JP2006095501A - Method for manufacturing abrasion-resistant matte decorative material - Google Patents
Method for manufacturing abrasion-resistant matte decorative material Download PDFInfo
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本発明は、耐擦傷性艶消し化粧材の製造方法に関する。具体的には、トップコート層を無溶剤型の電離放射線硬化型塗工剤から形成する耐擦傷性艶消し化粧材の製造方法に関する。 The present invention relates to a method for producing a scratch-resistant matte cosmetic material. Specifically, the present invention relates to a method for producing a scratch-resistant matte cosmetic material in which a topcoat layer is formed from a solventless ionizing radiation curable coating agent.
従来、耐擦傷性（耐スクラッチ性）の高い化粧材としては、トップコート層を電離放射線硬化型樹脂から形成したものが知られている。そして、近年では環境衛生面から電離放射線硬化型樹脂に有機溶剤が残留しないものが求められており、無溶剤（ノンソル）型の塗工剤からトップコート層を形成することが多くなっている。例えば、特許文献１には、基材に水性インキからなるインキ層を設け、該インキ層に、無溶剤電離放射線硬化性樹脂からなるトップコート層を設けてなる化粧材が開示されている。 Conventionally, as a decorative material having high scratch resistance (scratch resistance), a top coat layer formed from an ionizing radiation curable resin is known. In recent years, from the viewpoint of environmental hygiene, there has been a demand for an organic solvent that does not remain in the ionizing radiation curable resin, and a topcoat layer is often formed from a solvent-free (non-sol) type coating agent. For example, Patent Document 1 discloses a cosmetic material in which an ink layer made of water-based ink is provided on a base material, and a topcoat layer made of a solventless ionizing radiation curable resin is provided on the ink layer.
このような電離放射線硬化型樹脂からなるトップコート層を有する化粧材において、艶消し効果を得るためには、シリカ等の艶消し材がトップコート層に配合される。しかしながら、無溶剤型の電離放射線硬化型塗工剤の場合には、硬化速度が速い上に有機溶剤を含まないため、艶消しシリカを配合した場合に、有機溶剤を使用する場合に得られるリフティング効果（シリカがトップコート層のおもて側に集まる効果であり、有機溶剤を使用する場合には該溶剤の揮発時にシリカがリフティングされる）が得られないため、艶を低下させることが困難である。 In a decorative material having a topcoat layer made of such an ionizing radiation curable resin, a matting material such as silica is blended in the topcoat layer in order to obtain a matting effect. However, in the case of a solventless ionizing radiation curable coating agent, the curing speed is high and the organic solvent is not included. Therefore, when matte silica is blended, lifting obtained when using an organic solvent is used. It is difficult to reduce gloss because the effect (silica is gathered on the front side of the topcoat layer, and when an organic solvent is used, the silica is lifted when the solvent volatilizes) cannot be obtained. It is.
このような現状に鑑みて、ノンソル型の塗工剤からトップコート層を形成する場合でも、十分に艶消し効果が得られる技術の開発が望まれている。これまで、塗工膜厚よりも大粒径のシリカを配合して艶消し効果を高める試みがなされている。しかし、この方法では艶消し効果は得られるが、シリカの粒径増大に伴ってトップコート層の表面凹凸が顕著となりシート表面の手触り感を損なう問題が生じる。 In view of such a current situation, even when the topcoat layer is formed from a non-sol type coating agent, it is desired to develop a technique capable of sufficiently obtaining a matte effect. Up to now, attempts have been made to increase the matting effect by blending silica having a particle size larger than the coating film thickness. However, although the matte effect is obtained by this method, the surface unevenness of the topcoat layer becomes conspicuous as the silica particle size increases, and there arises a problem of impairing the feel of the sheet surface.
