JP3149747B2 - Cosmetic paper and manufacturing method thereof - Google Patents
Cosmetic paper and manufacturing method thereofInfo
- Publication number
- JP3149747B2 JP3149747B2 JP27108995A JP27108995A JP3149747B2 JP 3149747 B2 JP3149747 B2 JP 3149747B2 JP 27108995 A JP27108995 A JP 27108995A JP 27108995 A JP27108995 A JP 27108995A JP 3149747 B2 JP3149747 B2 JP 3149747B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- ionizing radiation
- resin
- decorative paper
- curable resin
- 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.)
- Expired - Lifetime
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は家具、住宅機器等に
使用する化粧板に使用する化粧紙およびその製造方法に
関し、特に表面硬度が高く、耐久性に優れた高級化粧板
に使用する化粧紙およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative paper used for a decorative panel used for furniture, housing equipment and the like and a method for producing the same, and more particularly to a decorative paper used for a high-grade decorative panel having a high surface hardness and excellent durability. And its manufacturing method.
【０００２】[0002]
【従来の技術】従来の前記用途の化粧紙としては、通常
の化粧紙用原紙に印刷を施したものに、熱硬化型や二液
硬化型や紫外線硬化型や電子線硬化型の樹脂からなるト
ップコート層を設けたものがある。しかしこれらのトッ
プコート層の塗布量は１０ｇ／ｍ2 以下が通常であり、
そのため高い表面強度と耐久性が要求される水平面用と
して必要な物性を得るのは極めて困難であった。2. Description of the Related Art Conventional decorative papers for the above-mentioned applications include those obtained by printing on ordinary base paper for decorative paper, heat-curable type, two-part curable type, ultraviolet curable type and electron beam curable type resins. Some have a top coat layer. However, the coating amount of these top coat layers is usually 10 g / m 2 or less,
Therefore, it has been extremely difficult to obtain the physical properties required for a horizontal surface requiring high surface strength and durability.
【０００３】水平面用として必要な物性を得るために
は、塗布量１５ｇ／ｍ2 以上のトップコート層が必要と
考えられるが、前記の熱硬化型や二液硬化型や紫外線硬
化型や電子線硬化型の樹脂のトップコート層を塗布量１
５ｇ／ｍ2 以上塗工した場合、化粧紙が強くカールして
しまい、生産加工時に巻き取ることが困難となる。カー
ルを抑えるために硬化後の柔軟性に優れた樹脂を用いる
方法もあるが、そうすると水平面用として必要な高い表
面強度が得られなくなってしまう。It is considered that a top coat layer having a coating amount of 15 g / m 2 or more is required in order to obtain physical properties required for a horizontal surface, but the above-mentioned thermosetting type, two-part curing type, ultraviolet curing type, electron beam, etc. Application amount of top coat layer of curable resin 1
When applied at 5 g / m 2 or more, the decorative paper is strongly curled, and it is difficult to wind it up during production processing. There is also a method of using a resin having excellent flexibility after curing in order to suppress curling, but in such a case, a high surface strength required for a horizontal surface cannot be obtained.
【０００４】その他の従来の家具や住宅機器類の水平面
に使用する化粧紙としては、チタン紙等の浸透性の良い
原紙に印刷を施した後、メラミン樹脂、ジアリルフタレ
ート樹脂等の熱硬化性樹脂を含浸させて作った樹脂含浸
紙を、フェノールコア紙やパーティクルボード等の基材
に乗せ、鏡面板を介して加熱圧縮して製造するものが知
られている。この方法によれば水平面用として必要な表
面硬度、耐摩耗性、および耐溶剤性を備えた化粧板がで
きるが、加熱圧縮加工のため、生産効率に極めて劣るも
のである。[0004] Other decorative papers used on the horizontal surface of furniture and household appliances are printed on a base paper having good permeability such as titanium paper and then cured with a thermosetting resin such as melamine resin and diallyl phthalate resin. A resin-impregnated paper made by impregnating with a resin is placed on a base material such as phenol core paper or particle board, and heated and compressed through a mirror surface plate to produce the paper. According to this method, a decorative plate having surface hardness, abrasion resistance and solvent resistance required for a horizontal surface can be obtained, but the production efficiency is extremely poor due to heat compression processing.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、以上のよう
な問題点を解決するためになされたもので、その課題と
するところは、水平面に使用可能な硬度や耐摩耗性を備
え意匠性に優れた高級化粧板を極めて能率的にかつ安価
に製造できるような、化粧紙及びその製造方法を提供す
ることにある。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a design having a hardness and abrasion resistance which can be used on a horizontal surface and having a design property. Another object of the present invention is to provide a decorative paper and a method for producing the same, which can produce a high-quality decorative board excellent in quality extremely efficiently and at low cost.
【０００６】[0006]
【課題を解決するための手段】本発明はこの課題を解決
するため、まず請求項１においては、化粧紙原紙の表面
に、任意に印刷層とアンカー層を設け、この上に１層が
５〜１４ｇ／ｍ2 である電離放射線硬化型樹脂を主成分
とする硬化樹脂塗膜層を合計１２ｇ／ｍ2 以上となるよ
うに１層か複数層積層して設け、さらにこの上に電離放
射線硬化型樹脂を主成分としシリコンもしくはフッ素か
らなる添加剤を含有する硬化樹脂塗膜層を３ｇ／ｍ2 以
上となるように設け、硬化樹脂塗膜層の総合計の膜厚が
１５ｇ／ｍ2 以上となることを特徴とする化粧紙を提供
するものである。According to the present invention, in order to solve this problem, a printing paper and an anchoring layer are arbitrarily provided on the surface of a base paper for decorative paper. ~14g / m provided 2 a is in a cured resin coating layer mainly composed of an ionizing radiation-curable resin is laminated total 12 g / m 2 or more and composed as one layer or multiple layers, further ionizing radiation curing on the A cured resin coating layer containing a mold resin as a main component and containing an additive composed of silicon or fluorine is provided so as to be 3 g / m 2 or more, and the total thickness of the cured resin coating layer is 15 g / m 2 or more. It is intended to provide a decorative paper characterized by the following.
