JP4742555B2 - Raw material for foam wallpaper and method for producing the same - Google Patents

Raw material for foam wallpaper and method for producing the same Download PDF

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JP4742555B2
JP4742555B2 JP2004284765A JP2004284765A JP4742555B2 JP 4742555 B2 JP4742555 B2 JP 4742555B2 JP 2004284765 A JP2004284765 A JP 2004284765A JP 2004284765 A JP2004284765 A JP 2004284765A JP 4742555 B2 JP4742555 B2 JP 4742555B2
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resin layer
resin
electron beam
wallpaper
raw material
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JP2006097184A (en
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優 岡本
俊和 西尾
修之 小野
義昭 根津
一弘 高橋
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Dai Nippon Printing Co Ltd
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Description

本発明は、非塩化ビニル系の発泡壁紙用原反及びその製造方法に関する。   The present invention relates to a non-vinyl chloride-based raw material for foam wallpaper and a method for producing the same.

壁紙メーカーは、非塩化ビニル発泡壁紙を製造するに際し、裏打紙、発泡樹脂層原料を自ら購入して原反（印刷、加熱発泡等を施す前のもの）を製造し、次いで印刷加工、発泡エンボス加工、小巻加工等を施す場合が多い。   When manufacturing non-vinyl chloride foam wallpaper, the wallpaper manufacturer purchases the backing paper and foamed resin layer raw material to produce the original fabric (before printing, heat foaming, etc.), then printing processing, foam embossing Processing, small winding processing, etc. are often performed.

しかしながら、状況に応じて、自ら原反製造を行わずに市販の発泡壁紙用原反を購入し、印刷加工、発泡エンボス加工、小巻加工等の後加工のみを行う場合がある。   However, depending on the situation, there is a case where a commercially available raw material for foam wallpaper is purchased without producing the raw material itself, and only post-processing such as printing, foam embossing, and small roll processing is performed.

発泡壁紙用原反としては、各種のものが販売されている。そして、発泡壁紙用原反の製造方法としては、例えば、特許文献１において、未発泡樹脂層をカレンダー成形法にてシート状に成形後、連続して、表面保護層として熱可塑性樹脂を該未発泡樹脂層上にＴダイ押出法にて積層することを特徴とする製造方法が開示されている。   Various types of foam wallpaper are available. For example, in Patent Document 1, after the non-foamed resin layer is formed into a sheet shape by a calender molding method, a thermoplastic resin is used as a surface protective layer. A manufacturing method characterized by laminating on a foamed resin layer by a T-die extrusion method is disclosed.

ところが、市販されている発泡壁紙用原反を利用する場合には、（１）印刷・発泡後の表面強度は塩化ビニル系壁紙よりも強いが、発泡による凹凸の発現が不十分なもの、及び（２）発泡による凹凸の発現は十分であるが、印刷・発泡後の表面強度が塩化ビニル系壁紙よりも弱いものの何れかが得られるのが現状である。   However, when using a commercially available raw material for foamed wallpaper, (1) the surface strength after printing / foaming is stronger than that of vinyl chloride wallpaper, but the unevenness due to foaming is insufficient, and (2) Although the development of unevenness due to foaming is sufficient, the present situation is that any one of which the surface strength after printing and foaming is weaker than the vinyl chloride wallpaper is obtained.

従って、発泡による凹凸の発現が十分であり、しかも印刷・発泡後の表面強度が塩化ビニル壁紙と比較して同程度又はより強い発泡壁紙を製造できる発泡壁紙用原反の開発が要求されている。
特開２００３−２６６５４９号公報 Therefore, there is a demand for the development of a foam wall paper which can produce foam wallpaper with sufficient surface roughness after printing and foaming, and capable of producing foam wallpaper having the same or stronger strength than vinyl chloride wallpaper. .
JP 2003-266549 A

本発明は、発泡による凹凸の発現が十分であり、しかも印刷・発泡後の表面強度が塩化ビニル壁紙と比較して同程度又はより強い発泡壁紙を製造できる発泡壁紙用原反を提供することを主な目的とする。   It is an object of the present invention to provide an original fabric for foamed wallpaper, which has sufficient surface roughness due to foaming and can produce foamed wallpaper whose surface strength after printing and foaming is comparable or stronger than that of vinyl chloride wallpaper. Main purpose.

本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、紙質基材上に少なくとも未発泡樹脂層を形成してなり、該層を構成する樹脂が電子線照射により架橋されている発泡壁紙用原反が上記目的を達成できることを見出し、本発明を完成するに至った。   As a result of intensive studies to achieve the above object, the present inventor has formed at least an unfoamed resin layer on a paper substrate, and the foamed resin is crosslinked by electron beam irradiation. The inventors have found that a wallpaper fabric can achieve the above-mentioned purpose, and have completed the present invention.