また、艶消しシリカの粒子径を小さくして艶消し効果を高める試みもあるが、この方法では艶消し効果を高めるためにシリカ量を増やすことが必要であり、シリカ量が増えると塗工剤が増粘して塗工性が悪くなるという問題がある。 There is also an attempt to increase the matting effect by reducing the particle size of matte silica, but this method requires an increase in the amount of silica in order to increase the matting effect. However, there is a problem that the coating property is deteriorated due to increase in viscosity.
その他、シリカ粒子径に特徴を持たせた艶消し化粧材としては、例えば、特許文献２に、トップコート層が積層されている基材に設けられた凹部の径よりも大きいシリカと該径よりも小さいシリカとを混合して用いた化粧材が開示されている。 In addition, as a matte cosmetic material characterized by the silica particle diameter, for example, in Patent Document 2, silica larger than the diameter of the recess provided in the base material on which the topcoat layer is laminated and Further, a cosmetic material using a mixture with small silica is disclosed.
しかしながら、これらの艶消し手段及びこれにより得られる艶消し材はさらなる改良の余地を残すものである。従って、ノンソル型の電離放射線硬化型塗工剤からトップコート層を形成する場合でも、塗工性の悪化、手触り感の悪化等をもたらすことなく容易に艶消し効果が得られる技術の開発が望まれている。
本発明は、無溶剤型の電離放射線硬化型塗工剤から形成されるトップコート層を有する耐擦傷性艶消し化粧材の好適な製造方法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 suitable method for producing a scratch-resistant matte cosmetic material having a topcoat layer formed from a solventless ionizing radiation curable coating agent.
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、無溶剤型の電離放射線硬化型塗工剤を塗工後、紫外線照射と電子線照射とを組み合わせて樹脂を硬化させることが、上記目的の達成に寄与することを見出し、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 can cure a resin by combining ultraviolet irradiation and electron beam irradiation after coating a solventless ionizing radiation curable coating agent. The present inventors have found that it contributes to the achievement of the above object and have completed the present invention.
即ち、本発明は、下記の艶消し化粧材の製造方法に係るものである。
１． トップコート層がシリカを含む電離放射線硬化型樹脂からなる耐擦傷性艶消し化粧材の製造方法であって、
（１）有機溶剤を含まずシリカ及び光重合開始剤を含む電離放射線硬化型塗工剤を、基材上にシリカの粒子径を超える厚みとなるように塗工し、次いで
（２）紫外線照射により電離放射線硬化型樹脂を半硬化させた後、電子線照射により該樹脂をトップコート層に要求される硬度となるまで完全硬化させる
ことを特徴とする製造方法。
２． シリカの粒子径が１〜１０μｍである上記項１記載の製造方法。
３． シリカの含有量が電離放射線硬化型樹脂１００重量部に対して５〜２５重量部である上記項１又は２記載の製造方法。
４． 光重合開始剤の含有量が電離放射線硬化型樹脂１００重量部に対して０．１〜５重量部である上記項１〜３のいずれかに記載の製造方法。
５． 上記項１〜４のいずれかに記載の製造方法により製造される耐擦傷性艶消し化粧材。
以下、本発明の耐擦傷性艶消し化粧材の製造方法について詳細に説明する。
That is, the present invention relates to the following method for producing a matte cosmetic material.
1. A method for producing a scratch-resistant matte cosmetic material comprising an ionizing radiation curable resin containing silica as a top coat layer,
(1) An ionizing radiation curable coating agent that does not contain an organic solvent and contains silica and a photopolymerization initiator is applied on the substrate so that the thickness exceeds the particle diameter of silica, and then (2) UV irradiation After the ionizing radiation curable resin is semi-cured by the above, the resin is completely cured by electron beam irradiation until the hardness required for the top coat layer is reached.
2. Item 2. The method according to Item 1, wherein the silica has a particle size of 1 to 10 µm.
3. Item 3. The method according to Item 1 or 2, wherein the silica content is 5 to 25 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
4). Item 4. The production method according to any one of Items 1 to 3, wherein the content of the photopolymerization initiator is 0.1 to 5 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
5. 5. A scratch-resistant matte cosmetic material produced by the production method according to any one of Items 1 to 4.