【０００７】また、請求項２においては、前記化粧紙原
紙の表面に、撥液性インキ印刷模様を設け、この上に前
記硬化樹脂塗膜層が撥液性インキ印刷模様にはじかれて
設けられてなることを特徴とする請求項１記載の化粧紙
を提供するものである。According to a second aspect of the present invention, a liquid-repellent ink printed pattern is provided on the surface of the decorative paper base paper, and the cured resin coating layer is provided on the decorative paper base paper by being flipped by the liquid-repellent ink printed pattern. A decorative paper according to claim 1, wherein the decorative paper comprises:
【０００８】また、請求項３においては、前記アンカー
層が、架橋型樹脂を主成分とし、塗工後熱乾燥で塗工表
面が乾燥状態となる塗工液からなることを特徴とする請
求項２記載の化粧紙を提供するものである。According to a third aspect of the present invention, the anchor layer is composed of a coating liquid containing a cross-linkable resin as a main component and having a coating surface in a dried state by thermal drying after coating. 2. A decorative paper according to item 2.
【０００９】また、請求項４においては、前記架橋型樹
脂が電離放射線硬化型樹脂からなることを特徴とする請
求項３記載の化粧紙を提供するものである。According to a fourth aspect of the present invention, there is provided a decorative paper according to the third aspect, wherein the cross-linkable resin comprises an ionizing radiation-curable resin.
【００１０】また、請求項５においては、化粧紙原紙の
表面に、任意に印刷した後、電離放射線硬化型樹脂を主
成分とする塗工液を５〜１４ｇ／ｍ2 となるよう塗工
し、半硬化状態となるように電離放射線を照射し半硬化
樹脂塗膜を形成し、この工程を１度以上行って合計１２
ｇ／ｍ2 となるようにした後、電離放射線硬化型樹脂を
主成分としシリコンもしくはフッ素からなる添加剤を含
有する塗工液を３ｇ／ｍ 2 以上となるように塗工し、電
離放射線を照射し、総合計１５ｇ／ｍ2 以上とした樹脂
塗膜を完全硬化させることを特徴とする化粧紙の製造方
法を提供するものである。According to a fifth aspect of the present invention, the decorative paper base paper is
After optional printing on the surface, ionizing radiation curable resin
5-14 g / m of coating liquid as a componentTwoCoating to become
And then irradiate it with ionizing radiation so that it is in a semi-cured state.
A resin coating film is formed, and this step is performed at least once to obtain a total of 12
g / mTwoAfter that, the ionizing radiation-curable resin is
Contains additives consisting mainly of silicon or fluorine
3 g / m of coating liquid TwoApply so that the above
Irradiation radiation, total 15g / mTwoThe above resin
A method for producing decorative paper characterized by completely curing the coating film
It provides the law.
【００１１】また、請求項６においては、化粧紙原紙の
表面に任意に印刷し、アンカー層を設けた後、撥液性イ
ンキ印刷模様を設け、電離放射線硬化型樹脂を主成分と
する塗工液を５〜１４ｇ／ｍ2 となり前記撥液性インキ
印刷模様にはじかれて塗工し、半硬化状態となるように
電離放射線を照射し半硬化樹脂塗膜を形成し、この工程
を１度以上行って合計１２ｇ／ｍ2 となるようにした
後、電離放射線硬化型樹脂を主成分としシリコンもしく
はフッ素からなる添加剤を含有する塗工液を３ｇ／ｍ2
以上となるよう前記撥液性インキ印刷模様にはじかれて
塗工し、電離放射線を照射し総合計１５ｇ／ｍ2 以上と
した樹脂塗膜を完全硬化させることを特徴とする化粧紙
の製造方法を提供するものである。According to a sixth aspect of the present invention, the printing is carried out arbitrarily on the surface of the decorative paper base paper, and after providing an anchor layer, a liquid-repellent ink printing pattern is provided, and a coating mainly composed of an ionizing radiation-curable resin. The liquid becomes 5 to 14 g / m 2 , is repelled by the lyophobic ink print pattern, is applied, and is irradiated with ionizing radiation so as to be in a semi-cured state to form a semi-cured resin coating film. After making the total amount to 12 g / m 2 as described above, a coating liquid containing an ionizing radiation-curable resin as a main component and containing an additive made of silicon or fluorine is applied at 3 g / m 2.
A method for producing a decorative paper, comprising: applying a repellent ink printed pattern as described above, applying the coating, and irradiating with ionizing radiation to completely cure a resin coating having a total total of 15 g / m 2 or more. Is provided.
【００１２】また、請求項７においては、前記アンカー
層が電離放射線硬化型樹脂を主成分とし、塗工後熱乾燥
で塗工表面を乾燥状態とし、後の電離放射線硬化型樹脂
塗膜と一体で完全硬化してなることを特徴とする請求項
６記載の化粧紙の製造方法を提供するものである。According to a seventh aspect of the present invention, the anchor layer contains an ionizing radiation-curable resin as a main component, and after application, heat-drys the coating surface to form a dry state. The present invention provides a method for producing decorative paper according to claim 6, wherein the method is completely cured.
【００１３】[0013]
【発明の実施の形態】以下、本発明を詳細に説明する。
図１、２に本発明による化粧紙の断面の構造の一例を示
す。図１は、原紙１の表面に印刷インキ層２、電離放射
線硬化型樹脂を主成分とする硬化樹脂塗膜層３および
３’、電離放射線硬化型樹脂を主成分としシリコンもし
くはフッ素からなる添加剤を含有する硬化樹脂塗膜層
４、よりなる化粧紙である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
1 and 2 show an example of a cross-sectional structure of the decorative paper according to the present invention. FIG. 1 shows a printing ink layer 2, a cured resin coating layer 3 and 3 'mainly composed of an ionizing radiation-curable resin on the surface of a base paper 1, an additive composed mainly of ionizing radiation-curable resin and made of silicon or fluorine. Is a decorative paper comprising a cured resin coating layer 4 containing
【００１４】図２は、原紙１の表面に印刷インキ層２、
アンカー層５、撥液性インキ印刷模様６、電離放射線硬
化型樹脂を主成分とする硬化樹脂塗膜層３および３’、
電離放射線硬化型樹脂を主成分としシリコンもしくはフ
ッ素からなる添加剤を含有する硬化樹脂塗膜層４、より
なる化粧紙である。FIG. 2 shows a printing ink layer 2 on the surface of a base paper 1.
