JP2005238498A - Decorative sheet and decorative steel panel using it - Google Patents
Decorative sheet and decorative steel panel using it Download PDFInfo
- Publication number
- JP2005238498A JP2005238498A JP2004048311A JP2004048311A JP2005238498A JP 2005238498 A JP2005238498 A JP 2005238498A JP 2004048311 A JP2004048311 A JP 2004048311A JP 2004048311 A JP2004048311 A JP 2004048311A JP 2005238498 A JP2005238498 A JP 2005238498A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- layer
- decorative sheet
- decorative
- transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910000831 Steel Inorganic materials 0.000 title claims description 19
- 239000010959 steel Substances 0.000 title claims description 19
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- 229920005989 resin Polymers 0.000 claims abstract description 88
- 239000011347 resin Substances 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 229920001225 polyester resin Polymers 0.000 claims abstract description 45
- 239000004645 polyester resin Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 29
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
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- 238000007759 kiss coating Methods 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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Images
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、化粧シート及びそれを用いた化粧鋼板に関する。 The present invention relates to a decorative sheet and a decorative steel sheet using the decorative sheet.
建築物の内装、建具の表面装飾、車両の内装等に用いられる化粧シートとして、一般に基材シート、ベタインキ層及び／又は絵柄インキ層からなるインキ層、接着剤層、透明性樹脂層等を順次積層させた複合シートが知られている。 As a decorative sheet used for the interior of buildings, surface decoration of fittings, interior of vehicles, etc., in general, an ink layer consisting of a base sheet, a solid ink layer and / or a pattern ink layer, an adhesive layer, a transparent resin layer, etc. Laminated composite sheets are known.
このような化粧シートにおいて、従来、インキ層及び接着剤層は、トルエン、キシレン等の芳香族溶剤、メチルエチルケトン、酢酸エチル等の脂肪族溶剤などを含む溶剤系塗工剤から形成されている（例えば、特許文献１参照）。 In such a decorative sheet, the ink layer and the adhesive layer are conventionally formed from a solvent-based coating agent containing an aromatic solvent such as toluene and xylene, an aliphatic solvent such as methyl ethyl ketone and ethyl acetate (for example, , See Patent Document 1).
上記した芳香族溶剤、脂肪族溶剤等は、いずれも有機性揮発物質（ＶＯＣ）であり、特にトルエン、キシレン等の芳香族溶剤はＰＲＴＲ法の指定化学物質及び室内空気中化学物質の指針値策定物質として挙げられている。また、化粧シート製造時における溶剤系塗工剤に含まれるＶＯＣの揮発による作業環境の問題、化粧シート使用時における残存ＶＯＣが一般の生活空間に拡散される環境安全性の問題等が指摘されている。そのため、化粧シート中のＶＯＣ使用量を低減することが最近の課題となっている。 All of the above-mentioned aromatic solvents and aliphatic solvents are organic volatile substances (VOC). In particular, aromatic solvents such as toluene and xylene are formulated as guidelines for PRTR-designated chemical substances and indoor air chemical substances. Listed as a substance. In addition, problems in the working environment due to volatilization of VOC contained in the solvent-based coating agent at the time of manufacturing the decorative sheet, environmental safety problems in which the residual VOC at the time of using the decorative sheet is diffused into a general living space, etc. have been pointed out. Yes. Therefore, reducing the amount of VOC used in the decorative sheet has become a recent issue.
従って、ＶＯＣ使用量が低減された化粧シートの開発が望まれている。また、化粧シートが各種耐候剤（紫外線吸収剤、光安定剤等）を含む場合には、耐候剤の滲出（いわゆるブリード）が抑制された取扱い容易な化粧シートの開発も望まれている。さらに、浴室等のように温度・湿度が高い環境下で使用しても、最表層の剥離、脱落、亀裂等が発生し難い化粧シートの開発も望まれている。
本発明は、ＶＯＣ使用量が低減された化粧シートを提供することを主な目的とする。 The main object of the present invention is to provide a decorative sheet with reduced VOC usage.
また、耐候剤のブリード抑制効果が高く、温度・湿度が高い環境下で使用しても優れた経時的安定性を発揮する化粧シートを提供することも目的とする。 It is another object of the present invention to provide a decorative sheet that has a high bleed-inhibiting effect of a weathering agent and exhibits excellent temporal stability even when used in an environment with high temperature and humidity.
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、特定の化粧シート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 inventors have found that a specific decorative sheet can achieve the above object, and have completed the present invention.
即ち、本発明は、下記の化粧シートに係る。
１．ポリオレフィン系樹脂又はポリエステル系樹脂からなる基材シート上に、絵柄模様層、透明性接着剤層及び透明性ポリエステル系樹脂層が順に積層されてなる化粧シートであって、化粧シートを構成する層の少なくとも１種が水性組成物から形成されていることを特徴とする化粧シート。
２．水性組成物が、塩基性中和剤を含む上記項１記載の化粧シート。
３．塩基性中和剤が、第２級アミン、第３級アミン、水酸化ナトリウム、水酸化カリウム及びアンモニアの少なくとも１種である上記項１又は２に記載の化粧シート。
４．基材シートと絵柄模様層との間に、さらに着色隠蔽層が形成されている上記項１〜３のいずれかに記載の化粧シート。
５．ポリエステル系樹脂が、ポリエチレンテレフタレート又はポリブチレンテレフタレートである上記項１〜４のいずれかに記載の化粧シート。
６．透明性ポリエステル系樹脂層を構成する樹脂のヘイズ値が５％以下である上記項１〜５のいずれかに記載の化粧シート。
７．透明性接着剤層が、ヒートシール材又は電離放射線硬化型樹脂から形成されている上記項１〜６のいずれかに記載の化粧シート。
８．透明性ポリエステル系樹脂層の上に、さらに電離放射線硬化型樹脂からなる透明性表面保護層が形成されている上記項１〜７のいずれかに記載の化粧シート。
９．上記項１〜８のいずれかに記載の化粧シートの基材シート側を、耐候剤を含む接着剤を介して鋼板に貼着してなる化粧鋼板。
１０．浴室用化粧鋼板である上記項９記載の化粧鋼板。
以下、本発明の化粧シート及び化粧鋼板について詳細に説明する。
That is, the present invention relates to the following decorative sheet.
1. A decorative sheet in which a pattern layer, a transparent adhesive layer, and a transparent polyester-based resin layer are sequentially laminated on a base sheet made of a polyolefin-based resin or a polyester-based resin, and a layer constituting the decorative sheet A decorative sheet, wherein at least one kind is formed from an aqueous composition.
2. Item 2. The decorative sheet according to Item 1, wherein the aqueous composition contains a basic neutralizing agent.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the basic neutralizing agent is at least one of a secondary amine, a tertiary amine, sodium hydroxide, potassium hydroxide, and ammonia.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein a colored concealing layer is further formed between the base sheet and the pattern layer.
5). Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the polyester resin is polyethylene terephthalate or polybutylene terephthalate.
6). Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a haze value of a resin constituting the transparent polyester resin layer is 5% or less.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the transparent adhesive layer is formed from a heat sealing material or an ionizing radiation curable resin.
8). The decorative sheet according to any one of Items 1 to 7, wherein a transparent surface protective layer made of an ionizing radiation curable resin is further formed on the transparent polyester resin layer.
9. A decorative steel sheet obtained by attaching the base sheet side of the decorative sheet according to any one of Items 1 to 8 to a steel sheet via an adhesive containing a weathering agent.
10. Item 10. The decorative steel sheet according to Item 9, which is a bathroom decorative steel sheet.
Hereinafter, the decorative sheet and decorative steel sheet of the present invention will be described in detail.