即ち、本発明は、下記の発泡壁紙用原反及びその製造方法に係るものである。
１． 紙質基材上に電子線架橋型樹脂からなる透明性樹脂層Ａ、未発泡樹脂層及び電子線架橋型樹脂からなる透明性樹脂層Ｂが順に積層されてなる発泡壁紙用原反であって、該層を構成する樹脂が酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂であり、少なくとも未発泡樹脂層及び透明性樹脂層Ｂを構成する樹脂は架橋されていることを特徴とする発泡壁紙用原反。
２． 透明性樹脂層Ａ及び透明性樹脂層Ｂを構成する電子線架橋型樹脂が、酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂である、請求項１記載の発泡壁紙用原反。
３． 紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理が施されている上記項１又は２に記載の発泡壁紙用原反。
４． 紙質基材上に、１）電子線架橋型樹脂を含む透明性樹脂層Ａ形成用組成物、２）酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂及び発泡剤を含む未発泡樹脂層形成用組成物、並びに、３）電子線架橋型樹脂を含む透明性樹脂層Ｂ形成用組成物を、紙質基材側からみて樹脂層Ａ、未発泡樹脂層及び樹脂層Ｂの順に積層するようにＴダイ押出し機により３層同時押出し成形後、押出された樹脂層に電子線を照射して少なくとも未発泡樹脂層及び透明性樹脂層Ｂを構成する樹脂を架橋させることを特徴とする発泡壁紙用原反の製造方法。
５． 電子線照射後、紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理をさらに施す上記項４記載の製造方法。

以下、本発明の発泡壁紙用原反及びその製造方法について詳細に説明する。 That is, this invention relates to the following raw material for foam wallpaper, and its manufacturing method.
1. A raw material for foamed wallpaper in which a transparent resin layer A composed of an electron beam crosslinkable resin, an unfoamed resin layer, and a transparent resin layer B composed of an electron beam crosslinkable resin are sequentially laminated on a paper substrate , the resin constituting the layer is ethylene vinyl acetate content of 15 to 30% by weight - a vinyl acetate copolymer resins, resin constituting at least unfoamed resin layer and the transparent resin layer B is crosslinked Raw material for foam wallpaper characterized by having
2. The foaming of Claim 1 whose electron beam crosslinkable resin which comprises the transparent resin layer A and the transparent resin layer B is ethylene-vinyl acetate copolymer resin whose vinyl acetate content is 15 to 30 weight%. Raw material for wallpaper.
3. Item 3. The foaming according to Item 1 or 2, wherein at least one treatment selected from the group consisting of corona treatment, atmospheric plasma treatment, and primer treatment is applied to the front surface of the resin layer farthest from the paper substrate. Raw material for wallpaper .
4 . On a paper substrate, 1) a composition for forming a transparent resin layer A containing an electron beam crosslinkable resin, 2) an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 15 to 30% by weight and a foaming agent 3) A composition for forming an unfoamed resin layer, and 3) a resin layer A, an unfoamed resin layer and a resin layer as viewed from the paper substrate side of the composition for forming a transparent resin layer B containing an electron beam crosslinkable resin After three layers are co-extruded by a T-die extruder so as to be laminated in the order of B, the extruded resin layer is irradiated with an electron beam to crosslink at least the resin constituting the unfoamed resin layer and the transparent resin layer B A method for producing an original fabric for foam wallpaper.
5 . After the electron beam irradiation, corona treatment on the front surface of the farthest resin layer from the paper quality substrates, No further subjected mounting the claim 4 Symbol at least one treatment selected from the group consisting of atmospheric plasma treatment and primer treatment Production method.

Hereinafter, the raw material for foamed wallpaper of the present invention and the production method thereof will be described in detail.

発泡壁紙用原反
本発明の発泡壁紙用原反は、紙質基材上に少なくとも未発泡樹脂層を形成してなり、該層を構成する樹脂が電子線架橋型樹脂であり、該樹脂は架橋されていることを特徴とする。 Foam wallpaper raw foam wallpaper for raw present invention is made by forming at least unfoamed resin layer on the paper quality substrate, a resin constituting the layer is an electron beam cross-linked resin, the resin is crosslinked It is characterized by being.