Hereinafter, the method for producing the scratch-resistant matte cosmetic material of the present invention will be described in detail.
本発明の製造方法は、トップコート層がシリカを含む電離放射線硬化型樹脂からなる耐擦傷性艶消し化粧材の製造方法であって、
（１）有機溶剤を含まずシリカ及び光重合開始剤を含む電離放射線硬化型塗工剤を、基材上にシリカの粒子径を超える厚みとなるように塗工し、次いで
（２）紫外線照射により電離放射線硬化型樹脂を半硬化させた後、電子線照射による該樹脂をトップコート層に要求される硬度となるまで完全硬化させる
ことを特徴とする。
The production method of the present invention is a method of producing a scratch-resistant matte cosmetic material comprising a top coat layer made of an ionizing radiation curable resin containing silica,
(1) An ionizing radiation curable coating agent that does not contain an organic solvent and contains silica and a photopolymerization initiator is applied on the substrate so that the thickness exceeds the particle diameter of silica, and then (2) UV irradiation After the ionizing radiation curable resin is semi-cured by, the resin by electron beam irradiation is completely cured until the hardness required for the top coat layer is reached.
本発明の製造方法は、電離放射線硬化型塗工剤を基材上に塗工後、紫外線照射により樹脂を半硬化させてから電子線照射により完全硬化させるため、紫外線照射時にシリカがリフティングされて艶消し効果が高い化粧材が得られる。また、電離放射線硬化型樹脂を完全硬化させたトップコート層を有するため、耐擦傷性が高い。さらに、塗工剤に含まれるシリカの粒子径を超える厚みとなるように塗工するため、トップコート層表面にシリカに起因する凹凸が生じ難く手触り感を損なうことがない。 In the production method of the present invention, after the ionizing radiation curable coating agent is applied on the substrate, the resin is semi-cured by ultraviolet irradiation and then completely cured by electron beam irradiation. A cosmetic material with a high matting effect can be obtained. Moreover, since it has the topcoat layer which hardened the ionizing radiation curable resin completely, it has high scratch resistance. Furthermore, since coating is performed so as to have a thickness exceeding the particle diameter of silica contained in the coating agent, unevenness due to silica hardly occurs on the surface of the topcoat layer, and the touch feeling is not impaired.
電離放射線硬化型塗工剤（以下「塗工剤」と略記する）は、有機溶剤を含まない無溶剤（ノンソル）型のものを用いる。塗工剤は、マトリックスとなる電離放射線硬化型樹脂に加えてシリカ及び光重合開始剤を含んでいる。 As the ionizing radiation curable coating agent (hereinafter abbreviated as “coating agent”), a non-solvent type that does not contain an organic solvent is used. The coating agent contains silica and a photopolymerization initiator in addition to the ionizing radiation curable resin serving as a matrix.
電離放射線硬化型樹脂
電離放射線硬化型樹脂としては、電子線照射及び光重合開始剤の存在下における紫外線照射により硬化（樹脂架橋）するものであれば特に限定されない。例えば、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、１種又は２種以上を混合して使用できる。
The ionizing radiation curable resin is not particularly limited as long as it is cured (resin crosslinking) by electron beam irradiation and ultraviolet irradiation in the presence of a photopolymerization initiator. For example, a prepolymer (including an oligomer) containing a radical polymerizable double bond in the molecule and / or a transparent resin mainly containing a monomer can be used. These prepolymers or monomers can be used alone or in combination.
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、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 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, for example, epoxy resins such as bisphenol type epoxy resins and novolak type epoxy compounds, fatty acid type vinyl ethers,
Examples include prepolymers of vinyl ether resins such as 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.