本発明の化粧シートは、ポリオレフィン系樹脂又はポリエステル系樹脂からなる基材シート上に、絵柄模様層、透明性接着剤層及び透明性ポリエステル系樹脂層が順に積層されてなる化粧シートであって、化粧シートを構成する層の少なくとも１種が水性組成物から形成されていることを特徴とする。 The decorative sheet of the present invention is a decorative sheet in which a pattern layer, a transparent adhesive layer, and a transparent polyester resin layer are sequentially laminated on a base sheet made of a polyolefin resin or a polyester resin, At least one of the layers constituting the decorative sheet is formed from an aqueous composition.
基材シート
基材シートとしては、ポリオレフィン系樹脂又はポリエステル系樹脂からなるシートを用いる。通常は、これらの樹脂からなるフィルムを使用すればよい。
As the base sheet, a sheet made of polyolefin resin or polyester resin is used. Usually, a film made of these resins may be used.
ポリオレフィン系樹脂としては特に限定されず、化粧シートの分野で通常用いられているものが使用できる。例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリメチルペンテン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−プロピレン−ブテン共重合体、ポリオレフィン系熱可塑性エラストマー等が挙げられる。これらの中でも、特にポリプロピレン、ポリオレフィン系熱可塑性エラストマー等が好ましい。 It does not specifically limit as polyolefin resin, What is normally used in the field | area of a decorative sheet can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.
ポリプロピレンを主成分とする単独又は共重合体も好ましく、例えば、ホモポリプロピレン樹脂、ランダムポリプロピレン樹脂、ブロックポリプロピレン樹脂、及び、ポリプロピレン結晶部を有し、且つプロピレン以外の炭素数２〜２０のα−オレフィンが挙げられる。その他、エチレン、ブテン−１、４−メチルペンテン−１、ヘキセン−１又はオクテン−１のコモノマーを１５モル％以上含有するプロピレン−α−オレフィン共重合体等も好ましい。 A homopolymer or a copolymer mainly composed of polypropylene is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and an α-olefin having 2 to 20 carbon atoms other than propylene. Is mentioned. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.
ポリオレフィン系熱可塑性エラストマーは、ハードセグメントに高結晶性で且つ高融点の芳香族ポリエステル、ソフトセグメントにガラス転移温度が−７０℃以下の非晶性ポリエーテルを使用したブロックポリマーである。特に、アイソタクチックポリプロピレンからなるハードセグメントとアタクチックポリプロピレンからなるソフトセグメントとを重量比８０：２０で混合したものが好ましい。 The polyolefin-based thermoplastic elastomer is a block polymer using a highly crystalline and high melting point aromatic polyester for a hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or less for a soft segment. In particular, a mixture of a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene at a weight ratio of 80:20 is preferable.
ポリエステル系樹脂としても特に限定されず、化粧シートの分野で通常用いられているものが使用できる。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート、ポリカーボネート、エチレンテレフタレート−イソフタレート共重合体、ポリアリレート等が挙げられる。この中でも、特にポリエチレンテレフタレート、ポリブチレンテレフタレート等が好ましい。 The polyester resin is not particularly limited, and those usually used in the field of decorative sheets can be used. Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer, polyarylate and the like. Among these, polyethylene terephthalate, polybutylene terephthalate and the like are particularly preferable.
ポリエステル系樹脂としても、ポリオレフィン系樹脂と同様に、各種ホモポリマーの他、樹脂の柔軟化等の目的で各種の共重合成分又は改質成分を添加した共重合ポリエステル系樹脂、ポリエステル系熱可塑性エラストマー等が使用できる。具体的には、テレフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸又はジカルボン酸エステルと、エチレングリコール、１，４−ブタンジオール等の脂肪族ジオールとの縮合重合反応において、ジカルボン酸成分として、例えば、セバシン酸、エイコ酸、ドデカンジオン酸、ダイマー酸、シクロヘキサンジカルボン酸等の長鎖脂肪族ジカルボン酸及び／又は脂環族ジカルボン酸を導入したり、及び／又は、ジオール成分としてポリエチレングリコール、ポリテトラメチレングリコール等の両末端に水酸基を有するポリエーテル系ジオールを導入したもの等が好ましいものとして挙げられる。 As with polyester resins, in addition to various homopolymers, polyester resins, polyester resins, and polyester thermoplastic resins added with various copolymer components or modifying components for the purpose of softening the resin, etc. Etc. can be used. Specifically, in a condensation polymerization reaction of an aromatic dicarboxylic acid or dicarboxylic acid ester such as terephthalic acid or naphthalenedicarboxylic acid and an aliphatic diol such as ethylene glycol or 1,4-butanediol, as a dicarboxylic acid component, for example, Long chain aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids such as sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, and / or polyethylene glycol, polytetra Preferred are those in which polyether diols having hydroxyl groups at both ends such as methylene glycol are introduced.
上記したポリオレフィン系樹脂及びポリエステル系樹脂は、例えば、カレンダー法、インフレーション法、Ｔダイ押し出し法等によりフィルム状にすればよい。 The above-described polyolefin resin and polyester resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.
基材シートの厚みは特に限定されず、製品特性に応じて設定できるが、通常２０〜２００μｍ、好ましくは４０〜１００μｍ程度である。 The thickness of the base sheet is not particularly limited and can be set according to product characteristics, but is usually 20 to 200 μm, preferably about 40 to 100 μm.
基材シートには、必要に応じて、添加剤が配合されてもよい。添加剤としては、例えば、炭酸カルシウム、クレー等の充填剤、水酸化マグネシウム等の難燃剤、酸化防止剤、滑剤、発泡剤、着色剤（下記参照）などが挙げられる。添加剤の配合量は、製品特性に応じて適宜設定できる。 An additive may be mix | blended with a base material sheet as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant (see below). The blending amount of the additive can be appropriately set according to the product characteristics.
着色剤としては特に限定されず、顔料、染料等の公知の着色剤を使用できる。例えば、チタン白、亜鉛華、弁柄、朱、群青、コバルトブルー、チタン黄、黄鉛、カーボンブラック等の無機顔料；イソインドリノン、ハンザイエローＡ、キナクリドン、パーマネントレッド４Ｒ、フタロシアニンブルー、インダスレンブルーＲＳ、アニリンブラック等の有機顔料（染料も含む）；アルミニウム、真鍮等の金属顔料；二酸化チタン被覆雲母、塩基性炭酸鉛等の箔粉からなる真珠光沢（パール）顔料などが挙げられる。基材シートの着色態様には、透明着色と不透明着色（隠蔽着色）があり、これらは任意に選択できる。例えば、被着材（化粧シートを接着する基材）の地色を着色隠蔽する場合には、不透明着色を選択すればよい。一方、被着材の地模様を目視できるようにする場合には、透明着色を選択すればよい。 It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of the adherend (base material to which the decorative sheet is bonded) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.
基材シートの片面又は両面には、必要に応じて、コロナ放電処理、オゾン処理、プラズマ処理、電離放射線処理、重クロム酸処理等の表面処理を施してもよい。例えば、コロナ放電処理を行う場合には、基材シート表面の表面張力が３０ｄｙｎｅ以上、好ましくは４０ｄｙｎｅ以上となるようにすればよい。表面処理は、各処理の常法に従って行えばよい。 One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.
基材シートの片面又は両面には、必要に応じて、プライマー層を設けてもよい。プライマー層を設けることにより、隣接層（例えば、被着材）との層間密着力を高めることができる。 A primer layer may be provided on one side or both sides of the base sheet as necessary. By providing the primer layer, interlayer adhesion with an adjacent layer (for example, an adherend) can be increased.