このような特徴を有する本発明の発泡壁紙用原反は、さらに印刷・発泡（加熱発泡）を施して得られる発泡壁紙の表面強度が高い上、発泡による凹凸意匠の発現性が高い。即ち、本発明の発泡壁紙用原反によれば、壁紙に適した所望の凹凸意匠性を具備し、しかも耐スクラッチ性に代表される表面強度も十分に具備した発泡壁紙が製造できる。
（紙質基材）
紙質基材としては特に限定されず、従来、壁紙用裏打紙として公知のものが使用できる。例えば、難燃紙（パルプ主体のシートをスルファミン酸グアニジン、リン酸グアニジンなどの難燃剤で処理したシート）；水酸化アルミニウム、水酸化マグネシウム等の無機質剤を混抄した無機質紙；上質紙、薄用紙、和紙等の一般紙などが挙げられる。 The raw material for foamed wallpaper of the present invention having such characteristics has a high surface strength of the foamed wallpaper obtained by further printing and foaming (heated foaming), and has a high expression of the uneven design due to foaming. That is, according to the raw material for foamed wallpaper of the present invention, it is possible to produce a foamed wallpaper having a desired uneven design suitable for wallpaper and having sufficient surface strength typified by scratch resistance.
(Paper base material)
The paper base is not particularly limited, and conventionally known paper backing paper can be used. For example, flame retardant paper (sheets made by treating pulp-based sheets with flame retardants such as guanidine sulfamate and guanidine phosphate); inorganic paper mixed with inorganic agents such as aluminum hydroxide and magnesium hydroxide; fine paper, thin paper And general paper such as Japanese paper.

紙質基材の坪量は特に限定的ではないが、通常２０〜３００ｇ／ｍ2、好ましくは４０〜１１０ｇ／ｍ2程度である。
（未発泡樹脂層）
本発明の発泡壁紙用原反は、紙質基材上に少なくとも未発泡樹脂層が形成されている。 The basis weight of the paper-based substrate is not particularly limited, but is usually about 20 to 300 g / m 2 , preferably about 40 to 110 g / m 2 .
(Unfoamed resin layer)
The raw material for foamed wallpaper of the present invention has at least an unfoamed resin layer formed on a paper-based substrate.

未発泡樹脂層は電子線架橋型樹脂を構成樹脂とし、該樹脂は電子線照射により架橋されている。また、未発泡樹脂層は発泡剤（加熱発泡型発泡剤）を含む。   The unfoamed resin layer uses an electron beam cross-linking resin as a constituent resin, and the resin is cross-linked by electron beam irradiation. The unfoamed resin layer contains a foaming agent (heated foaming foaming agent).

電子線架橋型樹脂としては特に限定されず、電子線照射により架橋するものであればよい。電子線架橋型樹脂としては、例えば、ポリエチレン、ポリプロピレン等のオレフィン系モノマーの単独重合体又は共重合体からなるポリオレフィン系樹脂；エチレン−酢酸ビニル共重合体樹脂（以下「ＥＶＡ」と略記する）、エチレン−メチルメタクリレート共重合体樹脂（以下「ＥＭＭＡ」と略記する）、エチレン−エチルメタクリレート共重合体樹脂、エチレン−メチルメタクリレート共重合体樹脂等のα−オレフィンと酢酸ビニル、アクリル酸系モノマー等との共重合体からなるポリオレフィン系樹脂；その他、ポリスチレン樹脂、アクリル樹脂、ポリエステル樹脂等の熱可塑性樹脂等が挙げられる。   The electron beam cross-linking resin is not particularly limited as long as it is cross-linked by electron beam irradiation. Examples of the electron beam cross-linking resin include polyolefin resins composed of homopolymers or copolymers of olefin monomers such as polyethylene and polypropylene; ethylene-vinyl acetate copolymer resins (hereinafter abbreviated as “EVA”), Α-olefin such as ethylene-methyl methacrylate copolymer resin (hereinafter abbreviated as “EMMA”), ethylene-ethyl methacrylate copolymer resin, ethylene-methyl methacrylate copolymer resin, vinyl acetate, acrylic acid monomer, etc. And other thermoplastic resins such as polystyrene resins, acrylic resins, and polyester resins.

上記樹脂の中でも、特に燃焼カロリーが比較的小さく（難燃性、準不燃性に関係）、しかも安価である点からＥＶＡ及びＥＭＭＡからなる群から選択された少なくとも１種が好ましい。ＥＶＡ及びＥＭＭＡの共重合比率は特に限定されないが、ＥＶＡにおける酢酸ビニル含有量は１５〜３０重量％が好ましく、２０〜２５重量％がより好ましい。ＥＭＭＡにおけるメチルメタクリレート含有量は１５〜３０重量％が好ましく、２０〜２５重量％がより好ましい。   Among the above resins, at least one selected from the group consisting of EVA and EMMA is preferable from the viewpoint that the calories burned is relatively small (related to flame retardancy and quasi-incombustibility) and is inexpensive. The copolymerization ratio of EVA and EMMA is not particularly limited, but the vinyl acetate content in EVA is preferably 15 to 30% by weight, and more preferably 20 to 25% by weight. The methyl methacrylate content in EMMA is preferably 15 to 30% by weight, and more preferably 20 to 25% by weight.