光重合開始剤
光重合開始剤としては、紫外線照射により電離放射線硬化型樹脂の樹脂架橋を開始できるものであれば特に限定されない。例えば、アセトフェノン類、ベンゾフェノン類、ミヒラーベンゾイルベンゾエート、α−アミノキシムエステル、テトラメチルチウラムモノサルファイド、チオキサントン類等が挙げられる。
The photopolymerization initiator is not particularly limited as long as it can initiate resin crosslinking of the ionizing radiation curable resin by ultraviolet irradiation. Examples include acetophenones, benzophenones, Michler benzoyl benzoate, α-amino oxime ester, tetramethyl thiuram monosulfide, thioxanthones, and the like.
光重合開始剤の含有割合は特に限定されないが、電離放射線硬化型樹脂１００重量部に対して０．１〜５重量部が好ましい。さらに、光重合促進剤（増感剤）を併用してもよい。光重合促進剤としては、例えば、ｎ−ブチルアミン、トリエチルアミン、トリ−ｎ−ブチルホスフィン等が挙げられる。光重合促進剤の含有割合も特に限定的ではないが、電離放射線硬化型樹脂１００重量部に対して０．１〜１０重量部程度である。 Although the content rate of a photoinitiator is not specifically limited, 0.1-5 weight part is preferable with respect to 100 weight part of ionizing radiation curable resins. Furthermore, a photopolymerization accelerator (sensitizer) may be used in combination. Examples of the photopolymerization accelerator include n-butylamine, triethylamine, tri-n-butylphosphine and the like. The content ratio of the photopolymerization accelerator is not particularly limited, but is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
シリカ
シリカはトップコート層に存在させることにより艶消し効果を発揮する。シリカとしては化粧シートの分野で公知のものが広く使用できる。本発明の製造方法では塗工剤を含有シリカの粒子径を超える厚みとなるように基材上に塗工するため、塗工厚みに応じてシリカの粒子径を設定すればよい。シリカの粒子径としては、通常１〜１０μｍ、好ましくは３〜５μｍ程度である。シリカの粒子形状は特に限定されないが、球状シリカが好ましい。
Silica Silica exhibits matting effect by the presence in the top coat layer. As silica, those known in the field of decorative sheets can be widely used. In the production method of the present invention, since the coating agent is coated on the base material so as to have a thickness exceeding the particle diameter of the containing silica, the particle diameter of silica may be set according to the coating thickness. The particle diameter of silica is usually 1 to 10 μm, preferably about 3 to 5 μm. The particle shape of the silica is not particularly limited, but spherical silica is preferable.
シリカ含有量は特に限定されないが、電離放射線硬化型樹脂１００重量部に対して通常５〜２５重量部、好ましくは１０〜２０重量部程度である。シリカ含有量が少なすぎる場合には艶消し効果が十分に得られないおそれがある。シリカ含有量が多すぎる場合には、塗工剤の塗工性が低下するおそれがある。 The silica content is not particularly limited, but is usually 5 to 25 parts by weight, preferably about 10 to 20 parts by weight, with respect to 100 parts by weight of the ionizing radiation curable resin. If the silica content is too low, the matting effect may not be sufficiently obtained. When there is too much silica content, there exists a possibility that the coating property of a coating agent may fall.
耐擦傷性化粧材の製造
本発明の製造方法では、上記の塗工剤を、基材上にシリカの粒子径を超える厚みとなるように塗工する。基材の種類は特に限定されず、化粧材の種類に応じて適宜設定できる。例えば、熱可塑性樹脂からなるフィルムであってもよく、又は該フィルム上に絵柄層、透明性樹脂層等を形成したものであってもよい。
Production of Scratch-Resistant Cosmetic Material In the production method of the present invention, the coating agent is applied on a substrate so as to have a thickness exceeding the particle diameter of silica. The kind of base material is not specifically limited, According to the kind of decorative material, it can set suitably. For example, a film made of a thermoplastic resin may be used, or a pattern layer, a transparent resin layer, or the like may be formed on the film.