プライマー層は、公知のプライマー剤を基材シートの片面又は両面に塗布することにより形成できる。プライマー剤としては、有機溶剤を含まない水性組成物、特に水性樹脂エマルションが好ましい。例えば、アクリル変性ウレタン樹脂等からなるウレタン樹脂系水性プライマー剤、具体的には、トリイソプロパノールアミンを中和剤とした水性ウレタン樹脂エマルションが挙げられる。 A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. As a primer agent, the aqueous composition which does not contain an organic solvent, especially an aqueous resin emulsion are preferable. For example, a urethane resin-based aqueous primer agent made of an acrylic-modified urethane resin or the like, specifically, an aqueous urethane resin emulsion using triisopropanolamine as a neutralizing agent.
プライマー剤の塗布量は特に限定されないが、通常０．１〜１００ｇ／ｍ2、好ましくは０．１〜５０ｇ／ｍ2程度である。 The application amount of the primer agent is not particularly limited, but is usually 0.1 to 100 g / m 2 , preferably about 0.1 to 50 g / m 2 .
プライマー層の厚みは特に限定されないが、通常０．０１〜１０μｍ、好ましくは０．１〜１μｍ程度である。 Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.
絵柄模様層
基材シートの上（被着材接合面とは逆面）には、絵柄模様層が形成されている。
A pattern layer is formed on the pattern layer base sheet (opposite to the adherend bonding surface).
絵柄模様層は、化粧シートに所望の絵柄による意匠性を付与するものであり、絵柄の種類等は特に限定的ではない。例えば、木目模様、石目模様、砂目模様、タイル貼模様、煉瓦積模様、布目模様、皮絞模様、幾何学図形、文字、記号、抽象模様等が挙げられる。 The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.
絵柄模様層の形成方法は特に限定されず、例えば、公知の着色剤（染料又は顔料）を結着材樹脂とともに溶剤（又は分散媒）中に溶解（又は分散）させて得られる着色インキ、コーティング剤等を用いた印刷法などにより形成すればよい。 The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent etc.
着色剤としては、例えば、カーボンブラック、チタン白、亜鉛華、弁柄、紺青、カドミウムレッド等の無機顔料；アゾ顔料、レーキ顔料、アントラキノン顔料、キナクリドン顔料、フタロシアニン顔料、イソインドリノン顔料、ジオキサジン顔料等の有機顔料；アルミニウム粉、ブロンズ粉等の金属粉顔料；酸化チタン被覆雲母、酸化塩化ビスマス等の真珠光沢顔料；蛍光顔料；夜光顔料等が挙げられる。これらの着色剤は、単独又は２種以上を混合して使用できる。これらの着色剤には、シリカ等のフィラー、有機ビーズ等の体質顔料、中和剤、界面活性剤等がさらに配合してもよい。 Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.
結着剤樹脂としては、例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル−酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。これらの樹脂は、単独又は２種以上を混合して使用できる。 Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in admixture of two or more.
溶剤（又は分散媒）としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の石油系有機溶剤；酢酸エチル、酢酸ブチル、酢酸−２−メトキシエチル、酢酸−２−エトキシエチル等のエステル系有機溶剤；メチルアルコール、エチルアルコール、ノルマルプロピルアルコール、イソプロピルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール等のアルコール系有機溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤；ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤、；ジクロロメタン、四塩化炭素、トリクロロエチレン、テトラクロロエチレン等の塩素系有機溶剤；水等の無機溶剤等が挙げられる。これらの溶剤（又は分散媒）は、単独又は２種以上を混合して使用できる。 Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.
このような着色インキの中でも、水性組成物（特に水性樹脂エマルション）からなるものが好ましい。水性組成物を用いることにより、化粧シート中のＶＯＣ使用量を低減することができる。 Among such colored inks, those composed of an aqueous composition (particularly an aqueous resin emulsion) are preferable. By using the aqueous composition, the amount of VOC used in the decorative sheet can be reduced.
水性組成物としては、水性樹脂エマルションが好ましく、例えば、水性ウレタン樹脂エマルション、水性ポリエステル樹脂エマルション、水性アクリル樹脂エマルション、セルロース樹脂エマルション、セラック樹脂エマルション、カゼイン樹脂エマルション、これらの混合系エマルション、これらに架橋成分を配合したエマルション等が挙げられる。 As the aqueous composition, an aqueous resin emulsion is preferable, for example, an aqueous urethane resin emulsion, an aqueous polyester resin emulsion, an aqueous acrylic resin emulsion, a cellulose resin emulsion, a shellac resin emulsion, a casein resin emulsion, a mixed emulsion of these, and a cross-linked to them. The emulsion etc. which mix | blended the component are mentioned.
架橋成分を導入した水性エマルションには、例えば、アミノ基を有する水性化合物を主剤とし、１分子中に２個以上のエポキシ基を有する水性化合物を架橋剤として含有する水性エマルション、活性水素基を有する水性化合物を主剤とし、１分子中に２個以上のイソシアネート基を有する水性化合物を架橋剤として含有する水性エマルション、カルボキシル基を有する水性化合物を主剤とし、１分子中に２個以上のカルボジイミド基を有する水性化合物を架橋剤として含有する水性エマルション等が挙げられる。 An aqueous emulsion having a crosslinking component introduced therein has, for example, an aqueous emulsion containing an amino group-containing aqueous compound as a main agent and an aqueous compound having two or more epoxy groups in one molecule as a crosslinking agent, and has an active hydrogen group. An aqueous emulsion containing an aqueous compound as a main component and an aqueous compound having two or more isocyanate groups in one molecule as a crosslinking agent, and an aqueous compound having a carboxyl group as a main component and having two or more carbodiimide groups in one molecule. And an aqueous emulsion containing the aqueous compound as a crosslinking agent.
樹脂エマルションからなる水性組成物の場合には、塩基性中和剤を含むことが好ましい。塩基性中和剤としては、樹脂中のカルボキシル基等を中和により親水化して水に分散（乳化）できるものであればよく、例えば、２級アミン、３級アミン、水酸化ナトリウム、水酸化カリウム、アンモニア等が好ましいものとして挙げられる。具体例を挙げると、ニトロセルロース系水性樹脂エマルション（インキ）には、２級アミン（例えば、ジエタノールアミン）を中和剤として用いることができる。 In the case of an aqueous composition comprising a resin emulsion, a basic neutralizing agent is preferably included. The basic neutralizing agent is not particularly limited as long as it can neutralize the carboxyl group in the resin by neutralization and disperse (emulsify) it in water. For example, secondary amine, tertiary amine, sodium hydroxide, hydroxide Preferred examples include potassium and ammonia. As a specific example, a secondary amine (for example, diethanolamine) can be used as a neutralizing agent in the nitrocellulose-based aqueous resin emulsion (ink).
このような水性組成物（特に、水性樹脂エマルション）からなる着色インキにも、上記と同じ着色剤が使用できる。 The same colorant as described above can also be used for a colored ink comprising such an aqueous composition (particularly an aqueous resin emulsion).
絵柄模様層の形成に用いる印刷法としては、例えば、グラビア印刷法、オフセット印刷法、スクリーン印刷法、フレキソ印刷法、静電印刷法、インクジェット印刷法等が挙げられる。また、全面ベタ状の絵柄模様層を形成する場合には、例えば、ロールコート法、ナイフコート法、エアーナイフコート法、ダイコート法、リップコート法、コンマコート法、キスコート法、フローコート法、ディップコート法等の各種コーティング法が挙げられる。その他、手描き法、墨流し法、写真法、転写法、レーザービーム描画法、電子ビーム描画法、金属等の部分蒸着法、エッチング法等を用いたり、他の形成方法と組み合わせて用いたりしてもよい。 Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.
絵柄模様層の厚みは特に限定されず、製品特性に応じて適宜設定できるが、塗工時の層厚は１〜１５μｍ程度、乾燥後の層厚は０．１〜１０μｍ程度である。 The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.