未発泡樹脂層は、発泡剤を含有している。発泡剤としては、従来公知の加熱発泡型の発泡剤を適宜選択すればよい。例えば、アゾ系発泡剤、特にアゾジカルボンアミド（ＡＤＣＡ）がコスト、発泡性能（発泡温度、安定性、発泡倍率）の観点から好ましい。   The unfoamed resin layer contains a foaming agent. As the foaming agent, a conventionally known heat foaming type foaming agent may be appropriately selected. For example, an azo foaming agent, particularly azodicarbonamide (ADCA) is preferable from the viewpoints of cost and foaming performance (foaming temperature, stability, foaming ratio).

発泡剤の含有量は特に限定されず、樹脂種、発泡倍率等により異なるが、通常は樹脂１００重量部に対して１〜２０重量部程度である。   The content of the foaming agent is not particularly limited and varies depending on the resin type, the expansion ratio, etc., but is usually about 1 to 20 parts by weight with respect to 100 parts by weight of the resin.

未発泡樹脂層は、必要に応じて、無機充填剤を含有してもよい。無機充填剤としては、例えば、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、三酸化アンチモン、ホウ酸亜鉛、モリブデン化合物等が挙げられる。この中でも、特に水酸化アルミニウム、炭酸カルシウムが好ましい。無機充填剤を配合することにより、発泡壁紙の目透き抑制効果、表面特性を高める効果等が得られる。無機充填剤の添加量としては、樹脂１００重量部に対して、通常３０〜２００重量部程度である。   The unfoamed resin layer may contain an inorganic filler as necessary. Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. Among these, aluminum hydroxide and calcium carbonate are particularly preferable. By blending the inorganic filler, an effect of suppressing the see-through of the foamed wallpaper, an effect of improving the surface characteristics, and the like can be obtained. The addition amount of the inorganic filler is usually about 30 to 200 parts by weight with respect to 100 parts by weight of the resin.

未発泡樹脂層は、必要に応じて、無機充填剤以外の添加剤を含んでもよい。例えば、顔料、発泡セル調整剤、熱安定剤、難燃剤等が挙げられる。これらの添加剤の含有量は特に限定されず、発泡壁紙の所望の特性に応じて適宜設定できる。   The unfoamed resin layer may contain an additive other than the inorganic filler as necessary. For example, pigments, foam cell regulators, heat stabilizers, flame retardants, etc. The content of these additives is not particularly limited, and can be appropriately set according to the desired characteristics of the foam wallpaper.

未発泡樹脂層の厚みは特に限定されないが、通常７０〜１３０μｍ、好ましくは９０〜１１０μｍである。
（具体的な原反の構成）
本発明の発泡壁紙原反は、紙質基材上に前記未発泡樹脂層を有していればよいが、他の層をさらに有していてもよい。 Although the thickness of an unfoamed resin layer is not specifically limited, Usually, 70-130 micrometers, Preferably it is 90-110 micrometers.
(Specific material composition)
Although the foamed wallpaper original fabric of this invention should just have the said non-foamed resin layer on a paper-like base material, you may further have another layer.

例えば、紙質基材上に電子線架橋型樹脂からなる透明性樹脂層Ａ、前記未発泡樹脂層及び電子線架橋型樹脂からなる透明性樹脂層Ｂ（表面保護層）が順に積層された層構成が好ましいものとして挙げられる。この層構成では、未発泡樹脂層に加えて、最表面樹脂層である透明性樹脂層Ｂを構成する樹脂も架橋されていることが好ましい。表面保護層が架橋されていれば、より優れた表面強度が得られるため好ましい。   For example, a transparent resin layer A composed of an electron beam crosslinkable resin, a transparent resin layer B (surface protective layer) composed of an unfoamed resin layer and an electron beam crosslinkable resin are sequentially laminated on a paper substrate. Is preferable. In this layer configuration, in addition to the unfoamed resin layer, the resin constituting the transparent resin layer B that is the outermost resin layer is preferably crosslinked. If the surface protective layer is cross-linked, it is preferable because more excellent surface strength can be obtained.