塗工剤の塗工方法は特に限定されず、例えば、ナイフコート、ノズルコート、グラビアコート、ロータリースクリーンコート、リバースロールコート等が挙げられる。このとき、シリカの粒子径を超える厚みとなるよう（硬化後のトップコート層の厚みがシリカの粒子径よりも大きくなるよう）に塗工する。塗膜の厚みはシリカの粒子径に応じて変わるが、通常２〜５０μｍ、好ましくは３〜１２μｍ程度である。 The coating method of the coating agent is not particularly limited, and examples thereof include knife coating, nozzle coating, gravure coating, rotary screen coating, and reverse roll coating. At this time, it coats so that it may become the thickness exceeding the particle diameter of silica (the thickness of the topcoat layer after hardening becomes larger than the particle diameter of silica). The thickness of the coating film varies depending on the silica particle diameter, but is usually 2 to 50 μm, preferably about 3 to 12 μm.
塗工後は先ず紫外線照射により、電離放射線硬化型樹脂を半硬化させる。紫外線照射装置としては、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、キセノンアーク、メタルハライドランプ等が使用できる。紫外線照射により、未硬化トップコート層の基材側から半硬化状態に推移する。これは、トップコート層のおもて面は大気と接触しているため、特に酸素との接触により硬化阻害を受けるためである。そして、基材側から半硬化状態に推移することに基づきシリカのリフティングが起こり、シリカがトップコート層のおもて面付近に集まる。紫外線照射量は、トップコート層を半硬化させる範囲内であって、具体的には、シリカのリフティングの程度に応じて調整すればよい。 After coating, the ionizing radiation curable resin is first semi-cured by ultraviolet irradiation. As the ultraviolet irradiation device, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. Due to ultraviolet irradiation, the uncured topcoat layer changes from the base material side to a semi-cured state. This is because the front surface of the top coat layer is in contact with the atmosphere, and thus is particularly hard to be inhibited by contact with oxygen. Then, lifting of the silica occurs based on the transition from the substrate side to the semi-cured state, and the silica collects in the vicinity of the front surface of the topcoat layer. The amount of ultraviolet irradiation is within a range in which the topcoat layer is semi-cured, and specifically, it may be adjusted according to the degree of lifting of silica.
紫外線照射により樹脂を半硬化させた後、電子線照射により樹脂をトップコート層に要求される硬度となるまで完全硬化させる。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５０〜１０００ＫｅＶ、好ましくは１００〜３００ＫｅＶ程度である。また、電子線の吸収線量は樹脂の完全硬化に要する量であればよく、通常１〜１０Ｍｒａｄ、好ましくは３〜５Ｍｒａｄ程度である。 After semi-curing the resin by ultraviolet irradiation, the resin is completely cured by electron beam irradiation until the hardness required for the topcoat layer is reached. 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 1000 KeV, preferably about 100 to 300 KeV. Moreover, the absorbed dose of an electron beam should just be the quantity required for complete hardening of resin, and is about 1-10 Mrad normally, Preferably it is about 3-5 Mrad.
上記過程を経て製造される化粧材は、トップコート層に含まれるシリカがリフティングによりトップコート層のおもて面側に集まっているため、艶消し効果が高い。また、シリカの粒子径を超える厚みとなるように塗工しているため、トップコート層表面にシリカに起因する凹凸が生じ難く、手触り感も滑らかなものである。さらに、トップコート層が完全硬化した電離放射線硬化型樹脂により形成されているため、耐擦傷性も高い。 The cosmetic material produced through the above process has a high matte effect because the silica contained in the topcoat layer is collected on the front surface side of the topcoat layer by lifting. In addition, since the coating is performed so as to have a thickness exceeding the particle diameter of silica, unevenness due to silica is hardly generated on the surface of the topcoat layer, and the touch feeling is also smooth. Furthermore, since the top coat layer is formed of a fully cured ionizing radiation curable resin, it has high scratch resistance.