着色隠蔽層
基材シートと絵柄模様層との間には、必要に応じて、さらに着色隠蔽層を形成してもよい。着色隠蔽層は、化粧シートのおもて面から被着材の地色を隠蔽したい場合に設けられる。基材シートが透明性である場合は勿論、基材シートが隠蔽着色されている場合でも、隠蔽性を安定化するために形成できる。
A colored concealment layer may be further formed between the colored concealment layer base sheet and the pattern layer, if necessary. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it can be formed to stabilize the concealment.
着色隠蔽層を形成するインクとしては、絵柄模様層を形成するインクであって隠蔽着色が可能なものが使用できる。このインクとしても、水性組成物（特に水性樹脂エマルション）が好ましく、さらに塩基性中和剤を含むことが好ましい。 As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used. This ink is also preferably an aqueous composition (particularly an aqueous resin emulsion) and further preferably contains a basic neutralizing agent.
着色隠蔽層の形成方法は、基材シート全体を被覆（全面ベタ状）するように形成できる方法が好ましい。例えば、前記したロールコート法、ナイフコート法、エアーナイフコート法、ダイコート法、リップコート法、コンマコート法、キスコート法、フローコート法、ディップコート法等が好ましいものとして挙げられる。 The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.
着色隠蔽層の厚みは特に限定されず、製品特性に応じて適宜設定できるが、塗工時の層厚は０．１〜１０μｍ程度、乾燥後の層厚は０．０５〜５μｍ程度である。 The thickness of the colored concealing layer is not particularly limited and can be appropriately set according to product characteristics. The layer thickness at the time of coating is about 0.1 to 10 μm, and the layer thickness after drying is about 0.05 to 5 μm.
透明性接着剤層
絵柄模様層の上には、透明性接着剤層が形成されている。透明性接着剤層は、透明性のものであれば特に限定されず、無色透明、着色透明、半透明等のいずれも含む。この接着剤層は、絵柄模様層と透明性ポリエステル系樹脂層とを接着するために形成されている。
Transparent adhesive layer A transparent adhesive layer is formed on the pattern layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. This adhesive layer is formed to bond the pattern layer and the transparent polyester resin layer.
接着剤としては特に限定されず、化粧シートの分野で公知の接着剤が使用できる。この中でも、水性組成物（特に、水性樹脂エマルション）からなるものが好ましい。また、水性組成物は、塩基性中和剤を含むことが好ましい。その他、電離放射線硬化型樹脂を接着剤としてもよいし、公知のフィルム状ヒートシール材を接着剤としてもよい。以下、これらの接着剤について説明する。
（公知の接着剤）
化粧シートの分野で公知の接着剤としては、例えば、ポリアミド樹脂、アクリル樹脂、酢酸ビニル樹脂等の熱可塑性樹脂、熱硬化性ウレタン樹脂等の硬化性樹脂等が挙げられる。また、イソシアネートを硬化剤とする二液硬化型ポリウレタン樹脂又はポリエステル樹脂も適用し得る。
It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet. Among these, what consists of an aqueous composition (especially aqueous resin emulsion) is preferable. Moreover, it is preferable that an aqueous composition contains a basic neutralizer. In addition, an ionizing radiation curable resin may be used as an adhesive, and a known film heat seal material may be used as an adhesive. Hereinafter, these adhesives will be described.
(Known adhesive)
Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.
上記の中でも、特に水性組成物（特に、水性樹脂エマルション）からなる接着剤が好ましい。例えば、水性ウレタン樹脂エマルション、水性ポリエステル樹脂エマルション、水性アクリル樹脂エマルション、セルロース樹脂エマルション等の少なくとも１種を含む接着剤が好ましい。 Among the above, an adhesive composed of an aqueous composition (particularly an aqueous resin emulsion) is particularly preferable. For example, an adhesive containing at least one of an aqueous urethane resin emulsion, an aqueous polyester resin emulsion, an aqueous acrylic resin emulsion, a cellulose resin emulsion and the like is preferable.
接着剤層は、例えば、接着剤を絵柄模様層の上に塗布し、透明性ポリエステル系樹脂層を構成する透明性ポリエステル系樹脂フィルムをラミネート後、乾燥・硬化させることにより形成できる。乾燥温度・乾燥時間等の条件は特に限定されず、接着剤の種類に応じて適宜設定すればよい。接着剤の塗布方法は特に限定されず、例えば、ロールコート、カーテンフローコート、ワイヤーバーコート、リバースコート、グラビアコート、グラビアリバースコート、エアーナイフコート、キスコート、ブレードコート、スムースコート、コンマコート等の方法が採用できる。 The adhesive layer can be formed, for example, by applying an adhesive on the pattern layer, laminating a transparent polyester resin film constituting the transparent polyester resin layer, and drying and curing. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.
接着剤層の厚みは特に限定されないが、乾燥後の厚みが０．１〜３０μｍ、好ましくは１〜２０μｍ程度である。
（電離放射線硬化型樹脂からなる接着剤層）
電離放射線硬化型樹脂としては特に限定されないが、例えば、分子中に重合性不飽和結合又は、エポキシ基を有するプレポリマー、オリゴマー、及び／又は単量体を適宜混合した組成物を用いる。これらの樹脂系としては、ウレタンアクリレート、ポリエステルアクリレート、エポキシアクリレート等のアクリレート、シロキサン等の珪素樹脂、ポリエステル、エポキシ等が挙げられる。前記プレポリマー及びオリゴマーの例としては、不飽和ポリエステル類、メタクリレート類が挙げられる。また、単量体の例としては、スチレン系単量体、アクリル酸エステル類、メタクリル酸エステル類、不飽和酸の置換アミノアルコールエステル類、不飽和カルボン酸アミド、その他の単量体が挙げられる。以上の化合物を１種若しくは２種以上混合して用いるが、樹脂組成物に通常の塗工適性を付与するために、前記プレポリマー又はオリゴマー及び／又は単量体を適宜の配合に混合する。
Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is 0.1-30 micrometers, Preferably it is about 1-20 micrometers.
(Adhesive layer made of ionizing radiation curable resin)
Although it does not specifically limit as ionizing radiation curable resin, For example, the composition which mixed the prepolymer, oligomer, and / or monomer which have a polymerizable unsaturated bond or an epoxy group in a molecule | numerator suitably is used. Examples of these resin systems include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, polyester, and epoxy. Examples of the prepolymer and oligomer include unsaturated polyesters and methacrylates. Examples of monomers include styrene monomers, acrylic esters, methacrylic esters, substituted amino alcohol esters of unsaturated acids, unsaturated carboxylic amides, and other monomers. . The above compounds are used singly or in combination of two or more. In order to impart ordinary coating suitability to the resin composition, the prepolymer or oligomer and / or monomer is mixed in an appropriate formulation.
接着剤層は、例えば、電離放射線硬化型樹脂を絵柄模様層の上に塗布し、透明性ポリエステル系樹脂層を構成する透明性ポリエステル系樹脂フィルムをラミネート後、電離放射線硬化型樹脂を硬化させる電離放射線を透明性ポリエステル系樹脂層の上から照射することにより形成できる。電離放射線硬化型樹脂の塗布方法は、前記した公知の接着剤の塗布方法と同様である。 For example, the adhesive layer is formed by applying an ionizing radiation curable resin on the pattern layer, laminating a transparent polyester resin film constituting the transparent polyester resin layer, and then curing the ionizing radiation curable resin. It can be formed by irradiating radiation from above the transparent polyester resin layer. The application method of the ionizing radiation curable resin is the same as the above-described known adhesive application method.
電離放射線としては、電磁波又は荷電粒子線のうち分子を重合、架橋し得るエネルギーを有するものが使用でき、通常は紫外線、電子線等が使用できる。電離放射線の照射時間等は、電離放射線硬化型樹脂の種類等に応じて適宜設定できる。 As the ionizing radiation, electromagnetic waves or charged particle beams having energy capable of polymerizing and crosslinking molecules can be used, and usually ultraviolet rays, electron beams, and the like can be used. The irradiation time of ionizing radiation can be appropriately set according to the type of ionizing radiation curable resin.