透明性樹脂層Ａ及びＢは、電子線架橋型樹脂を構成樹脂とする。電子線架橋型樹脂の種類は前記と同様であり、特にＥＶＡ及びＥＭＭＡからなる群から選択された少なくとも１種が好ましい。ＥＶＡ及びＥＭＭＡの共重合比率は特に限定されないが、ＥＶＡにおける酢酸ビニル含有量は１５〜２５重量％が好ましく、１９〜２３重量％がより好ましい。ＥＭＭＡにおけるメチルメタクリレート含有量は１５〜２５重量％が好ましく、１９〜２３重量％がより好ましい。なお、紙質基材との密着性の観点からは、ＥＶＡ及びＥＭＭＡの共重合比率は高く設定する方が好ましい。   The transparent resin layers A and B have an electron beam crosslinkable resin as a constituent resin. The kind of electron beam cross-linking resin is the same as described above, and at least one selected from the group consisting of EVA and EMMA is particularly preferable. The copolymerization ratio of EVA and EMMA is not particularly limited, but the vinyl acetate content in EVA is preferably 15 to 25% by weight, more preferably 19 to 23% by weight. The methyl methacrylate content in EMMA is preferably 15 to 25% by weight, more preferably 19 to 23% by weight. From the viewpoint of adhesion to the paper-based substrate, it is preferable to set the copolymerization ratio of EVA and EMMA high.

なお、透明性樹脂層Ｂは樹脂架橋されていることが好ましいため、必要に応じて、架橋助剤を含んでもよい。架橋助剤の種類、含有量等は特に限定されず適宜設定できる。   In addition, since it is preferable that the transparent resin layer B is resin-crosslinked, it may contain a crosslinking aid as necessary. The type and content of the crosslinking aid are not particularly limited and can be appropriately set.

透明性樹脂層Ａ及びＢの厚みも特に限定されないが、透明性樹脂層Ａの厚みは、通常２〜１５μｍ、好ましくは５〜１０μｍである。透明性樹脂層Ｂの厚みは、通常１０〜４０μｍ、好ましくは１５〜３０μｍである。   Although the thickness of the transparent resin layers A and B is not particularly limited, the thickness of the transparent resin layer A is usually 2 to 15 μm, preferably 5 to 10 μm. The thickness of the transparent resin layer B is usually 10 to 40 μm, preferably 15 to 30 μm.

本発明の発泡壁紙原反は、紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理が施されていることが好ましい。処理後の表面の濡れ指数としては４０ｄｙｎｅ／ｃｍ以上が好ましく、５０ｄｙｎｅ／ｃｍ以上がより好ましい。これらの処理が施されていれば、さらにプライマー処理を施すことなく容易に印刷加工を施せるため好ましい。コロナ処理、大気プラズマ処理及びプライマー処理は常法に従って行えばよい。   The foamed wallpaper original fabric of the present invention is subjected to at least one treatment selected from the group consisting of corona treatment, atmospheric plasma treatment and primer treatment on the front surface of the resin layer farthest from the paper-based substrate. It is preferable. The surface wetting index after the treatment is preferably 40 dyne / cm or more, and more preferably 50 dyne / cm or more. It is preferable that these treatments are performed because printing can be easily performed without further primer treatment. Corona treatment, atmospheric plasma treatment and primer treatment may be performed according to conventional methods.

発泡壁紙用原反の製造方法
本発明の発泡壁紙原反の製造方法は特に限定されないが、紙質基材上に電子線架橋型樹脂及び発泡剤を含む未発泡樹脂層形成用組成物をＴダイ押出し機によりシート状に押出し成形後、押出された樹脂層に電子線を照射して樹脂を架橋させることを特徴とする製造方法が好ましい。 Method for Producing Foamed Wallpaper Raw Material The method for producing the foamed wallpaper raw material of the present invention is not particularly limited, but a composition for forming an unfoamed resin layer containing an electron beam cross-linking resin and a foaming agent on a paper base is used as a T-die. A production method is preferred in which the resin layer is cross-linked by irradiating the extruded resin layer with an electron beam after being extruded into a sheet by an extruder.

