水蒸気Ｖの供給は、噴霧時間を０．５分、１分、２分、及び４分と変えて行った。 The superheated steam V was supplied at each steam amount at a temperature of 170 ° C., 200 ° C., and 240 ° C. for each temperature of the superheated steam V. In the present embodiment, the water vapor temperature of the superheated water vapor V is substantially the same set temperature as the water vapor temperature immediately after being sprayed from the spray nozzle 12. In addition, the superheated steam V was supplied at each steam amount and each steam temperature by changing the spraying time to 0.5 minutes, 1 minute, 2 minutes, and 4 minutes.
その後、上述した条件で架橋処理を行った樹脂組成物層５を紙基材３上に積層し、熱プレス機を用いて、温度１２０℃、プレス圧力５ＭＰａの条件で２分間の熱圧着を行った。なお、紙基材３としては、裏打ち紙（株式会社興人製、商品名「ＷＫ−６６５ＩＨＴ」）を用いた。そして、熱圧着した積層シート１の樹脂組成物層５側の表面にコロナ放電処理を施した後、グラビア印刷機により水性インキを用いて織物絵柄を印刷した。その後、２２０℃で４０秒間加熱して樹脂組成物層５中に含まれる発泡剤を加熱発泡させ、発泡積層シート１ａを得た。 Thereafter, the resin composition layer 5 subjected to the crosslinking treatment under the above-described conditions is laminated on the paper substrate 3, and thermocompression bonding is performed for 2 minutes under the conditions of a temperature of 120 ° C. and a press pressure of 5 MPa using a hot press machine. It was. In addition, as the paper base material 3, backing paper (manufactured by Kojin Co., Ltd., trade name “WK-665IHT”) was used. And after giving the corona discharge process to the surface by the side of the resin composition layer 5 of the laminated sheet 1 which carried out thermocompression bonding, the textile pattern was printed using the water-based ink with the gravure printer. Then, it heated at 220 degreeC for 40 second, the foaming agent contained in the resin composition layer 5 was heat-foamed, and the foaming lamination sheet 1a was obtained.
そして、取得した発泡積層シート１ａにおいて、発泡倍率の評価を行った。なお、発泡倍率が高いほど、架橋処理の段階での発泡剤の発泡が抑制されたことを示している。以下の表２，３にその結果を示す。なお、以下の表２，３においては、発泡倍率だけでなく、ラミネート強度についての評価結果も示している。また、発泡倍率、ラミネート強度、及び噴霧時間に基づいた、発泡積層シート１１ａの生産性に対する総合評価も示している。表２における「サンプル温度」は、過熱水蒸気Ｖの供給が終了したときの樹脂組成物層５（積層シート１）の温度である。樹脂組成物層５の温度は、過熱水蒸気Ｖを供給する時間が長くなるほど上昇し、過熱水蒸気Ｖの供給開始時から供給終了時までの間では、供給終了時に最も高くなる。よって、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度は、少なくともサンプル温度以下となっている。 And in the acquired foam lamination sheet 1a, the foaming magnification was evaluated. In addition, it has shown that foaming of the foaming agent in the step of the crosslinking process was suppressed, so that foaming ratio was high. The results are shown in Tables 2 and 3 below. In Tables 2 and 3 below, not only the expansion ratio but also the evaluation results for the laminate strength are shown. Moreover, the comprehensive evaluation with respect to the productivity of the foam lamination sheet 11a based on foaming magnification, laminate strength, and spraying time is also shown. “Sample temperature” in Table 2 is the temperature of the resin composition layer 5 (laminated sheet 1) when the supply of the superheated steam V is completed. The temperature of the resin composition layer 5 increases as the time for supplying the superheated steam V becomes longer, and becomes highest at the end of the supply from the start of the supply of the superheated steam V to the end of the supply. Therefore, the temperature of the resin composition layer 5 between the start of supply of the superheated steam V and the end of supply is at least the sample temperature.