電離放射線硬化型樹脂からなる接着剤層の厚みも、前記と同じである。
（ヒートシール材からなる接着剤層）
ヒートシール材（熱硬化性樹脂）としては特に限定されないが、例えば、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、グアナミン樹脂、不飽和ポリエステル系樹脂、ポリウレタン系樹脂、エポキシ樹脂、アミノアルキッド樹脂、メラミン−尿素共縮合樹脂、珪素樹脂、ポリシロキサン樹脂等が挙げられる。これらの樹脂には、必要に応じて、架橋剤、樹脂開始剤等の硬化剤、重合促進剤、溶剤、粘度調整剤、体質顔料等が添加されていてもよい。不飽和ポリエステル系樹脂、ポリウレタン系樹脂等の硬化剤としては、イソシアネートが好ましく、エポキシ樹脂の硬化剤としては、アミンが好ましく、不飽和ポリエステル系樹脂の硬化剤としては、メチルエチルケトンパーオキサイド等の過酸化物、アゾビスイソブチロニトリル等のラジカル開始剤が好ましい。
The thickness of the adhesive layer made of ionizing radiation curable resin is also the same as described above.
(Adhesive layer made of heat seal material)
The heat seal material (thermosetting resin) is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin Melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like. A curing agent such as a crosslinking agent and a resin initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender pigment, and the like may be added to these resins as necessary. As curing agents for unsaturated polyester resins, polyurethane resins and the like, isocyanates are preferred, amines are preferred as curing agents for epoxy resins, and peroxides such as methyl ethyl ketone peroxide are preferred as curing agents for unsaturated polyester resins. And radical initiators such as azobisisobutyronitrile are preferred.
接着剤層は、絵柄模様層の上に、上記した熱硬化性樹脂からなるフィルム状ヒートシール材を配置し、その上に透明性ポリエステル系樹脂フィルムをラミネート後、熱処理することにより形成できる。熱処理温度は特に限定されないが、通常８０〜１８０℃、好ましくは１００〜１８０℃である。熱処理時間は特に限定されないが、通常は一瞬（数秒）程度である。 The adhesive layer can be formed by arranging a film-like heat seal material made of the above-mentioned thermosetting resin on the pattern layer, laminating a transparent polyester resin film thereon, and then heat-treating it. Although the heat processing temperature is not specifically limited, Usually, it is 80-180 degreeC, Preferably it is 100-180 degreeC. The heat treatment time is not particularly limited, but is usually about a moment (several seconds).
ヒートシール材からなる接着剤層の厚みも、前記と同じである。 The thickness of the adhesive layer made of the heat seal material is also the same as described above.
透明性ポリエステル系樹脂層
接着剤層の上には、透明性ポリエステル系樹脂層が形成されている。
A transparent polyester resin layer is formed on the transparent polyester resin layer adhesive layer.
透明性ポリエステル系樹脂層としては、公知のポリエステル系樹脂のフィルムであって、透明性のものであれば特に限定されず、無色透明、着色透明、半透明等の何れも含む。ポリエステル系樹脂の種類、フィルム成膜方法等については、基材シートの項目で説明した通りである。なお、透明性ポリエステル系樹脂層を構成する樹脂としても、特にポリエチレンテレフタレート、ポリブチレンテレフタレート等が好ましい。 The transparent polyester-based resin layer is a known polyester-based resin film and is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. About the kind of polyester-type resin, the film-forming method, etc., it is as having demonstrated with the item of the base material sheet. The resin constituting the transparent polyester resin layer is particularly preferably polyethylene terephthalate, polybutylene terephthalate, or the like.
透明性ポリエステル系樹脂層を形成する樹脂中に不純物が少なく、透明性が優れている場合には、高い鮮映性が発揮される。不純物量は少なければ少ないほど好ましいが、通常は樹脂中のヘイズ値が１０％以下、好ましくは５％以下であればよい。なお、本明細書におけるヘイズ値は、ＪＩＳ Ｋ−７１０５の規定に準拠して測定した値である。 When the resin forming the transparent polyester-based resin layer has few impurities and excellent transparency, high definition is exhibited. The smaller the amount of impurities, the better. However, the haze value in the resin is usually 10% or less, preferably 5% or less. In addition, the haze value in this specification is the value measured based on prescription | regulation of JISK-7105.
透明性ポリエステル系樹脂層の厚みは特に限定されないが、通常は２０〜１５０μｍ程度である。 Although the thickness of a transparent polyester-type resin layer is not specifically limited, Usually, it is about 20-150 micrometers.
電離放射線硬化型樹脂からなる透明性表面保護層
透明性ポリエステル系樹脂層の上には、必要に応じて、さらに電離放射線硬化型樹脂からなる透明性表面保護層が形成されていてもよい。電離放射線硬化型樹脂からなる表面保護層を形成することにより、化粧シートの耐摩性、耐衝撃性、耐汚染性、耐擦傷性、耐候性等を高めることができる。
Transparent surface protective layer made of ionizing radiation curable resin On the transparent polyester resin layer, a transparent surface protective layer made of ionizing radiation curable resin may be further formed as necessary. By forming a surface protective layer made of an ionizing radiation curable resin, the abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, etc. of the decorative sheet can be improved.
電離放射線硬化型樹脂としては特に限定されず、紫外線、電子線等の電離放射線の照射により重合架橋反応可能なラジカル重合性二重結合を分子中に含むプレポリマー（オリゴマーを含む）及び／又はモノマーを主成分とする透明性樹脂が使用できる。これらのプレポリマー又はモノマーは、単体又は複数を混合して使用できる。硬化反応は、通常、架橋硬化反応である。 The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.
具体的には、前記プレポリマー又はモノマーとしては、分子中に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基等のラジカル重合性不飽和基、エポキシ基等のカチオン重合性官能基等を有する化合物が挙げられる。また、ポリエンとポリチオールとの組み合わせによるポリエン／チオール系のプレポリマーも好ましい。ここで、（メタ）アクリロイル基とは、アクリロイル基又はメタクリロイル基の意味である。 Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
ラジカル重合性不飽和基を有するプレポリマーとしては、例えば、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、メラミン（メタ）アクリレート、トリアジン（メタ）アクリレート、シリコーン（メタ）アクリレート等が挙げられる。これらの分子量としては、通常２５０〜１０００００程度が好ましい。 Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.
ラジカル重合性不飽和基を有するモノマーとしては、例えば、単官能モノマーとして、メチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。また、多官能モノマーとしては、例えば、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイドトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
カチオン重合性官能基を有するプレポリマーとしては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ化合物等のエポキシ系樹脂、脂肪酸系ビニルエーテル、芳香族系ビニルエーテル等のビニルエーテル系樹脂のプレポリマーが挙げられる。また、チオールとしては、例えば、トリメチロールプロパントリチオグリコレート、ペンタエリスリトールテトラチオグリコレート等のポリチオールが挙げられる。ポリエンとしては、例えば、ジオール及びジイソシアネートによるポリウレタンの両端にアリルアルコールを付加したものが挙げられる。 Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.
これらの電離放射線硬化型樹脂としても、水性組成物（特に、水性樹脂エマルション）が好ましく、特に塩基性中和剤を含む水性樹脂エマルションが好ましい。 As these ionizing radiation curable resins, an aqueous composition (particularly an aqueous resin emulsion) is preferable, and an aqueous resin emulsion containing a basic neutralizing agent is particularly preferable.
電離放射線硬化型樹脂を硬化させるために用いる電離放射線としては、電離放射線硬化型樹脂（組成物）中の分子を硬化反応させ得るエネルギーを有する電磁波又は荷電粒子が用いられる。通常は紫外線又は電子線を用いればよいが、可視光線、Ｘ線、イオン線等を用いてもよい。 As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.