未発泡樹脂層形成用組成物は、電子線架橋型樹脂及び発泡剤を含み、必要に応じて、前記した添加剤を含んでもよい。該組成物は紙質基材上にＴダイ押出し機によりシート状に押出し成形される。該組成物に含まれる樹脂の押出し時のメルトフローレート（ＭＦＲ）としては、５０〜１５０ｇ／１０分、好ましくは７０〜１２０ｇ／１０分程度である。該組成物のＭＦＲとしては、３５〜５５ｇ／１０分程度が好ましい。押出し時の組成物温度は１２０〜１３０℃程度が好ましい。   The composition for forming an unfoamed resin layer includes an electron beam cross-linking resin and a foaming agent, and may include the above-described additives as necessary. The composition is extruded into a sheet by a T-die extruder on a paper substrate. The melt flow rate (MFR) at the time of extrusion of the resin contained in the composition is 50 to 150 g / 10 minutes, preferably about 70 to 120 g / 10 minutes. The MFR of the composition is preferably about 35 to 55 g / 10 minutes. As for the composition temperature at the time of extrusion, about 120-130 degreeC is preferable.

なお、未発泡樹脂層に加えて、前記透明性樹脂層Ａ及びＢも形成する場合には、Ｔダイ押出し機を用いた３層同時押出し成形が好ましい。３層同時押出し成形時は、３層に含まれる樹脂のＭＦＲを近似させることが３層の厚み比率を安定化できる点で好ましい。透明性樹脂層Ａ及びＢを形成するための組成物に含まれる樹脂のＭＦＲは、未発泡樹脂層形成用組成物に含まれる樹脂のＭＦＲを考慮して設定すればよいが、例えば、透明性樹脂層Ａ形成用組成物に含まれる樹脂のＭＦＲは７０〜１２０ｇ／１０分程度である。また、透明性樹脂層Ａ形成用組成物に含まれる樹脂のＭＦＲは７０〜１２０ｇ／１０分程度である。押出し時の各層の厚みは製品である原反における各層の厚みを考慮して設定すればよい。   When forming the transparent resin layers A and B in addition to the unfoamed resin layer, three-layer coextrusion molding using a T-die extruder is preferable. At the time of three-layer coextrusion molding, it is preferable that the MFR of the resin contained in the three layers is approximated in that the thickness ratio of the three layers can be stabilized. The MFR of the resin contained in the composition for forming the transparent resin layers A and B may be set in consideration of the MFR of the resin contained in the composition for forming an unfoamed resin layer. The MFR of the resin contained in the composition for forming the resin layer A is about 70 to 120 g / 10 minutes. Moreover, MFR of resin contained in the composition for transparent resin layer A formation is about 70-120 g / 10min. What is necessary is just to set the thickness of each layer at the time of extrusion in consideration of the thickness of each layer in the raw material which is a product.

押出し成形後、電子線照射により樹脂架橋する。未発泡樹脂層を構成する電子線架橋型樹脂は電子線照射により架橋されている。また、透明性樹脂層Ｂを形成する場合には、透明性樹脂層Ｂも樹脂架橋されていることが好ましい。電子線照射装置としては、例えば、コックロフトワルトン型、バンデグラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等が使用できる。照射される電子線のエネルギーは、通常５０〜５００ＫｅＶ、好ましくは１００〜２００ＫｅＶ程度である。また、電子線の吸収線量としては、通常２〜７Ｍｒａｄ、好ましくは３〜５Ｍｒａｄ程度である。   After extrusion molding, resin crosslinking is performed by electron beam irradiation. The electron beam cross-linking resin constituting the unfoamed resin layer is cross-linked by electron beam irradiation. Moreover, when forming the transparent resin layer B, it is preferable that the transparent resin layer B is also resin-crosslinked. As the electron beam irradiation device, for example, a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, a high frequency type, or the like can be used. The energy of the irradiated electron beam is usually 50 to 500 KeV, preferably about 100 to 200 KeV. Further, the absorbed dose of the electron beam is usually 2 to 7 Mrad, preferably about 3 to 5 Mrad.

電子線照射後は、紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理をさらに施すことが好ましい。これにより、後工程の印刷加工を容易化できる。コロナ処理、大気プラズマ処理及びプライマー処理は常法に従って行えばよい。処理の程度は、処理面の濡れ指数が前記範囲内となるように設定することが好ましい。   After the electron beam irradiation, it is preferable to further perform at least one treatment selected from the group consisting of corona treatment, atmospheric plasma treatment and primer treatment on the front surface of the resin layer farthest from the paper-based substrate. Thereby, the printing process of a post process can be made easy. Corona treatment, atmospheric plasma treatment and primer treatment may be performed according to conventional methods. The degree of treatment is preferably set so that the wetting index of the treated surface is within the above range.