発泡積層シート１ａにおける発泡倍率とは、発泡積層シート１ａの単位体積あたりの重量に対応し、発泡積層シート１ａの硬さを示す指標である。架橋が十分に行われていない場合、架橋後の発泡処理時にガスが保持できず外部にガス抜けしてしまい、発泡倍率が低下する。このため、発泡倍率が大きいほど、架橋がより進んだと評価することができる。また、発泡倍率は、架橋処理の段階で樹脂組成物層５に含まれる発泡剤の一部が発泡してしまうことにも起因して変化する。発泡倍率が大きいほど、架橋処理の段階における発泡剤の発泡度合いが少なく、発泡積層シート１ａの表面が綺麗であると評価することができる。 The expansion ratio in the foam laminate sheet 1a corresponds to the weight per unit volume of the foam laminate sheet 1a and is an index indicating the hardness of the foam laminate sheet 1a. If the crosslinking is not sufficiently performed, the gas cannot be retained during the foaming treatment after the crosslinking, and the gas escapes to the outside, so that the expansion ratio is lowered. For this reason, it can be evaluated that as the expansion ratio is larger, the crosslinking is more advanced. In addition, the expansion ratio changes due to a part of the foaming agent contained in the resin composition layer 5 being foamed at the stage of the crosslinking treatment. It can be evaluated that the higher the expansion ratio, the less the foaming degree of the foaming agent at the stage of the crosslinking treatment, and the more beautiful the surface of the foamed laminated sheet 1a.
発泡倍率の評価として、発泡倍率が少なくとも３．１倍よりも大きい場合には好適とまではいえないものの適正であり、発泡倍率が５．０倍以上である場合には好適であるとした。なお、表２における「（セル×）」は、セルが大きいことを示している。セルが大きい場合には、発泡倍率が５．０倍以上であっても好適とまではいえず適正であるとした。ここで、「適正」とは、十分に架橋されていると共に、発泡積層シート１ａの表面の荒れが許容範囲に抑制されていることを示す。「好適」とは、より十分に架橋されていると共に、発泡積層シート１ａの表面の荒れがより好適に抑制されていることを示す。 As an evaluation of the expansion ratio, it is appropriate although it is not suitable when the expansion ratio is at least larger than 3.1 times, and it is preferable when the expansion ratio is 5.0 times or more. Note that “(cell ×)” in Table 2 indicates that the cell is large. When the cell is large, even if the expansion ratio is 5.0 times or more, it is not suitable and is considered appropriate. Here, “appropriate” indicates that the surface of the foamed laminated sheet 1 a is sufficiently cross-linked and suppressed to an allowable range. “Preferable” indicates that the surface of the foamed laminated sheet 1a is more suitably suppressed while being more fully cross-linked.
発泡積層シート１ａにおけるラミネート強度とは、ラミネート処理によってラミネートされた紙基材３と樹脂組成物層５との貼り付き度合いを示す指標である。ラミネート強度の評価は、紙基材から樹脂組成物層が剥がれず、紙基材側で層間剥離してしまう程度の強度を「◎」、すなわち良好な強度であるとした。また、十分にラミネートされており、素手で剥がれない程度の強度を「○」、すなわち十分な強度であるとした。 The laminate strength in the foam laminated sheet 1a is an index indicating the degree of sticking between the paper base material 3 and the resin composition layer 5 laminated by the laminating process. In the evaluation of the laminate strength, the resin composition layer was not peeled off from the paper substrate, and the strength to the extent that the paper substrate was delaminated was “層 間”, that is, good strength. Further, the strength to the extent that it was sufficiently laminated and could not be peeled with bare hands was defined as “◯”, that is, sufficient strength.
発泡積層シート１１ａの生産性に対する総合評価は、次の基準で行った。
（総合評価）
Ａ：発泡倍率が５．０倍以上、且つ、ラミネート強度が「◎」、且つ、噴霧時間が１分未満のもの
Ｂ：Ａの条件に対し、発泡倍率及びラミネート強度のいずれかが劣っている、又は、噴霧時間が１分以上かかるもの
Ｃ：発泡倍率が３．１倍以下のもの
なお、上記総合評価のうち、Ｃ、Ｂ、及びＡの順で、発泡積層シート１ａの生産性がより高いことを示している。
Comprehensive evaluation for the productivity of the foam laminated sheet 11a was performed according to the following criteria.