紫外線源としては、例えば、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライト、メタルハライドランプ等の光源が使用できる。紫外線の波長としては、通常１９０〜３８０ｎｍが好ましい。 As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.
電子線源としては、例えば、コッククロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、又は直線型、ダイナミトロン型、高周波型等の各種電子線加速器が使用できる。その中でも、特に１００〜１０００ｋｅＶ、好ましくは１００〜３００ｋｅＶのエネルギーをもつ電子を照射できるものが好ましい。 As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.
表面保護層は、例えば、透明性ポリエステル系樹脂層の上に電離放射線硬化型樹脂をグラビアコート、ロールコート等の公知の塗工法により塗工後、電離放射線を照射して該樹脂を硬化させることにより形成できる。 The surface protective layer is formed by, for example, applying an ionizing radiation curable resin on a transparent polyester resin layer by a known coating method such as gravure coating or roll coating, and then irradiating the ionizing radiation to cure the resin. Can be formed.
表面保護層の厚さは特に限定されず、最終製品の特性に応じて適宜設定できるが、通常０．１〜５０μｍ、好ましくは１〜２０μｍ程度である。 The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.
耐候剤
本発明の化粧シートを構成する層の少なくとも１種には、必要に応じて、耐候剤を配合してもよい。耐候剤としては、紫外線吸収剤、ヒンダードアミン系光安定剤等が好ましい。これらの耐候剤は、単独又は２種以上を混合して使用できる。
（紫外線吸収剤）
紫外線吸収剤としては、特に塩基性成分（特にヒドロキシル基）を有するものが好ましい。例えば、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−アミル−５’−イソブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−イソブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−イソブチル−５’−プロピルフェニル）−５−クロロベンゾトリアゾール等の、２’−ヒドロキシフェニル−５−クロロベンゾトリアゾール系紫外線吸収剤類、２−（２’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール等の、２’−ヒドロキシフェニルベンゾトリアゾール系紫外線吸収剤類等の、ベンゾトリアゾール系紫外線吸収剤、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン等の、２，２’−ジヒドロキシベンゾフェノン系紫外線吸収剤類、２−ヒドロキシ−４−メトキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン等の、２ヒドロキシベンゾフェノン系紫外線吸収剤類、等のベンゾフェノン系紫外線吸収剤、サリチル酸フェニル、４−ｔｅｒｔ−ブチル−フェニル−サリシレート等のサリチル酸エステル系紫外線吸収剤が用いられる。その他に、ベンゾトリアゾール骨格にアクリロイル基又はメタクリロイル基を導入した反応性紫外線吸収剤等も用いられる。上記の中でも、特にベンゾトリアゾール系紫外線吸収剤が好ましい。なお、これら紫外線吸収剤の添加量は、樹脂分に対して、通常０．１〜５質量％程度である。
Weathering agent A weathering agent may be blended in at least one of the layers constituting the decorative sheet of the present invention, if necessary. As the weathering agent, an ultraviolet absorber, a hindered amine light stabilizer and the like are preferable. These weathering agents can be used alone or in admixture of two or more.
(UV absorber)
As the ultraviolet absorber, those having a basic component (particularly a hydroxyl group) are particularly preferable. For example, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) ) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5) 2'-hydroxyphenyl-5-chlorobenzo such as' -methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole Triazole ultraviolet absorbers, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy) 5'-methylphenyl) benzotriazole, 2'-hydroxyphenylbenzotriazole UV absorbers, such as benzotriazole UV absorbers, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'- 2,2′-dihydroxybenzophenone ultraviolet absorbers such as dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, Benzophenone ultraviolet absorbers such as 2-dihydroxybenzophenone ultraviolet absorbers such as 4-dihydroxybenzophenone, and salicylic acid ester ultraviolet absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate are used. In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton is also used. Of these, benzotriazole-based ultraviolet absorbers are particularly preferable. In addition, the addition amount of these ultraviolet absorbers is about 0.1-5 mass% normally with respect to a resin part.
このような紫外線吸収剤を添加することにより、各層の耐候性を高められる。また、塩基性成分を含む紫外線吸収剤を用いる場合には、各層を形成するのに使用できる樹脂エマルションに含まれる樹脂骨格（カルボキシル基）と相互作用して、紫外線吸収剤のブリードを抑止する効果も得られる。例えば、分子中に水酸基を有する紫外線吸収剤を基材シートに添加し、隣接層を構成する樹脂成分としてイソシアネート基を有するウレタン樹脂等を用いる場合には、紫外線吸収剤が基材シートからブリードして隣接層に染み込んでも、水酸基とイソシアネート基とがウレタン結合することにより捕捉できる。 By adding such an ultraviolet absorber, the weather resistance of each layer can be enhanced. Moreover, when using the ultraviolet absorber containing a basic component, it interacts with the resin skeleton (carboxyl group) contained in the resin emulsion that can be used to form each layer, and the effect of suppressing bleeding of the ultraviolet absorber. Can also be obtained. For example, when an ultraviolet absorber having a hydroxyl group in the molecule is added to the base sheet and a urethane resin having an isocyanate group is used as a resin component constituting the adjacent layer, the ultraviolet absorbent bleeds from the base sheet. Even if it penetrates into the adjacent layer, it can be captured by the urethane bond between the hydroxyl group and the isocyanate group.
紫外線吸収剤の含有量は特に限定されないが、各層に１００〜１００００重量ｐｐｍ程度、好ましくは５００〜７５００重量ｐｐｍ程度である。添加する層は特に限定されず、製品特性に応じて適宜設定できる。
（ヒンダードアミン系光安定剤）
紫外線による各層の劣化をさらに防止し、耐候性を向上させるためには、他の耐候剤としてヒンダードアミン系光安定剤を添加することが好ましい。例えば、ビス−（２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、ビス−（Ｎ−メチル−２，２，６，６−テトラメチル−４−ピペリジニル）セバケート、その他、例えば特公平４−８２６２５号公報に開示されている化合物等が挙げられる。これらの光安定剤の添加量は特に限定されないが、通常、樹脂分に対して０．１〜５重量％程度である。
Although content of a ultraviolet absorber is not specifically limited, About 100-10000 weight ppm in each layer, Preferably it is about 500-7500 weight ppm. The layer to be added is not particularly limited, and can be appropriately set according to product characteristics.
(Hindered amine light stabilizer)
In order to further prevent deterioration of each layer due to ultraviolet rays and improve weather resistance, it is preferable to add a hindered amine light stabilizer as another weathering agent. For example, bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, etc. Examples thereof include compounds disclosed in Japanese Patent Publication No. 4-82625. The addition amount of these light stabilizers is not particularly limited, but is usually about 0.1 to 5% by weight with respect to the resin content.
なお、ヒンダードアミン系光安定剤を添加する場合には、基材シートをはじめ、化粧シートを構成する層中に塩素原子を含む樹脂を用いないことが耐候性向上の点から好ましい。例えば、バインダー樹脂に塩化ビニル−酢酸ビニル共重合体、塩素化ポリオレフィン等の分子中に塩素原子を含む樹脂を用いると、紫外線又は熱の作用によりこれら塩素含有樹脂から脱塩素反応で塩化水素が発生した場合に、これがヒンダードアミン系光安定剤と反応してその作用を失活・阻害するため、該捕捉剤による耐候性向上効果が十分に発揮されないおそれがあるからである。 In addition, when adding a hindered amine light stabilizer, it is preferable from the point of a weather resistance improvement not to use resin containing a chlorine atom in the layer which comprises a base sheet and a decorative sheet. For example, if a resin containing a chlorine atom in the molecule, such as vinyl chloride-vinyl acetate copolymer or chlorinated polyolefin, is used as the binder resin, hydrogen chloride is generated from the chlorine-containing resin by the action of ultraviolet rays or heat. In this case, it reacts with the hindered amine light stabilizer to deactivate / inhibit its action, so that the effect of improving the weather resistance by the scavenger may not be sufficiently exhibited.