本発明の発泡壁紙用原反は、さらに印刷・発泡（加熱発泡）を施して得られる発泡壁紙の表面強度が高い上、発泡による凹凸意匠の発現性が高い。即ち、本発明の発泡壁紙用原反によれば、壁紙に適した所望の凹凸意匠性を具備し、しかも耐スクラッチ性に代表される表面強度も十分に具備した発泡壁紙が製造できる。   The raw material for foamed wallpaper of the present invention has high surface strength of the foamed wallpaper obtained by further printing and foaming (heating foaming), and also has a high expressiveness of the uneven design due to foaming. That is, according to the raw material for foamed wallpaper of the present invention, it is possible to produce a foamed wallpaper having a desired uneven design suitable for wallpaper and having sufficient surface strength typified by scratch resistance.

本発明の製造方法によれば、凹凸意匠を発現し易く、しかも表面強度の高い発泡壁紙の製造に適した発泡壁紙用原反を容易に製造できる。   According to the production method of the present invention, it is possible to easily produce a raw material for foamed wallpaper suitable for production of a foamed wallpaper having high surface strength that easily expresses an uneven design.

以下に実施例及び比較例を示し、本発明をより具体的に説明する。但し、本発明は実施例に限定されない。   Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

実施例１
ＥＶＡ（ＭＦＲ７０ｇ／１０分、ＶＡ含有量２０重量％、住友化学ＣＶ５０５３）を透明性樹脂層Ａ形成用組成物とした。 Example 1
EVA (MFR 70 g / 10 min, VA content 20% by weight, Sumitomo Chemical CV5053) was used as the composition for forming the transparent resin layer A.

ＥＶＡ（ＭＦＲ７０ｇ／１０分、ＶＡ含有量２０重量％、住友化学ＣＶ５０５３）１００重量部に対してＥＶＡ（ＭＦＲ１５０ｇ／１０分、ＶＡ含有量２０重量％、住友化学ＨＣ１０）３０重量部、炭酸カルシウム（白石工業ホワイトンＨ）３０重量部、酸化チタン（デュポンＲ１０８）２０重量部、発泡剤（♯３）３重量部、発泡剤（♯５０００）１重量部、セル調整剤（旭電化工業ＯＦ１０１）５重量部及び架橋助剤（ＪＳＲアクリルモノマー）１重量部を添加したものを未発泡樹脂層形成用組成物とした。   EVA (MFR 150 g / 10 min, VA content 20% by weight, Sumitomo Chemical HC10) 30 parts by weight, calcium carbonate (Shiraishi) for 100 parts by weight of EVA (MFR 70 g / 10 min, VA content 20% by weight, Sumitomo Chemical CV5053) Industrial whiten H) 30 parts by weight, titanium oxide (DuPont R108) 20 parts by weight, foaming agent (# 3) 3 parts by weight, foaming agent (# 5000) 1 part by weight, cell regulator (Asahi Denka Kogyo OF101) 5 parts by weight A composition for forming an unfoamed resin layer was obtained by adding 1 part by weight of a part and a crosslinking aid (JSR acrylic monomer).

ＥＶＡ（ＭＦＲ７０ｇ／１０分、ＶＡ含有量２０重量％、住友化学ＣＶ５０５３）１００重量部に対して架橋助剤（ＪＳＲアクリルモノマー）２重量部を添加したものを透明性樹脂層Ｂ形成用組成物とした。   A composition for forming a transparent resin layer B is obtained by adding 2 parts by weight of a crosslinking assistant (JSR acrylic monomer) to 100 parts by weight of EVA (MFR 70 g / 10 min, VA content 20% by weight, Sumitomo Chemical CV5053). did.

紙質基材上に、紙質基材側からみて樹脂層Ａ、未発泡樹脂層及び樹脂層Ｂの順に積層するようにＴダイ押出し機により３層同時押出し成形した。各層の厚みは、樹脂層Ａが１０μｍ、未発泡樹脂層が９０μｍ、樹脂層Ｂが２０μｍとした。   On the paper base, three layers were coextruded by a T-die extruder so that the resin layer A, the unfoamed resin layer, and the resin layer B were laminated in this order when viewed from the paper base. The thickness of each layer was 10 μm for the resin layer A, 90 μm for the unfoamed resin layer, and 20 μm for the resin layer B.

押出し後の樹脂層に電子線照射して樹脂架橋を行った。電子線エネルギーは１７５ｋＶ、吸収線量５Ｍｒａｄとした。   The resin layer after extrusion was irradiated with an electron beam for resin crosslinking. The electron beam energy was 175 kV and the absorbed dose was 5 Mrad.

次いで、透明性樹脂層Ｂのおもて面に大気プラズマ処理を施した。処理後の濡れ指数が５０ｄｙｎｅ／ｃｍとなるように処理した。   Next, atmospheric plasma treatment was performed on the front surface of the transparent resin layer B. It processed so that the wetness index after a process might be set to 50 dyne / cm.