(Comprehensive evaluation)
A: When the expansion ratio is 5.0 times or more, the laminate strength is “」 ”, and the spray time is less than 1 minute. B: Either the expansion ratio or the laminate strength is inferior to the condition of A. Or, spraying time is 1 minute or more C: foaming ratio is 3.1 times or less In addition, among the above comprehensive evaluation, the productivity of the foamed laminated sheet 1a is more in the order of C, B, and A It is high.
表２には、樹脂組成物層５に供給される過熱水蒸気Ｖの蒸気量が１５ｋｇ/時間である場合の実施例の評価結果を示している。水蒸気温度が１７０℃の場合、サンプル温度は、噴霧時間０．５分で過熱水蒸気Ｖが供給された場合には１００℃となり、噴霧時間１分で過熱水蒸気Ｖが供給された場合には１００℃となり、噴霧時間２分で過熱水蒸気Ｖが供給された場合には１６１℃となり、噴霧時間４分で過熱水蒸気Ｖが供給された場合には１７０℃となった。よって、いずれの噴霧時間で過熱水蒸気Ｖが供給された場合であっても、サンプル温度は、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃（本実施形態においては、約２０５℃）を超えない温度であった。これは、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度も、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度であったことを示している。噴霧時間が０．５分の場合、ラミネート強度が「○」であり、且つ、発泡倍率が３．８倍であった。すなわち、この条件下では、噴霧時間が０．５分まで短くなっても、ラミネート強度が十分であり、且つ、発泡倍率が適正な発泡積層シート１ａが取得できた（総合評価：Ｂ）。発泡倍率が適正であることから、十分に架橋されていると共に、発泡積層シート１ａの表面の荒れが許容範囲に抑制されていると評価できる。 Table 2 shows the evaluation results of the examples when the amount of superheated steam V supplied to the resin composition layer 5 is 15 kg / hour. When the steam temperature is 170 ° C., the sample temperature is 100 ° C. when the superheated steam V is supplied at a spray time of 0.5 minutes, and 100 ° C. when the superheated steam V is supplied at a spray time of 1 minute. When the superheated steam V was supplied in a spraying time of 2 minutes, the temperature was 161 ° C., and when the superheated steam V was supplied in a spraying time of 4 minutes, the temperature was 170 ° C. Therefore, the sample temperature is + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5 (in the present embodiment, approximately approximately) even when the superheated steam V is supplied at any spraying time. (205 ° C.). This is because the temperature of the resin composition layer 5 from the start of the supply of the superheated steam V to the end of the supply also does not exceed + 65 ° C. with respect to the decomposition temperature of the blowing agent contained in the resin composition layer 5. It shows that. When the spraying time was 0.5 minutes, the laminate strength was “◯” and the foaming ratio was 3.8 times. That is, under these conditions, even when the spraying time was shortened to 0.5 minutes, a foamed laminated sheet 1a having sufficient laminate strength and an appropriate foaming ratio could be obtained (overall evaluation: B). Since the expansion ratio is appropriate, it can be evaluated that the surface is sufficiently crosslinked and the surface roughness of the foamed laminated sheet 1a is suppressed within an allowable range.