Anchor layer 5, liquid-repellent ink printed pattern 6, cured resin coating layers 3 and 3 'mainly composed of ionizing radiation-curable resin,
A decorative paper comprising a cured resin coating layer 4 containing an ionizing radiation-curable resin as a main component and containing an additive made of silicon or fluorine.
【００１５】本発明に係る化粧紙用原紙としては、坪量
２０〜２００ｇ／ｍ2 の化粧紙用原紙が使用可能であ
り、通常の薄葉紙、チタン紙等が挙げられる。坪量２０
ｇ／ｍ2 未満であると、紙力が弱いため、生産加工時に
紙切れ等のトラブルを引き起こしやすく、また、坪量２
００ｇ／ｍ2 をこえると化粧板にした場合に原紙の厚さ
が化粧板としての強度を低下させてしまう恐れがある。As the base paper for decorative paper according to the present invention, a base paper for decorative paper having a basis weight of 20 to 200 g / m 2 can be used, and examples thereof include ordinary thin paper and titanium paper. Basis weight 20
If it is less than g / m 2 , the paper strength is weak, so that troubles such as paper breakage during production processing are likely to occur.
If it exceeds 00 g / m 2 , the thickness of the base paper may decrease the strength of the decorative board when the decorative board is formed.
【００１６】印刷インキ層２のインキとしては、通常の
印刷インキが使用できる。印刷方法はグラビア印刷法等
の公知の印刷方法で良い。As the ink for the printing ink layer 2, a normal printing ink can be used. The printing method may be a known printing method such as a gravure printing method.
【００１７】アンカー層５に使用する架橋型樹脂を主成
分とした塗工後熱乾燥で塗工表面が乾燥状態となる塗工
液の、架橋型樹脂としては、熱硬化型樹脂や電離放射線
硬化型樹脂が使用可能である。The cross-linking resin of the coating liquid whose coating surface is in a dry state by thermal drying after coating, which is mainly composed of the cross-linking resin used for the anchor layer 5, may be a thermosetting resin or an ionizing radiation-curable resin. Mold resin can be used.
【００１８】熱硬化型樹脂とした場合には、アクリル
系、ウレタン系、エポキシ系等の一液硬化型もしくは２
液硬化型の熱硬化型樹脂等が使用可能であり、これらと
溶媒、無機および有機顔料、体質顔料等のフィラーを分
散させてもよい。When a thermosetting resin is used, a one-component curing type such as an acrylic, urethane, or epoxy resin or a two-component curing type resin may be used.
A liquid-curable thermosetting resin or the like can be used, and a filler such as a solvent, an inorganic or organic pigment, or an extender may be dispersed therein.
【００１９】電離放射線硬化型樹脂とした場合には、電
離放射線反応性の２重結合を有する水性エマルジョンま
たは電離放射線反応性の２重結合を有する水溶性又は溶
剤可溶性樹脂等であり、該樹脂のＴｇが４０℃以上さら
には６０℃以上であるものが好適であり、これに無機お
よび有機顔料、体質顔料等のフィラーを分散させてもよ
い。また、紫外線硬化型樹脂とした場合には、さらに光
開始剤が適量添加される。When the resin is an ionizing radiation-curable resin, it may be an aqueous emulsion having an ionizing radiation-reactive double bond or a water-soluble or solvent-soluble resin having an ionizing radiation-reactive double bond. Those having a Tg of 40 ° C. or more, more preferably 60 ° C. or more, are suitable, and fillers such as inorganic and organic pigments and extenders may be dispersed therein. When an ultraviolet-curable resin is used, an appropriate amount of a photoinitiator is further added.
【００２０】これら塗工液の塗工方法は任意であるが、
グラビアコーター、ロールコーター、リバースロールコ
ーター、ナイフコーター等の公知の塗工方法が使用可能
である。塗工後の乾燥は従来の熱乾燥が用いられ、溶媒
を揮発させた後、塗工表面が乾燥状態となれば良い。The method of applying these coating liquids is optional,
Known coating methods such as a gravure coater, a roll coater, a reverse roll coater, and a knife coater can be used. Conventional heat drying is used for drying after coating, and it is only necessary that the coated surface be in a dry state after the solvent is volatilized.
【００２１】撥液性印刷模様６に用いる撥液性インキと
しては通常の印刷インキにシリコン系もしくはフッ素系
の添加剤したインキ等が使用可能である。また、インキ
の樹脂分として、印刷後熱乾燥で塗工表面が乾燥状態と
なる電離放射線硬化型樹脂を用いるのが好適である。As the liquid-repellent ink used for the liquid-repellent print pattern 6, an ink or the like obtained by adding a silicon-based or fluorine-based additive to a normal printing ink can be used. Further, as the resin component of the ink, it is preferable to use an ionizing radiation-curable resin whose coated surface is in a dry state by thermal drying after printing.
【００２２】電離放射線硬化型樹脂を主成分とする硬化
樹脂塗膜層３および３’の電離放射線硬化型樹脂として
は、分子末端にアクリル基又はメタクリル基を有してい
るものが好ましく、ポリエステルアクリレート、ウレタ
ンアクリレート、エポキシアクリレート、ポリエステル
メタクリレート、ウレタンメタクリレート、エポキシメ
タクリレート等である。紫外線硬化の場合は光開始剤が
添加される。さらに、無機および有機顔料、体質顔料等
のフィラーを分散させても良い。As the ionizing radiation-curable resin of the cured resin coating layers 3 and 3 'mainly composed of an ionizing radiation-curable resin, those having an acryl group or a methacryl group at the molecular terminal are preferable, and polyester acrylate is preferred. , Urethane acrylate, epoxy acrylate, polyester methacrylate, urethane methacrylate, epoxy methacrylate and the like. In the case of ultraviolet curing, a photoinitiator is added. Further, fillers such as inorganic and organic pigments and extenders may be dispersed.
【００２３】塗工方法は任意であるが、グラビア塗工、
ロールコーター、リバースロールコーター、ナイフコー
ター、ブレードコーター、ロッドコーター、エアードク
ターコーター、ダイコーター、キャストコーター等の公
知の塗工方法で良い。The coating method is optional, but includes gravure coating,
Known coating methods such as a roll coater, a reverse roll coater, a knife coater, a blade coater, a rod coater, an air doctor coater, a die coater, and a cast coater may be used.