試験例１
実施例１で得られた発泡壁紙用原反に熱処理を施した。加熱発泡により得られた凹凸意匠性は良好であった。 Test example 1
The raw material for foamed wallpaper obtained in Example 1 was subjected to heat treatment. The uneven design obtained by heat foaming was good.

また、ビニル工業会表面強度試験法に従って、発泡壁紙の表面強度を測定したところ、評価は５級であった。評価は１級〜５級まであり、５級が最も優れた表面強度を有することを意味する。   In addition, when the surface strength of the foamed wallpaper was measured according to the vinyl industry association surface strength test method, the evaluation was grade 5. Evaluation is from grade 1 to grade 5, meaning that grade 5 has the best surface strength.

参考のため、他の発泡壁紙の表面強度との比較データを下記表１に示す。   For reference, the comparison data with the surface strength of other foamed wallpaper is shown in Table 1 below.

Figure 0004742555
Figure 0004742555

Claims (5)

紙質基材上に電子線架橋型樹脂からなる透明性樹脂層Ａ、未発泡樹脂層及び電子線架橋型樹脂からなる透明性樹脂層Ｂが順に積層されてなる発泡壁紙用原反であって、該未発泡樹脂層を構成する樹脂が酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂であり、少なくとも未発泡樹脂層及び透明性樹脂層Ｂを構成する樹脂は架橋されていることを特徴とする発泡壁紙用原反。 A raw material for foamed wallpaper in which a transparent resin layer A composed of an electron beam crosslinkable resin, an unfoamed resin layer, and a transparent resin layer B composed of an electron beam crosslinkable resin are sequentially laminated on a paper substrate , yet-ethylene resin forming the foamed resin layer is 15 to 30 wt% vinyl acetate content - a vinyl acetate copolymer resins, resin constituting at least unfoamed resin layer and the transparent resin layer B A raw material for foam wallpaper characterized by being crosslinked. 透明性樹脂層Ａ及び透明性樹脂層Ｂを構成する電子線架橋型樹脂が、酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂である、請求項１記載の発泡壁紙用原反。The foaming of Claim 1 whose electron beam crosslinkable resin which comprises the transparent resin layer A and the transparent resin layer B is ethylene-vinyl acetate copolymer resin whose vinyl acetate content is 15 to 30 weight%. Raw material for wallpaper. 紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理が施されている請求項１又は２に記載の発泡壁紙用原反。   The foaming according to claim 1 or 2, wherein at least one treatment selected from the group consisting of corona treatment, atmospheric plasma treatment and primer treatment is applied to the front surface of the resin layer farthest from the paper substrate. Raw material for wallpaper. 紙質基材上に、１）電子線架橋型樹脂を含む透明性樹脂層Ａ形成用組成物、２）酢酸ビニル含有量が１５〜３０重量％であるエチレン−酢酸ビニル共重合体樹脂及び発泡剤を含む未発泡樹脂層形成用組成物、並びに、３）電子線架橋型樹脂を含む透明性樹脂層Ｂ形成用組成物を、紙質基材側からみて樹脂層Ａ、未発泡樹脂層及び樹脂層Ｂの順に積層するようにＴダイ押出し機により３層同時押出し成形後、押出された樹脂層に電子線を照射して少なくとも未発泡樹脂層及び透明性樹脂層Ｂを構成する樹脂を架橋させることを特徴とする発泡壁紙用原反の製造方法。 On a paper substrate, 1) a composition for forming a transparent resin layer A containing an electron beam crosslinkable resin, 2) an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 15 to 30% by weight and a foaming agent 3) A composition for forming an unfoamed resin layer, and 3) a resin layer A, an unfoamed resin layer and a resin layer as viewed from the paper substrate side of the composition for forming a transparent resin layer B containing an electron beam crosslinkable resin After three layers are co-extruded by a T-die extruder so as to be laminated in the order of B, the extruded resin layer is irradiated with an electron beam to crosslink at least the resin constituting the unfoamed resin layer and the transparent resin layer B A method for producing an original fabric for foam wallpaper. 電子線照射後、紙質基材から最も離れた樹脂層のおもて面にコロナ処理、大気プラズマ処理及びプライマー処理からなる群から選択された少なくとも１種の処理をさらに施す請求項４記載の製造方法。 After the electron beam irradiation, corona treatment on the front surface of the farthest resin layer from the paper quality substrates, No further subjected mounting according to claim 4 Symbol at least one treatment selected from the group consisting of atmospheric plasma treatment and primer treatment Production method.
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