また、樹脂組成物層５に供給される過熱水蒸気Ｖの蒸気量が１５ｋｇ/時間で且つ水蒸気温度が２００℃の場合、サンプル温度は、噴霧時間０．５分で過熱水蒸気Ｖが供給された場合には１０１℃となり、噴霧時間１分で過熱水蒸気Ｖが供給された場合には１４５℃となり、噴霧時間２分で過熱水蒸気Ｖが供給された場合には１９５℃となり、噴霧時間４分で過熱水蒸気Ｖが供給された場合には２００℃となった。よって、いずれの噴霧時間で過熱水蒸気Ｖが供給された場合であっても、サンプル温度は、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃（本実施形態においては、約２０５℃）を超えない温度であった。これは、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度も、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度であったことを示している。噴霧時間が０．５分の場合、ラミネート強度が「◎」であり、且つ、発泡倍率が３．５倍であった。すなわち、この条件下では、噴霧時間が０．５分まで短くなっても、ラミネート強度が良好であり、且つ、発泡倍率が適正な発泡積層シート１ａが取得できた（総合評価：Ｂ）。発泡倍率が適正であることから、十分に架橋されていると共に、発泡積層シート１ａの表面の荒れが許容範囲に抑制されていると評価できる。 When the amount of superheated steam V supplied to the resin composition layer 5 is 15 kg / hour and the steam temperature is 200 ° C., the sample temperature is when the superheated steam V is supplied with a spray time of 0.5 minutes. When the superheated steam V is supplied at a spraying time of 1 minute, the temperature is 145 ° C. When the superheated steam V is supplied at a spraying time of 2 minutes, the temperature is 195 ° C. When steam V was supplied, the temperature reached 200 ° C. Therefore, the sample temperature is + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5 (in the present embodiment, approximately approximately) even when the superheated steam V is supplied at any spraying time. (205 ° C.). This is because the temperature of the resin composition layer 5 from the start of the supply of the superheated steam V to the end of the supply also does not exceed + 65 ° C. with respect to the decomposition temperature of the blowing agent contained in the resin composition layer 5. It shows that. When the spraying time was 0.5 minutes, the laminate strength was “◎” and the expansion ratio was 3.5 times. That is, under these conditions, even when the spraying time was shortened to 0.5 minutes, a foamed laminated sheet 1a having good laminate strength and appropriate foaming ratio could be obtained (overall evaluation: B). Since the expansion ratio is appropriate, it can be evaluated that the surface is sufficiently crosslinked and the surface roughness of the foamed laminated sheet 1a is suppressed within an allowable range.
また、樹脂組成物層５に供給される過熱水蒸気Ｖの蒸気量が１５ｋｇ/時間で且つ水蒸気温度が２４０℃の場合、サンプル温度は、噴霧時間０．５分で過熱水蒸気Ｖが供給された場合には１４２℃となり、噴霧時間１分で過熱水蒸気Ｖが供給された場合には２０２℃となった。よって、いずれの噴霧時間で過熱水蒸気Ｖが供給された場合であっても、サンプル温度は、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃（本実施形態においては、約２０５℃）を超えない温度であった。これは、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度も、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度であったことを示している。噴霧時間が０．５分の場合、ラミネート強度が「◎」であり、且つ、セルは大きいものの発泡倍率が５．５倍であった。すなわち、この条件下では、噴霧時間が０．５分まで短くなっても、ラミネート強度が良好であり、且つ、発泡倍率が適正な発泡積層シート１ａが取得できた（総合評価：Ｂ）。発泡倍率が適正であることから、十分に架橋されていると共に、発泡積層シート１ａの表面の荒れが許容範囲に抑制されていると評価できる。なお、この結果は、水蒸気温度が２４０℃という高温であっても、噴霧時間０．５〜１分という短時間の噴霧であれば、問題なく処理できるということを示している。 When the amount of superheated steam V supplied to the resin composition layer 5 is 15 kg / hour and the steam temperature is 240 ° C., the sample temperature is when the superheated steam V is supplied with a spray time of 0.5 minutes. Was 142 ° C., and was 202 ° C. when superheated steam V was supplied in 1 minute of spraying time. Therefore, the sample temperature is + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5 (in the present embodiment, approximately approximately) even when the superheated steam V is supplied at any spraying time. (205 ° C.). This is because the temperature of the resin composition layer 5 from the start of the supply of the superheated steam V to the end of the supply also does not exceed + 65 ° C. with respect to the decomposition temperature of the blowing agent contained in the resin composition layer 5. It shows that. When the spraying time was 0.5 minutes, the laminate strength was “◎”, and the cell was large, but the expansion ratio was 5.5 times. That is, under these conditions, even when the spraying time was shortened to 0.5 minutes, a foamed laminated sheet 1a having good laminate strength and appropriate foaming ratio could be obtained (overall evaluation: B). Since the expansion ratio is appropriate, it can be evaluated that the surface is sufficiently crosslinked and the surface roughness of the foamed laminated sheet 1a is suppressed within an allowable range. This result shows that even if the water vapor temperature is as high as 240 ° C., the spray can be processed without problems if the spray is performed for a short time of spraying time of 0.5 to 1 minute.