【００２４】塗布後、電離放射線照射により、塗膜を半
硬化させる。半硬化状態とは、塗膜表面はタックフリー
の状態であるが、完全に架橋はしていない状態である。
（ゲル分率７０〜９５％程度が好ましい）この工程を一
度以上行ない、１２ｇ／ｍ2以上の硬化樹脂塗膜層を形
成する。After application, the coating is semi-cured by irradiation with ionizing radiation. The semi-cured state is a state in which the surface of the coating film is tack-free but not completely crosslinked.
(The gel fraction is preferably about 70 to 95%.) This step is performed once or more to form a cured resin coating layer of 12 g / m 2 or more.
【００２５】次に、電離放射線硬化型樹脂を主成分とし
シリコンもしくはフッ素からなる添加剤を含有する硬化
樹脂塗膜層４を形成する。電離放射線硬化型樹脂として
は、分子末端にアクリル基又はメタクリル基を有してい
るものが好ましく、ポリエステルアクリレート、ウレタ
ンアクリレート、エポキシアクリレート、ポリエステル
メタクリレート、ウレタンメタクリレート、エポキシメ
タクリレート等である。また、紫外線硬化の場合は光開
始剤が添加される。さらに、無機および有機顔料、体質
顔料等のフィラーを分散させても良い。Next, a cured resin coating layer 4 containing an ionizing radiation curable resin as a main component and containing an additive made of silicon or fluorine is formed. As the ionizing radiation-curable resin, those having an acrylic group or a methacryl group at the molecular terminal are preferable, and examples thereof include polyester acrylate, urethane acrylate, epoxy acrylate, polyester methacrylate, urethane methacrylate, and epoxy methacrylate. In the case of ultraviolet curing, a photoinitiator is added. Further, fillers such as inorganic and organic pigments and extenders may be dispersed.
【００２６】シリコンもしくはフッ素からなる添加剤
は、反応性または非反応性のスリップ剤として添加され
る。これらにはシリコンアクリレート、フッ素アクリレ
ート、市販のシリコンオイル、フッ素パウダー等が使用
可能である。これらの添加量は全体１００重量部に対し
て０．１〜１０重量部が適当である。０．１重量部より
少ないと効果が発現できず、１０重量部以上であると表
面がすべりすぎてしまい、またコスト的に不適なものと
なってしまう。The additive consisting of silicon or fluorine is added as a reactive or non-reactive slip agent. For these, silicon acrylate, fluorine acrylate, commercially available silicone oil, fluorine powder and the like can be used. The appropriate amount of these additives is 0.1 to 10 parts by weight with respect to 100 parts by weight in total. If the amount is less than 0.1 part by weight, the effect cannot be exhibited, and if the amount is more than 10 parts by weight, the surface becomes too slippery and the cost is unsuitable.
【００２７】この工程で３ｇ／ｍ2 以上の硬化樹脂塗膜
層を形成し、硬化樹脂塗膜層全体として合計１５ｇ／ｍ
2 以上となるよう硬化樹脂塗膜層を形成する。塗工方法
は任意であるが、グラビア塗工、ロールコーター、リバ
ースロールコーター、ナイフコーター、ブレードコータ
ー、ロッドコーター、エアードクターコーター、ダイコ
ーター、キャストコーター等の公知の塗工方法で良い。In this step, a cured resin coating layer of 3 g / m 2 or more is formed, and a total of 15 g / m 2
A cured resin coating layer is formed so as to be 2 or more. The coating method is arbitrary, but may be a known coating method such as gravure coating, roll coater, reverse roll coater, knife coater, blade coater, rod coater, air doctor coater, die coater, or cast coater.
【００２８】以上の工程の後、電離放射線照射により、
塗膜を完全硬化させる。電子線硬化の場合、電子線照射
装置より照射する電子線の加速電圧は１５０〜２００ｋ
Ｖ、照射量は３〜５Ｍｒａｄ程度が良い。紫外線硬化の
場合の照射量は４００〜６００ｍｊ／ｃｍ2 程度が良
い。通常この処理は５０〜１５０ｍ／ｍｉｎのライン速
度で可能であるから極めて生産効率が高い。After the above steps, by irradiation with ionizing radiation,
Completely cure the coating. In the case of electron beam curing, the acceleration voltage of the electron beam irradiated from the electron beam irradiation device is 150 to 200 k
V, the irradiation amount is preferably about 3 to 5 Mrad. The irradiation amount in the case of ultraviolet curing is preferably about 400 to 600 mj / cm 2 . Usually, this process is possible at a line speed of 50 to 150 m / min, so that the production efficiency is extremely high.
【００２９】以上に述べたように、本発明の化粧紙は原
紙表面に印刷した後、電離放射線硬化型樹脂を主成分と
する塗工液を塗工し電離放射線を照射し半硬化状態の塗
膜を形成する工程を一度以上行った後、電離放射線硬化
型樹脂を主成分としシリコンもしくはフッ素からなる添
加剤を含有する塗工液を塗工し電離放射線を照射し塗膜
を完全硬化させることにより、水平面に使用可能な硬度
や耐摩耗性を備え意匠性に優れた高級化粧板を極めて能
率的にかつ安価に製造できるような化粧紙が得られる。As described above, after the decorative paper of the present invention is printed on the base paper surface, it is coated with a coating liquid containing an ionizing radiation-curable resin as a main component and irradiated with ionizing radiation to obtain a semi-cured coating. After performing the film forming process at least once, apply a coating liquid containing an ionizing radiation-curable resin as a main component and containing an additive consisting of silicon or fluorine, and irradiate with ionizing radiation to completely cure the coating film. As a result, a decorative paper which can be used to manufacture a high-grade decorative plate having hardness and abrasion resistance which can be used on a horizontal surface and having excellent design properties can be produced extremely efficiently and inexpensively.