本発明の製造方法は、電離放射線硬化型塗工剤を基材上に塗工後、紫外線照射による樹脂の半硬化を経てから電子線照射により樹脂を完全硬化させるため、紫外線照射時にシリカがリフティングされて艶消し効果が高い化粧材が得られる。また、電離放射線硬化型樹脂を完全硬化させたトップコート層を有するため、耐擦傷性が高い。さらに、塗工剤に含まれるシリカの粒子径を超える厚みとなるように塗工するため、トップコート層表面にシリカに起因する凹凸が生じ難く手触り感を損なうことがない。 In the production method of the present invention, after the ionizing radiation curable coating agent is applied on the substrate, the resin is completely cured by electron beam irradiation after semi-curing of the resin by ultraviolet irradiation. As a result, a cosmetic material having a high matting effect can be obtained. Moreover, since it has the topcoat layer which hardened the ionizing radiation curable resin completely, it has high scratch resistance. Furthermore, since coating is performed so as to have a thickness exceeding the particle diameter of silica contained in the coating agent, unevenness due to silica hardly occurs on the surface of the topcoat layer, and the touch feeling is not impaired.
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
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、１６０Ｗ／ｃｍの２燈の高圧水銀燈により紫外線を照射して樹脂を半硬化させた後、加速電圧１７５ｋｅＶ、吸収線量５Ｍｒａｄの条件で電子線を照射して樹脂を完全硬化させて化粧材を得た。
Example 1
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Next, the resin was semi-cured by irradiating ultraviolet rays with 2 W high-pressure mercury lamp of 160 W / cm, and then the resin was completely cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 keV and an absorbed dose of 5 Mrad. Obtained.
比較例１
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、１６０Ｗ／ｃｍの２燈の高圧水銀燈により紫外線を照射して樹脂を完全硬化させて化粧材を得た。
Comparative Example 1
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Subsequently, the resin was completely cured by irradiating ultraviolet rays with 2 W high-pressure mercury lamps of 160 W / cm to obtain a cosmetic material.
比較例２
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、加速電圧１７５ｋｅＶ、吸収線量５Ｍｒａｄの条件で電子線を照射して樹脂を完全硬化させて化粧材を得た。
Comparative Example 2
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Next, the resin was completely cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 keV and an absorbed dose of 5 Mrad to obtain a cosmetic material.
比較例３
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、加速電圧１７５ｋｅＶ、吸収線量５Ｍｒａｄの条件で電子線を照射して樹脂を完全硬化させて化粧材を得た。
Comparative Example 3
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Next, the resin was completely cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 keV and an absorbed dose of 5 Mrad to obtain a cosmetic material.
比較例４
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、加速電圧１７５ｋｅＶ、吸収線量５Ｍｒａｄの条件で電子線を照射して樹脂を完全硬化させて化粧材を得た。
Comparative Example 4
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Next, the resin was completely cured by irradiating an electron beam under the conditions of an acceleration voltage of 175 keV and an absorbed dose of 5 Mrad to obtain a cosmetic material.
比較例５
下記表１に示す組成の電離放射線硬化型塗工剤をロールコート方式により基材表面に塗工した。塗工厚みは５μｍ（５ｇ／ｍ2）であった。次いで、加速電圧１７５ｋｅＶ、吸収線量５Ｍｒａｄの条件で電子線を照射して樹脂を完全硬化させた後、さらに１６０Ｗ／ｃｍの２燈の高圧水銀燈により紫外線を照射して化粧材を得た。
Comparative Example 5
An ionizing radiation curable coating agent having the composition shown in Table 1 below was applied to the substrate surface by a roll coating method. The coating thickness was 5 μm (5 g / m 2 ). Next, the resin was completely cured by irradiating with an electron beam under the conditions of an acceleration voltage of 175 keV and an absorbed dose of 5 Mrad, and then further irradiated with ultraviolet rays with 2 W high-pressure mercury lamp of 160 W / cm to obtain a cosmetic material.