塩基性成分を含むヒンダードアミン系光安定剤を含める場合には、各層を形成し得る樹脂エマルションに含まれる樹脂骨格（カルボキシル基）と相互作用して、紫外線吸収剤のブリードを抑止する効果も得られる。 When a hindered amine light stabilizer containing a basic component is included, the effect of suppressing bleeding of the ultraviolet absorber by interacting with the resin skeleton (carboxyl group) contained in the resin emulsion capable of forming each layer is also obtained. .
ヒンダードアミン系光安定剤の含有量は特に限定されないが、各層に１００〜１００００重量ｐｐｍ程度、好ましくは５００〜７５００重量ｐｐｍ程度である。添加する層は特に限定されず、製品特性に応じて適宜設定できる。 Although content of a hindered amine light stabilizer is not specifically limited, About 100-10000 weight ppm in each layer, Preferably it is about 500-7500 weight ppm. The layer to be added is not particularly limited, and can be appropriately set according to product characteristics.
化粧材
本発明の化粧シートは、各種被着材と接合することにより、化粧材とできる。被着材の材質は特に限定されず、例えば、無機非金属系、金属系、木質系、プラスチック系等の材質が挙げられる。
Cosmetic Material The decorative sheet of the present invention can be made into a cosmetic material by bonding with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood materials, and plastic materials.
具体的には、無機非金属系では、例えば、抄造セメント、押出しセメント、スラグセメント、ＡＬＣ（軽量気泡コンクリート）、ＧＲＣ（ガラス繊維強化コンクリート）、パルプセメント、木片セメント、石綿セメント、硅酸カルシウム、石膏、石膏スラグ等の非陶磁器窯業系材料、土器、陶器、磁器、セッ器、硝子、琺瑯等のセラミックス材料などが挙げられる。 Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.
金属系では、例えば、鉄、アルミニウム、銅等の金属材料（金属鋼板）が挙げられる。 In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.
木質系では、例えば、杉、檜、樫、ラワン、チーク等からなる単板、合板、パーティクルボード、繊維板、集成材等が挙げられる。 In the wood system, for example, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, teak and the like can be mentioned.
プラスチック系では、例えば、ポリプロピレン、ＡＢＳ樹脂、フェノール樹脂等の樹脂材料が挙げられる。 In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.
このような被着体の形状は特に限定されず、例えば、平板、曲面板、多角柱等の形状を任意に採用できる。 The shape of such an adherend is not particularly limited, and for example, shapes such as a flat plate, a curved plate, and a polygonal column can be arbitrarily adopted.
本発明の化粧シートを上記した被着材の表面に貼着して得られる化粧材は、例えば、壁、天井等の建築物内装材、扉、扉枠、窓枠等の建具の表面材、回縁、幅木等の造作部材の表面材、箪笥、キャビネット等の家具の表面材などに使用できる。また、被着材を用いずに、化粧シート自体を建材部材に対するラミネート材、ラッピング材等として使用することもできる。例えば、浴室等に用いられる鋼板基材の表面に化粧シートの基材シート側を貼着して装飾を施してもよい。 The decorative material obtained by adhering the decorative sheet of the present invention to the surface of the adherend described above is, for example, a building interior material such as a wall or ceiling, a surface material of a fitting such as a door, door frame, or window frame, It can be used as a surface material for construction members such as rounded edges and skirting boards, and as a surface material for furniture such as bags and cabinets. Further, the decorative sheet itself can be used as a laminate material, a wrapping material or the like for the building material member without using an adherend. For example, the decorative sheet may be decorated by sticking the base sheet side of the decorative sheet to the surface of a steel sheet base used in a bathroom or the like.
被着体と化粧シートの基材シート側を積層するのに用いる接着剤は特に限定されず、化粧シートの分野で公知の接着剤を使用できるが、その中でも、特に耐候剤を含む接着剤が好ましい。耐候剤としては、前記した紫外線吸収剤及び光安定剤が挙げられる。 The adhesive used for laminating the adherend and the base sheet side of the decorative sheet is not particularly limited, and known adhesives in the field of decorative sheets can be used, and among them, particularly adhesives including weathering agents are used. preferable. Examples of the weathering agent include the aforementioned ultraviolet absorbers and light stabilizers.
本発明の化粧シートは、化粧シートを構成する層の少なくとも１種が水性組成物からなるため、ＶＯＣ使用量が低減できる。また、耐候剤を含む場合でも耐候剤のブリード抑止効果が高い。 In the decorative sheet of the present invention, since at least one of the layers constituting the decorative sheet is composed of an aqueous composition, the amount of VOC used can be reduced. Moreover, even when a weathering agent is included, the bleed suppressing effect of the weathering agent is high.
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
ポリプロピレンを主成分とし、顔料により着色された６０μｍ厚のポリオレフィンフィルムを基材シートとし、その表裏両面にはコロナ放電処理を施して、表裏両面の表面張力を４８ｄｙｎ／ｃｍ以上とした。基材シートの裏面には、トリイソプロパノールアミンを中和剤としたウレタン樹脂エマルションからなる厚み２μｍの裏面プライマー層を設けた。
Example 1
A polyolefin film having a thickness of 60 μm mainly composed of polypropylene and colored with a pigment was used as a base sheet, and both the front and back surfaces thereof were subjected to corona discharge treatment so that the surface tension on both the front and back surfaces was 48 dyn / cm or more. On the back surface of the base sheet, a back primer layer having a thickness of 2 μm made of a urethane resin emulsion using triisopropanolamine as a neutralizing agent was provided.
基材シートのおもて面には、水酸化ナトリウムを中和剤としたポリエーテルウレタン系樹脂エマルションからなる着色隠蔽層（２μｍ）及び絵柄模様層（３μｍ）を形成した。着色隠蔽層及び絵柄模様層は、グラビア印刷により形成した。 A colored hiding layer (2 μm) and a pattern layer (3 μm) made of a polyether urethane resin emulsion using sodium hydroxide as a neutralizing agent were formed on the front surface of the base sheet. The coloring hiding layer and the pattern layer were formed by gravure printing.
次いで、絵柄模様層の上に、ヒンダードアミン系光安定剤５００重量ｐｐｍを配合した６０μｍ厚の透明性ポリエステル樹脂フィルム（ヘイズ２％）を、水酸化ナトリウムを中和剤とした２液硬化型の水性ポリエステルウレタン１０ｇ／ｍ2からなる接着剤層（１０μｍ）を介してコーティングラミネートした。 Subsequently, a 60 μm thick transparent polyester resin film (haze 2%) blended with 500 ppm by weight of a hindered amine light stabilizer on the pattern layer is a two-part curable aqueous solution using sodium hydroxide as a neutralizing agent. Coating lamination was carried out through an adhesive layer (10 μm) composed of 10 g / m 2 of polyester urethane.
接着剤を乾燥させて、化粧シートを作製した。 The adhesive was dried to prepare a decorative sheet.
作製した化粧シートを１２０℃で１０分間熱処理して残留溶剤を除去後、ガスクロマトグラフィーにかけたところ、化粧シート中の残留ＶＯＣ量は２０ｍｇ／ｍ2であった。 The produced decorative sheet was heat treated at 120 ° C. for 10 minutes to remove the residual solvent and then subjected to gas chromatography. As a result, the residual VOC amount in the decorative sheet was 20 mg / m 2 .
作製した化粧シートおもて面の１ｋｇ荷重の鉛筆硬度（ＪＩＳ−Ｋ５４００の規定に準拠した測定結果）は、ＨＢであった。 The pencil hardness (measurement result in accordance with JIS-K5400) of 1 kg load on the front surface of the produced decorative sheet was HB.