【００３０】[0030]
＜実施例１＞化粧紙用原紙として坪量６０ｇ／ｍ2 の含
浸紙を用い、これに木目柄を水性インキ（東洋インキ製
造（株）製）で印刷し、電離放射線硬化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 を用い、これをグラビア方式により１４ｇ／ｍ2 塗工
し、電子線照射装置（日新ハイボルテージ（株）製：
「キュアトロン」）の照射下を通過させ、照射線量約
１．０Ｍｒａｄのエネルギーで塗膜を半硬化させ、巻き
取った。<Example 1> An impregnated paper having a basis weight of 60 g / m 2 was used as a base paper for decorative paper, and a grain pattern was printed on the impregnated paper with an aqueous ink (manufactured by Toyo Ink Mfg. Co., Ltd.). Using 60 parts by weight of “EB-230” manufactured by Daicel UCB Co., Ltd., and 40 parts by weight of 1,6 hexanediol diacrylate (monomer), applying 14 g / m 2 by a gravure method, and applying an electron beam irradiation device ( Nissin High Voltage Co., Ltd .:
The coating was semi-cured with an irradiation dose of about 1.0 Mrad and wound up.
【００３１】さらに、電子線硬化型塗工液として 東亞合成化学工業（株）製「アロニックスＭ−８０３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 富士シリシア化学（株）製：「サイリシア350 」（マット剤） ８重量部 を用い、これにフッ素系添加剤としてShamrock社製：
「FluoroSlip231 」３重量部を添加し、これをグラビア
方式により５ｇ／ｍ2 塗工し、電子線照射装置（日新ハ
イボルテージ（株）製：「キュアトロン」）の照射下を
通過させ、照射線量約３．０Ｍｒａｄのエネルギーで塗
膜を完全硬化させ、巻き取った。Further, as an electron beam-curable coating liquid, 60 parts by weight of "Aronix M-8030" manufactured by Toagosei Chemical Industry Co., Ltd. 40 parts by weight of 1,6 hexanediol diacrylate (monomer) 40 parts by weight manufactured by Fuji Silysia Chemical Ltd. : 8 parts by weight of "Sylysia 350" (a matting agent) to which was added a fluorine-based additive manufactured by Shamrock:
3 parts by weight of “FluoroSlip231” was added, and this was coated at 5 g / m 2 by a gravure method, and passed under irradiation of an electron beam irradiation device (“Curetron” manufactured by Nissin High Voltage Co., Ltd.) to irradiate. The coating was completely cured with a dose of about 3.0 Mrad of energy and wound up.
【００３２】前記化粧紙を尿素・酢酸ビニル系の接着剤
にてパーチクルボードと貼り合わせ、化粧板にしたとこ
ろ、非常に優れた表面強度および耐久性を有しており、
水平面への使用は問題ないものであった。When the decorative paper was bonded to a particle board with a urea / vinyl acetate adhesive to form a decorative board, it had extremely excellent surface strength and durability.
Use on a horizontal surface was no problem.
【００３３】＜実施例２＞化粧紙用原紙として坪量３０
ｇ／ｍ2 の混抄紙を用い、これに木目柄を水性インキ
（東洋インキ製造（株）製）で印刷し、これに電子線硬
化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 を用い、これをグラビア方式により７ｇ／ｍ2 塗工し、
電子線照射装置（日新ハイボルテージ（株）製：「キュ
アトロン」）の照射下を通過させ、照射線量約１．０Ｍ
ｒａｄのエネルギーで塗膜を半硬化させた。<Example 2> The basis weight was 30 as a base paper for decorative paper.
g / m 2 of mixed paper, and a woodgrain pattern was printed on the paper with an aqueous ink (manufactured by Toyo Ink Mfg. Co., Ltd.), and an “EB” manufactured by Daicel UCB Co., Ltd. was used as an electron beam-curable coating liquid. -230 "60 parts by weight 1,6 hexanediol diacrylate (monomer) 40 parts by weight, and this was applied by a gravure method at 7 g / m 2 ,
It is passed under the irradiation of an electron beam irradiation device (manufactured by Nissin High Voltage Co., Ltd .: "Curetron"), and the irradiation dose is about 1.0 M
The coating was semi-cured with rad energy.
【００３４】さらに、紫外線硬化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 チバガイギー（株）製：「ダロキュア１１７３」（光開始剤） ３重量部 を用い、これをグラビア方式により７ｇ／ｍ2 塗工し、
１２０Ｗ／ｃｍの高圧水銀灯照射下を通過させ、照射線
量約３００ｍＪ／ｃｍ2 のエネルギーで塗膜を半硬化さ
せ、巻き取った。Further, as an ultraviolet curable coating liquid, "EB-230" manufactured by Daicel UCB Co., Ltd. 60 parts by weight 1,6 hexanediol diacrylate (monomer) 40 parts by weight Ciba Geigy Co., Ltd .: "Darocur 1173""(Photoinitiator) 3 parts by weight, and this was coated at 7 g / m 2 by a gravure method,
The film was passed under irradiation with a high-pressure mercury lamp of 120 W / cm, semi-cured with an irradiation dose of about 300 mJ / cm 2 , and wound up.
【００３５】これに、電子線硬化型塗工液として 東亞合成化学工業（株）製「アロニックスＭ−８０３０」 ７０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ３０重量部 を用い、これにシリコン系添加剤シリコンアクリレート
（ダイセル・ユーシービー（株）製「エベクリル３５
０」）を５重量部添加し、これをグラビア方式により５
ｇ／ｍ2 塗工し、電子線照射装置（日新ハイボルテージ
（株）製：「キュアトロン」）の照射下を通過させ、照
射線量約３．０Ｍｒａｄのエネルギーで塗膜を完全硬化
させ、巻き取った。As an electron beam-curable coating liquid, 70 parts by weight of "Aronix M-8030" manufactured by Toagosei Chemical Industry Co., Ltd. 30 parts by weight of 1,6 hexanediol diacrylate (monomer) was used, and silicon was added thereto. -Based additive silicon acrylate (Evecryl 35 manufactured by Daicel UCB Co., Ltd.)
0 ") was added by 5 parts by weight, and
g / m 2 , and passed under irradiation of an electron beam irradiation device (manufactured by Nissin High Voltage Co., Ltd .: “Curetron”), and the coating film was completely cured with an irradiation dose of about 3.0 Mrad. Wound up.