以上、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度が、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度となるように、蒸気量１５ｋｇ/時間の過熱水蒸気Ｖが樹脂組成物層５に供給されている場合には、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シート１ａを製造することが可能であると示された。 As described above, the temperature of the resin composition layer 5 from the start of supply of the superheated steam V to the end of supply is such that the temperature does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5. In addition, when superheated steam V having a steam amount of 15 kg / hour is supplied to the resin composition layer 5, the foamed laminated sheet 1 a that can be sufficiently and quickly crosslinked and hardly forms poorly on the surface is manufactured. It was shown to be possible.
表３には、樹脂組成物層５に供給される過熱水蒸気Ｖの蒸気量が６０ｋｇ/時間である場合の実施例を示している。水蒸気温度が１７０℃の場合、サンプル温度は、噴霧時間０．５分で過熱水蒸気Ｖが供給された場合には１００℃となり、噴霧時間１分で過熱水蒸気Ｖが供給された場合には１０１℃となり、噴霧時間２分で過熱水蒸気Ｖが供給された場合には１６４℃となり、噴霧時間４分で過熱水蒸気Ｖが供給された場合には１７０℃となった。よって、いずれの噴霧時間で過熱水蒸気Ｖが供給された場合であっても、サンプル温度は、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃（本実施形態においては、約２０５℃）を超えない温度であった。これは、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度も、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度であったことを示している。噴霧時間が０．５分の場合、ラミネート強度が「○」であり、且つ、発泡倍率が４．２倍であった。すなわち、この条件下では、噴霧時間が０．５分まで短くなっても、ラミネート強度が好適であり、且つ、発泡倍率が適正な発泡積層シート１ａが取得できた（総合評価：Ｂ）。発泡倍率が適正であることから、十分に架橋されていると共に、発泡積層シート１ａの表面の荒れが許容範囲に抑制されていると評価できる。 Table 3 shows an example in which the amount of superheated steam V supplied to the resin composition layer 5 is 60 kg / hour. When the steam temperature is 170 ° C., the sample temperature is 100 ° C. when superheated steam V is supplied at a spray time of 0.5 minutes, and 101 ° C. when superheated steam V is supplied at a spray time of 1 minute. When the superheated steam V was supplied in a spraying time of 2 minutes, the temperature was 164 ° C., and when the superheated steam V was supplied in a spraying time of 4 minutes, the temperature was 170 ° C. Therefore, the sample temperature is + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5 (in the present embodiment, approximately approximately) even when the superheated steam V is supplied at any spraying time. (205 ° C.). This is because the temperature of the resin composition layer 5 from the start of the supply of the superheated steam V to the end of the supply also does not exceed + 65 ° C. with respect to the decomposition temperature of the blowing agent contained in the resin composition layer 5. It shows that. When the spraying time was 0.5 minutes, the laminate strength was “◯” and the foaming ratio was 4.2 times. That is, under these conditions, even when the spraying time was shortened to 0.5 minutes, a foamed laminated sheet 1a having a suitable laminate strength and an appropriate expansion ratio could be obtained (overall evaluation: B). Since the expansion ratio is appropriate, it can be evaluated that the surface is sufficiently crosslinked and the surface roughness of the foamed laminated sheet 1a is suppressed within an allowable range.