作製した化粧シートは、透明性ポリエステル樹脂フィルムのヘイズ値が２％と低いため、鮮映性に優れており、発光している蛍光灯をかざした場合に鮮映に映っていた。 The produced decorative sheet was excellent in sharpness because the haze value of the transparent polyester resin film was as low as 2%, and was clearly visible when a fluorescent lamp emitting light was held over.
実施例２
ポリブチレンテレフタレートを主成分とし、顔料により着色された６０μｍ厚のポリエステルフィルムを基材シートとし、その表裏両面にはコロナ放電処理を施して、表裏両面の表面張力を４８ｄｙｎ／ｃｍ以上とした。基材シートの裏面には、トリイソプロパノールアミンを中和剤としたウレタン樹脂エマルションからなる厚み２μｍの裏面プライマー層を設けた。
Example 2
A 60 μm thick polyester film containing polybutylene terephthalate as a main component and colored with a pigment was used as a base sheet, and both surfaces were subjected to corona discharge treatment so that the surface tension on both sides was 48 dyn / cm or more. On the back surface of the base sheet, a back primer layer having a thickness of 2 μm made of a urethane resin emulsion using triisopropanolamine as a neutralizing agent was provided.
基材シートのおもて面には、水酸化ナトリウムを中和剤としたポリエーテルウレタン系樹脂エマルションからなる着色隠蔽層（２μｍ）及び絵柄模様層（３μｍ）を形成した。着色隠蔽層及び絵柄模様層の形成は、グラビア印刷により形成した。 A colored hiding layer (2 μm) and a pattern layer (3 μm) made of a polyether urethane resin emulsion using sodium hydroxide as a neutralizing agent were formed on the front surface of the base sheet. The colored hiding layer and the pattern layer were formed by gravure printing.
次いで、絵柄模様層の上に、ヒンダードアミン系光安定剤５００重量ｐｐｍを配合した６０μｍ厚の透明性ポリエステル樹脂フィルム（ヘイズ２％）を、ベンゾトリアゾール系紫外線吸収剤１０００重量ｐｐｍを含み、トリイソプロパノールアミンを中和剤として含む２液硬化型の水性ポリウレタン１０ｇ／ｍ2からなる接着剤層（１０μｍ）を介してコーティングラミネートした。 Next, a transparent polyester resin film (hazy 2%) having a thickness of 60 μm blended with 500 wt ppm of a hindered amine light stabilizer on the pattern layer, containing 1000 wt ppm of benzotriazole UV absorber, and triisopropanolamine Was laminated through an adhesive layer (10 μm) composed of 10 g / m 2 of a two-component curable aqueous polyurethane containing as a neutralizing agent.
次いで、透明性ポリエステル樹脂層の上に、電離放射線硬化性樹脂からなる透明性表面保護層をさらに形成するためにベンゾトリアゾール系紫外線吸収剤を５０００重量ｐｐｍ含み、トリイソプロパノールアミンを中和剤として含む、２官能ウレタンオリゴマーと６官能ジペンタエリスリトールヘキサアクリレートとの９：１（重量比）混合物を水：イソプロピルアルコール（ＩＰＡ）＝（重量比７：３）の混合物に溶解したものを５ｇ／ｍ2塗布した。その後、おもて面から電子線を１７５ｅＶ、５Ｍｒａｄで照射することにより電離放射線硬化性樹脂を硬化させて、化粧シートを作製した。 Next, in order to further form a transparent surface protective layer made of an ionizing radiation curable resin on the transparent polyester resin layer, it contains 5000 ppm by weight of a benzotriazole-based ultraviolet absorber and triisopropanolamine as a neutralizing agent. A solution obtained by dissolving a 9: 1 (weight ratio) mixture of a bifunctional urethane oligomer and hexafunctional dipentaerythritol hexaacrylate in a mixture of water: isopropyl alcohol (IPA) = (weight ratio 7: 3) is 5 g / m 2. Applied. Then, the ionizing radiation-curable resin was cured by irradiating an electron beam from the front surface at 175 eV and 5 Mrad, and a decorative sheet was produced.
作製した化粧シートおもて面の１ｋｇ荷重の鉛筆硬度（ＪＩＳ−Ｋ５４００の規定に準拠した測定結果）は、２Ｈであった。 The pencil hardness of the produced decorative sheet front surface with a 1 kg load (measurement result in accordance with JIS-K5400) was 2H.
比較例１
実施例１において、各層の形成に水性組成物を使用せずに溶剤系組成物（市販品）を使用し、また透明性ポリエステル樹脂フィルムのヘイズを２０％とした以外は、実施例１と同じ層構成の化粧シートを作製した。
Comparative Example 1
In Example 1, the same composition as in Example 1 except that the solvent-based composition (commercial product) was used without forming the aqueous composition for forming each layer, and the haze of the transparent polyester resin film was 20%. A layered decorative sheet was prepared.
作製した化粧シートを１２０℃で１０分間熱処理して残留溶剤を除去後、ガスクロマトグラフィーにかけたところ、化粧シート中の残留ＶＯＣ量は２００ｍｇ／ｍ2であった。 The produced decorative sheet was heat-treated at 120 ° C. for 10 minutes to remove the residual solvent and then subjected to gas chromatography. As a result, the residual VOC amount in the decorative sheet was 200 mg / m 2 .
作製した化粧シートは、透明性ポリエステル樹脂フィルムのヘイズ値が２０％と高いため、鮮映性が低く、発光している蛍光灯をかざした場合に蛍光灯が大きく歪んで映っていた。 Since the produced decorative sheet had a high haze value of 20% for the transparent polyester resin film, the sharpness was low, and when the fluorescent lamp was lit, the fluorescent lamp was greatly distorted.
化粧鋼板の作製
実施例及び比較例で作製した化粧シートの基材シート側を、メッキを施した鋼板に接着剤１０ｇ／ｍ2を介してラミネートし、３種類の化粧鋼板を作製した。
Preparation of decorative steel sheet The base sheet side of the decorative sheet prepared in Examples and Comparative Examples was laminated on a plated steel sheet with an adhesive of 10 g / m 2 to prepare three types of decorative steel sheets.
接着剤としては、トリイソプロパノールアミンを中和剤として含む２液硬化型ウレタン系接着剤であって、これにベンゾトリアゾール系紫外線吸収剤１０００ｐｐｍを配合したものと配合しないものとを２種類使用した。 As the adhesive, two types of two-component curable urethane-based adhesives containing triisopropanolamine as a neutralizing agent and those not containing 1000 ppm of benzotriazole-based ultraviolet absorbers were used.
使用する接着剤の種類と化粧鋼板サンプルの種類とを下記表１に示す。 Table 1 below shows the type of adhesive used and the type of decorative steel sheet sample.
試験例１
上記で得られた各化粧鋼板サンプルに対して耐候性試験を行った。
Test example 1
A weather resistance test was performed on each decorative steel sheet sample obtained above.
耐候性評価は、カーボンアーク燈型サンシャインウェザーメーターを用いて、ブラックパネル温度６３℃、降雨時間１２０分中１８分の条件で１０００時間照射後、各サンプルおもて面（鋼板とは反対側）の変色、サンプルの亀裂、剥離等の外観変化の有無を肉眼により目視観察することにより行った。 The weather resistance was evaluated by using a carbon arc saddle type sunshine weather meter for 1000 hours under conditions of black panel temperature of 63 ° C and 18 minutes of rainfall for 120 minutes, then the front surface of each sample (opposite to the steel plate) The presence or absence of appearance changes such as discoloration, cracks in the sample, and peeling was visually observed with the naked eye.
耐候性評価結果を下記表２に示す。 The weather resistance evaluation results are shown in Table 2 below.
Claims (10)
The decorative steel sheet according to claim 9, which is a decorative steel sheet for bathrooms.
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