【００３６】上記化粧紙を尿素・酢酸ビニル系の接着剤
にてパーチクルボードと貼り合わせ、化粧板にしたとこ
ろ、非常に優れた表面強度および耐久性を有しており、
水平面への使用は問題ないものであった。When the decorative paper was bonded to a particle board with a urea / vinyl acetate adhesive to form a decorative board, it had extremely excellent surface strength and durability.
Use on a horizontal surface was no problem.
【００３７】＜実施例３＞化粧紙用原紙として坪量６０
ｇ／ｍ2 の含浸紙を用い、これに木目柄を水性インキ
（東洋インキ製造（株）製）で印刷し、２液硬化型ウレ
タン系塗工液（東洋インキ製造（株）製）を塗工し、１
４０℃の乾燥ゾーンで乾燥させた後、溌液性水性インキ
（東洋インキ製造（株）製）で木目導管模様を印刷し、
これに電子線硬化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 を用い、これをグラビア方式により１５ｇ／ｍ2 塗工
し、電子線照射装置（日新ハイボルテージ（株）製：
「キュアトロン」）の照射下を通過させ、照射線量約
１．０Ｍｒａｄのエネルギーで塗膜を半硬化させ、巻き
取った。<Example 3> As basis paper for decorative paper, basis weight was 60
g / m 2 of impregnated paper, and the woodgrain pattern is printed with an aqueous ink (manufactured by Toyo Ink Mfg. Co., Ltd.), and a two-component curable urethane coating solution (manufactured by Toyo Ink Mfg. Co., Ltd.) is applied. Work, 1
After drying in a drying zone at 40 ° C., a wood grain conduit pattern was printed with a liquid-repellent aqueous ink (manufactured by Toyo Ink Mfg. Co., Ltd.)
For this, 60 parts by weight of “EB-230” manufactured by Daicel UCB Ltd. and 40 parts by weight of 1,6 hexanediol diacrylate (monomer) as an electron beam-curable coating liquid were used, and this was gravure method at 15 g / m 2. 2 Coating, electron beam irradiation device (Nissin High Voltage Co., Ltd .:
The coating was semi-cured with an irradiation dose of about 1.0 Mrad and wound up.
【００３８】これに、電子線硬化型塗工液として、 東亞合成化学工業（株）製「アロニックスＭ−８０３０」 ７０重量部 １，６ヘキサンジオールジアクリレート ３０重量部 を用い、これにシリコン系添加剤（ダイセル・ユーシー
ビー（株）製「エベクリル３５０」）５重量部を添加
し、これをグラビア方式により５ｇ／ｍ2 塗工し、電子
線照射装置（日新ハイボルテージ（株）製：「キュアト
ロン」）の照射下を通過させ、照射線量約３．０Ｍｒａ
ｄのエネルギーで塗膜を完全硬化させ、巻き取った。As an electron beam-curable coating liquid, 70 parts by weight of "Aronix M-8030" manufactured by Toagosei Chemical Industry Co., Ltd. 30 parts by weight of 1,6 hexanediol diacrylate was used, and a silicon-based additive was added thereto. 5 parts by weight of an agent (“Evecryl 350” manufactured by Daicel UCB) is coated by a gravure method at 5 g / m 2, and an electron beam irradiation device (manufactured by Nissin High Voltage Co., Ltd .: “ Curetron ") and an irradiation dose of about 3.0 Mra
The coating film was completely cured with the energy of d and wound up.
【００３９】上記化粧紙を尿素・酢酸ビニル系の接着剤
にてパーチクルボードと貼り合わせ、化粧板にしたとこ
ろ、非常に優れた表面強度、耐溶剤性および耐久性を有
しており、水平面への使用は問題ないものであった。When the decorative paper was bonded to a particle board with a urea / vinyl acetate adhesive to form a decorative board, it had very excellent surface strength, solvent resistance and durability, Use was fine.
【００４０】＜実施例４＞坪量３０ｇ／ｍ2 の混抄紙に
木目柄を水性インキ（東洋インキ製造（株）製）で印刷
し、分子末端にアクリル基を有するエマルジョン塗工液
を塗工し、１４０℃の乾燥ゾーンで乾燥させた後、溌液
性水性インキ（東洋インキ製造（株）製）で木目導管模
様を印刷し、電子線硬化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 を用い、これをグラビア方式により７ｇ／ｍ2 塗工し、
電子線照射装置（日新ハイボルテージ（株）製：「キュ
アトロン」）の照射下を通過させ、照射線量約１．０Ｍ
ｒａｄのエネルギーで塗膜を半硬化させた。Example 4 A woodgrain pattern was printed on a mixed paper having a basis weight of 30 g / m 2 with an aqueous ink (manufactured by Toyo Ink Mfg. Co., Ltd.), and an emulsion coating liquid having an acrylic group at the molecular terminal was applied. Then, after drying in a drying zone at 140 ° C., a wood grain pattern is printed with a liquid-repellent water-based ink (manufactured by Toyo Ink Mfg. Co., Ltd.), and as an electron beam-curable coating solution, Daicel UCB Co., Ltd. "EB-230", 60 parts by weight 1,6 hexanediol diacrylate (monomer) 40 parts by weight, and this was coated by a gravure method at 7 g / m 2 ,
It is passed under the irradiation of an electron beam irradiation device (manufactured by Nissin High Voltage Co., Ltd .: "Curetron"), and the irradiation dose is about 1.0 M
The coating was semi-cured with rad energy.
【００４１】さらに、紫外線硬化型塗工液として ダイセル・ユーシービー（株）製「ＥＢ−２３０」 ６０重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４０重量部 チバガイギー（株）製：「ダロキュア１１７３」（光開始剤） ８重量部 を用い、をグラビア方式により７ｇ／ｍ2 塗工し、１２
０Ｗ／ｃｍの高圧水銀灯照射下を通過させ、照射線量約
３００ｍｊ／ｃｍ2 のエネルギーで塗膜を半硬化させ、
巻き取った。Further, as an ultraviolet-curable coating liquid, "EB-230" manufactured by Daicel UCB Co., Ltd. 60 parts by weight 1,6 hexanediol diacrylate (monomer) 40 parts by weight Ciba Geigy Co., Ltd .: "Darocur 1173" (Photoinitiator), 8 g by weight, and 7 g / m 2 were coated by gravure method to obtain 12 g
Passing under 0 W / cm high pressure mercury lamp irradiation, semi-curing the coating film with energy of irradiation dose of about 300 mj / cm 2 ,
Wound up.