また、樹脂組成物層５に供給される過熱水蒸気Ｖの蒸気量が６０ｋｇ/時間で且つ水蒸気温度が２００℃の場合、サンプル温度は、噴霧時間０．５分で過熱水蒸気Ｖが供給された場合には１０５℃となり、噴霧時間１分で過熱水蒸気Ｖが供給された場合には１５５℃となり、噴霧時間２分で過熱水蒸気Ｖが供給された場合には２００℃となり、噴霧時間４分で過熱水蒸気Ｖが供給された場合には２００℃となった。よって、いずれの噴霧時間で過熱水蒸気Ｖが供給された場合であっても、サンプル温度は、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃（本実施形態においては、約２０５℃）を超えない温度であった。これは、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度も、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度であったことを示している。噴霧時間が０．５分の場合、ラミネート強度が「◎」であり、且つ、発泡倍率が５．０倍であった。すなわち、この条件下では、噴霧時間が０．５分まで短くなっても、ラミネート強度が良好であり、且つ、発泡倍率が好適な発泡積層シート１１ａが取得でき、特に好ましかった（総合評価：Ａ）。発泡倍率が好適であることから、より十分に架橋されていると共に、発泡積層シート１ａの表面の荒れがより好適に抑制されていると評価できる。 When the amount of superheated steam V supplied to the resin composition layer 5 is 60 kg / hour and the steam temperature is 200 ° C., the sample temperature is when the superheated steam V is supplied with a spray time of 0.5 minutes. 105 ° C, 155 ° C when superheated steam V is supplied in 1 minute of spraying time, 200 ° C when superheated steam V is supplied in 2 minutes of spraying time, and overheated in 4 minutes of spraying time When steam V was supplied, the temperature reached 200 ° C. Therefore, the sample temperature is + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5 (in the present embodiment, approximately approximately) even when the superheated steam V is supplied at any spraying time. (205 ° C.). This is because the temperature of the resin composition layer 5 from the start of the supply of the superheated steam V to the end of the supply also does not exceed + 65 ° C. with respect to the decomposition temperature of the blowing agent contained in the resin composition layer 5. It shows that. When the spraying time was 0.5 minutes, the laminate strength was “◎” and the expansion ratio was 5.0 times. That is, under these conditions, even when the spraying time was shortened to 0.5 minutes, it was possible to obtain a foamed laminated sheet 11a having good laminate strength and suitable foaming ratio, which was particularly preferable (overall evaluation). : A). Since the expansion ratio is suitable, it can be evaluated that the surface of the foamed laminated sheet 1a is more suitably suppressed while being more fully cross-linked.
以上、過熱水蒸気Ｖの供給開始から供給終了時までの間における樹脂組成物層５の温度が、樹脂組成物層５に含まれる発泡剤の分解温度に対して＋６５℃を超えない温度となるように、蒸気量６０ｋｇ/時間の過熱水蒸気Ｖが樹脂組成物層５に供給されている場合には、十分且つ迅速に架橋させることができると共に、表面に形成不良を生じ難い発泡積層シート１ａを製造することが可能であると示された。 As described above, the temperature of the resin composition layer 5 from the start of supply of the superheated steam V to the end of supply is such that the temperature does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent contained in the resin composition layer 5. In addition, when superheated steam V having a steam amount of 60 kg / hour is supplied to the resin composition layer 5, the foamed laminated sheet 1 a that can be sufficiently and quickly crosslinked and hardly forms poorly on the surface is manufactured. It was shown to be possible.
１…積層シート、１ａ…発泡積層シート、３…紙基材、５…樹脂組成物層、５ａ…発泡樹脂層、１０…架橋処理装置、１２…噴霧ノズル、Ｖ…過熱水蒸気。 DESCRIPTION OF SYMBOLS 1 ... Laminated sheet, 1a ... Foam laminated sheet, 3 ... Paper base material, 5 ... Resin composition layer, 5a ... Foamed resin layer, 10 ... Crosslinking processing apparatus, 12 ... Spray nozzle, V ... Superheated steam.
Claims (5)
発泡剤及びシラン架橋性樹脂層を含有する樹脂組成物層に対し、前記樹脂組成物層の温度が前記発泡剤の分解温度に対して＋６５℃を超えない温度となるように過熱水蒸気を供給する工程を含み、
前記過熱水蒸気を供給する工程において、前記過熱水蒸気を１５ｋｇ/時間以上且つ１００ｋｇ/時間以下の噴霧蒸気量となるように前記樹脂組成物層に対して供給することにより、前記樹脂組成物層に含まれる前記シラン架橋性樹脂層を前記過熱水蒸気により架橋し、架橋後の樹脂組成物層を形成することを特徴とする発泡積層シートの製造方法。 A method for producing a foam laminate sheet comprising a substrate and a foamed resin layer formed on the substrate,
Superheated steam is supplied to the resin composition layer containing the foaming agent and the silane crosslinkable resin layer so that the temperature of the resin composition layer does not exceed + 65 ° C. with respect to the decomposition temperature of the foaming agent. Including steps,
In the step of supplying the superheated steam, the superheated steam is included in the resin composition layer by supplying the superheated steam to the resin composition layer so that the amount of sprayed steam is 15 kg / hour or more and 100 kg / hour or less. The method for producing a foamed laminated sheet is characterized in that the silane crosslinkable resin layer is crosslinked with the superheated steam to form a crosslinked resin composition layer.
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