試験例１
実施例１及び比較例１〜５で用いた塗工剤の塗工適性を評価した。また、得られた化粧材の表面特性、手触り感及び艶消し効果を評価した。評価方法及び評価基準は次の通りである。評価結果を下記表２に示す。
＜塗工適性＞
塗工が容易であるものを○とした。塗工が困難（不適）であるものを×とした。
＜表面特性＞
スチールウール＃００００を学振型摩耗試験機に取りつけたものを荷重１５００ｇで化粧シート表面に押し当てて往復２０回擦ることにより擦傷がつくかどうかを調べた。擦傷がつかない場合の評価を○とし、擦傷がついた場合の評価を×とした。
＜手触り感＞
表面の手触りを触感により評価した。ザラツキがないものを○とした。ザラツキがあるものを×とした。
＜艶消し効果＞
ＪＩＳ−Ｚ−８７４１規定の測定方法に基づいて艶を測定した。艶の数値が小さいほど、低艶であり艶消し効果が高い。
Test example 1
The coating suitability of the coating agents used in Example 1 and Comparative Examples 1 to 5 was evaluated. In addition, the surface properties, hand feeling and matting effect of the obtained cosmetics were evaluated. Evaluation methods and evaluation criteria are as follows. The evaluation results are shown in Table 2 below.
<Coating suitability>
The ones that were easy to coat were marked with ◯. The case where coating was difficult (unsuitable) was marked with x.
<Surface characteristics>
A steel wool # 0000 attached to a Gakushoku-type wear tester was pressed against the decorative sheet surface with a load of 1500 g and rubbed 20 times back and forth to determine whether or not scratching would occur. The evaluation when no scratches were made was rated as “◯”, and the evaluation when scratches were made was marked as “X”.
<Hand feeling>
The touch of the surface was evaluated by tactile sensation. The one without the roughness was marked with a circle. The thing with a rough surface was set as x.
<Matte effect>
The gloss was measured based on the measurement method defined in JIS-Z-8741. The smaller the gloss value, the lower the gloss and the higher the matting effect.
Claims (5)
（１）有機溶剤を含まずシリカ及び光重合開始剤を含む電離放射線硬化型塗工剤を、基材上にシリカの粒子径を超える厚みとなるように塗工し、次いで
（２）紫外線照射により電離放射線硬化型樹脂を半硬化させた後、電子線照射により該樹脂をトップコート層に要求される硬度となるまで完全硬化させる
ことを特徴とする製造方法。 A method for producing a scratch-resistant matte cosmetic material comprising an ionizing radiation curable resin containing silica as a top coat layer,
(1) An ionizing radiation curable coating agent that does not contain an organic solvent and contains silica and a photopolymerization initiator is applied on the substrate so that the thickness exceeds the particle diameter of silica, and then (2) UV irradiation After the ionizing radiation curable resin is semi-cured by the above, the resin is completely cured by electron beam irradiation until the hardness required for the top coat layer is reached.
A scratch-resistant matte cosmetic material produced by the production method according to claim 1.
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| JP2011073379A (en) * | 2009-09-30 | 2011-04-14 | Dainippon Printing Co Ltd | Decorative sheet |
| JP2012077405A (en) * | 2010-09-30 | 2012-04-19 | Dainippon Printing Co Ltd | Wallpaper with visible light type photocatalytic function |
| JP2014184675A (en) * | 2013-03-25 | 2014-10-02 | Dainippon Printing Co Ltd | Decorative sheet and decorative laminate using the same |
| JP2016204483A (en) * | 2015-04-20 | 2016-12-08 | 東亞合成株式会社 | Production method of resin sheet |
| JP2017516873A (en) * | 2014-03-21 | 2017-06-22 | アベリー・デニソン・コーポレイションＡｖｅｒｙ Ｄｅｎｎｉｓｏｎ Ｃｏｒｐｏｒａｔｉｏｎ | Dual stage cured acrylic composition and related methods |
| JP2018065915A (en) * | 2016-10-19 | 2018-04-26 | 東亞合成株式会社 | Method for producing resin sheet |
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