【００４２】これに、電子線硬化型塗工液として、 東亞合成化学工業（株）製「アロニックスＭ−８０３０」 ６５重量部 １，６ヘキサンジオールジアクリレート（モノマー） ４５重量部 を用い、これにシリコン系添加剤（ダイセル・ユーシー
ビー（株）製「エベクリル３５０」）５重量部を添加
し、これをグラビア方式により５ｇ／ｍ2 塗工し、電子
線照射装置（日新ハイボルテージ（株）製：「キュアト
ロン」）の照射下を通過させ、照射線量約３．０Ｍｒａ
ｄのエネルギーで塗膜を完全硬化させ、巻き取った。As an electron beam-curable coating liquid, 65 parts by weight of "Aronix M-8030" manufactured by Toagosei Chemical Industry Co., Ltd. and 45 parts by weight of 1,6 hexanediol diacrylate (monomer) were used. 5 parts by weight of a silicon-based additive (“Evecryl 350” manufactured by Daicel UCB Co., Ltd.) was added, and this was coated at 5 g / m 2 by a gravure method, and an electron beam irradiation device (Nissin High Voltage Co., Ltd.) Manufactured by “Curetron”), and the irradiation dose is about 3.0 Mra.
The coating film was completely cured with the energy of d and wound up.
【００４３】上記化粧紙を尿素・酢酸ビニル系の接着剤
にてパーチクルボードと貼り合わせ、化粧板にしたとこ
ろ、非常に優れた表面強度および耐久性を有しており、
水平面への使用は問題ないものであった。When the decorative paper was bonded to a particle board with a urea / vinyl acetate adhesive to form a decorative board, it had extremely excellent surface strength and durability.
Use on a horizontal surface was no problem.
【００４４】[0044]
【発明の効果】以上に示したように、本発明により、１
層以上の電離放射線硬化型樹脂を主成分とする合計１２
ｇ／ｍ2 以上の硬化樹脂塗膜層、電離放射線硬化型樹脂
を主成分としシリコンもしくはフッ素からなる添加剤を
含有する３ｇ／ｍ2 以上の硬化樹脂塗膜層、からなる合
計１５ｇ／ｍ2 以上の硬化樹脂塗膜層を有する構成を採
ることにより、極めて表面強度および耐久性に優れてお
り、水平面に使用可能な硬度や耐摩耗性を備えた化粧紙
を提供することを可能とした。また、半硬化状態の塗膜
を形成する工程を一度以上行った後、電離放射線硬化型
樹脂を主成分としシリコンもしくはフッ素からなる添加
剤を含有する塗工液を塗工し、電離放射線を照射して塗
膜を完全硬化させる工程の製造方法を採ることにより、
化粧紙のカールを低くおさえることが可能となり、極め
て能率的にかつ安価に前記化粧紙を製造することを可能
にした。As described above, according to the present invention, 1
12 layers or more containing ionizing radiation-curable resin as a main component
g / m 2 or more, a total of 15 g / m 2 consisting of a cured resin coating layer of 3 g / m 2 or more containing an ionizing radiation-curable resin as a main component and containing an additive composed of silicon or fluorine. By adopting the configuration having the above cured resin coating layer, it is possible to provide a decorative paper having extremely excellent surface strength and durability and having hardness and abrasion resistance that can be used on a horizontal surface. In addition, after performing the step of forming a semi-cured coating film once or more, a coating liquid containing an ionizing radiation-curable resin as a main component and containing an additive composed of silicon or fluorine is applied, and ionizing radiation is applied. By adopting the manufacturing method of the step of completely curing the coating film,
The curl of the decorative paper can be suppressed low, and the decorative paper can be manufactured extremely efficiently and at low cost.
【図１】本発明の化粧紙の一例の断面の構成を示す説明
図である。FIG. 1 is an explanatory diagram showing a cross-sectional configuration of an example of the decorative paper of the present invention.
【図２】本発明の化粧紙の一例の断面の構成を示す説明
図である。FIG. 2 is an explanatory diagram showing a cross-sectional configuration of an example of the decorative paper of the present invention.
１…原紙 ２…印刷インキ層 ３、３’…電離放射線硬化型樹脂を主成分とする硬化樹
脂塗膜層 ４…電離放射線硬化型樹脂を主成分としシリコンもしく
はフッ素からなる添加剤を含有する硬化樹脂塗膜層 ５…アンカー層 ６…撥液性インキ印刷模様DESCRIPTION OF SYMBOLS 1 ... Base paper 2 ... Printing ink layer 3, 3 '... Cured resin coating layer mainly composed of ionizing radiation-curable resin 4 ... Curing containing ionizing radiation-curable resin as a main component and containing an additive composed of silicon or fluorine Resin coating layer 5: Anchor layer 6: Liquid-repellent ink print pattern
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 33/00 B05D 3/06 B05D 7/24 301 B32B 27/36 101 ──────────────────────────────────────────────────の Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) B32B 33/00 B05D 3/06 B05D 7/24 301 B32B 27/36 101
Claims (7)
カー層を設け、この上に１層が５〜１４ｇ／ｍ2 である
電離放射線硬化型樹脂を主成分とする硬化樹脂塗膜層を
合計１２ｇ／ｍ2 以上となるように１層か複数層積層し
て設け、さらにこの上に電離放射線硬化型樹脂を主成分
としシリコンもしくはフッ素からなる添加剤を含有する
硬化樹脂塗膜層を３ｇ／ｍ2 以上となるように設け、硬
化樹脂塗膜層の総合計の膜厚が１５ｇ／ｍ2 以上となる
ことを特徴とする化粧紙。1. A hardened resin coating mainly comprising an ionizing radiation-curable resin having a printing layer and an anchor layer optionally on the surface of a decorative paper base paper, one layer of which is 5 to 14 g / m 2. One layer or a plurality of layers are provided so as to have a total thickness of 12 g / m 2 or more, and a cured resin coating layer containing an ionizing radiation-curable resin as a main component and an additive made of silicon or fluorine is further provided thereon. Is provided so as to be 3 g / m 2 or more, and the total thickness of the cured resin coating layer is 15 g / m 2 or more.
刷模様を設け、この上に前記硬化樹脂塗膜層が撥液性イ
ンキ印刷模様にはじかれて設けられてなることを特徴と
する請求項１記載の化粧紙。2. A liquid repellent ink printed pattern is provided on the surface of the decorative paper base paper, and the cured resin coating layer is provided on the decorative paper base paper by being flipped by the liquid repellent ink printed pattern. The decorative paper according to claim 1,
し、塗工後熱乾燥で塗工表面が乾燥状態となる塗工液か
らなることを特徴とする請求項２記載の化粧紙。3. The decorative paper according to claim 2, wherein the anchor layer is composed of a coating liquid containing a cross-linkable resin as a main component and a coating surface being dried by thermal drying after coating.
らなることを特徴とする請求項３記載の化粧紙。4. The decorative paper according to claim 3, wherein said cross-linkable resin comprises an ionizing radiation-curable resin.
電離放射線硬化型樹脂を主成分とする塗工液を５〜１４
ｇ／ｍ2 となるよう塗工し、半硬化状態となるように電
離放射線を照射し半硬化樹脂塗膜を形成し、この工程を
１度以上行って合計１２ｇ／ｍ2 となるようにした後、
電離放射線硬化型樹脂を主成分としシリコンもしくはフ
ッ素からなる添加剤を含有する塗工液を３ｇ／ｍ2 以上
となるように塗工し、電離放射線を照射し、総合計１５
ｇ／ｍ2 以上とした樹脂塗膜を完全硬化させることを特
徴とする化粧紙の製造方法。5. After arbitrarily printing on the surface of decorative paper base paper,
5-14 coating liquids mainly composed of ionizing radiation-curable resin
g / m 2, and irradiation with ionizing radiation so as to be in a semi-cured state to form a semi-cured resin coating film. This step was performed once or more so that a total of 12 g / m 2 was obtained. rear,
A coating liquid containing an ionizing radiation-curable resin as a main component and containing an additive made of silicon or fluorine is applied so as to be 3 g / m 2 or more, and is irradiated with ionizing radiation.
A method for producing decorative paper, which comprises completely curing a resin coating having a g / m 2 or more.
ー層を設けた後、撥液性インキ印刷模様を設け、電離放
射線硬化型樹脂を主成分とする塗工液を５〜１４ｇ／ｍ
2 となり前記撥液性インキ印刷模様にはじかれて塗工
し、半硬化状態となるように電離放射線を照射し半硬化
樹脂塗膜を形成し、この工程を１度以上行って合計１２
ｇ／ｍ2 となるようにした後、電離放射線硬化型樹脂を
主成分としシリコンもしくはフッ素からなる添加剤を含
有する塗工液を３ｇ／ｍ2 以上となるよう前記撥液性イ
ンキ印刷模様にはじかれて塗工し、電離放射線を照射し
総合計１５ｇ／ｍ 2 以上とした樹脂塗膜を完全硬化させ
ることを特徴とする化粧紙の製造方法。6. The method according to claim 6, further comprising the steps of:
-Layer is provided, then a liquid-repellent ink printed pattern is provided, and ionized
5-14 g / m2 of coating liquid containing radiation-curable resin as a main component
TwoBeing repelled by the lyophobic ink print pattern
And then irradiate it with ionizing radiation so that it is in a semi-cured state.
A resin coating film is formed, and this step is performed at least once to obtain a total of 12
g / mTwoAfter that, the ionizing radiation-curable resin is
Contains additives consisting mainly of silicon or fluorine
3 g / m of coating liquidTwoThe liquid-repellent a
The coating is repelled and printed with ionizing radiation
Total 15g / m TwoCompletely cure the resin coating
A method for producing decorative paper.
主成分とし、塗工後熱乾燥で塗工表面を乾燥状態とし、
後の電離放射線硬化型樹脂塗膜と一体で完全硬化してな
ることを特徴とする請求項６記載の化粧紙の製造方法。7. An anchor layer comprising an ionizing radiation-curable resin as a main component, a coating surface being dried by heat drying after coating,
7. The method for producing decorative paper according to claim 6, wherein the coating is completely cured integrally with the subsequent ionizing radiation-curable resin coating film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27108995A JP3149747B2 (en) | 1995-10-19 | 1995-10-19 | Cosmetic paper and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27108995A JP3149747B2 (en) | 1995-10-19 | 1995-10-19 | Cosmetic paper and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09109347A JPH09109347A (en) | 1997-04-28 |
| JP3149747B2 true JP3149747B2 (en) | 2001-03-26 |
Family
ID=17495216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27108995A Expired - Lifetime JP3149747B2 (en) | 1995-10-19 | 1995-10-19 | Cosmetic paper and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3149747B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000025166A (en) * | 1998-07-14 | 2000-01-25 | Toppan Printing Co Ltd | Formation of surface protective layer and decorative sheet |
| JP4857455B2 (en) * | 1999-12-24 | 2012-01-18 | 大日本印刷株式会社 | Cosmetic material with excellent weather resistance |
| JP3610454B2 (en) * | 1999-12-28 | 2005-01-12 | イビデン株式会社 | Veneer |
| JP4522563B2 (en) * | 2000-09-13 | 2010-08-11 | 大日本印刷株式会社 | Cosmetic material |
| JP2002347201A (en) * | 2001-05-28 | 2002-12-04 | Dainippon Printing Co Ltd | Decorative material |
| JP2003011315A (en) * | 2001-07-04 | 2003-01-15 | Dainippon Printing Co Ltd | Decorative material |
| JP4641126B2 (en) * | 2001-08-23 | 2011-03-02 | 大日本印刷株式会社 | Cosmetic material |
| JP4789522B2 (en) * | 2005-07-08 | 2011-10-12 | 東洋インキＳｃホールディングス株式会社 | Decorative paper and makeup materials |
| JP2009113274A (en) * | 2007-11-05 | 2009-05-28 | Toppan Printing Co Ltd | Decorative sheet |
| JP4918914B2 (en) * | 2008-01-10 | 2012-04-18 | 凸版印刷株式会社 | Decorative paper manufacturing method |
-
1995
- 1995-10-19 JP JP27108995A patent/JP3149747B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09109347A (en) | 1997-04-28 |
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