JP4244167B2 - Transfer sheet and ink composition used therefor - Google Patents
Transfer sheet and ink composition used therefor Download PDFInfo
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- JP4244167B2 JP4244167B2 JP2003270599A JP2003270599A JP4244167B2 JP 4244167 B2 JP4244167 B2 JP 4244167B2 JP 2003270599 A JP2003270599 A JP 2003270599A JP 2003270599 A JP2003270599 A JP 2003270599A JP 4244167 B2 JP4244167 B2 JP 4244167B2
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- transfer sheet
- foam
- foaming
- ink
- transfer
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- 239000000203 mixture Substances 0.000 title claims description 6
- 230000001629 suppression Effects 0.000 claims description 68
- 239000006260 foam Substances 0.000 claims description 66
- 238000005187 foaming Methods 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 239000003112 inhibitor Substances 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004606 Fillers/Extenders Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- 239000000976 ink Substances 0.000 description 79
- 239000000463 material Substances 0.000 description 24
- 229920000915 polyvinyl chloride Polymers 0.000 description 19
- 239000004800 polyvinyl chloride Substances 0.000 description 19
- 238000007639 printing Methods 0.000 description 8
- 230000002688 persistence Effects 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- 238000007646 gravure printing Methods 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Decoration By Transfer Pictures (AREA)
- Laminated Bodies (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、住宅、店舗等の建築物や、電車、自動車等の車両や、飛行機、船舶等の内装、外装材や、床材等の表面に化粧のために転写して使用するための転写シート及びそれに用いるインキ組成物に関する。 The present invention is a transfer for use on a surface of a building such as a house, a store, a vehicle such as a train or an automobile, an interior of an airplane or a ship, an exterior material or a floor material for makeup. The present invention relates to a sheet and an ink composition used therefor.
転写シートの転写層を転写するための被転写材としての熱発泡性のポリ塩化ビニル樹脂には、その発泡を促進させるために、一般に亜鉛やバリウムといった安定剤が添加されている。この安定剤の働きにより、通常は高温で発泡するポリ塩化ビニル樹脂が、その温度以下で発泡できるようになる。 A heat-foamable polyvinyl chloride resin as a transfer material for transferring a transfer layer of a transfer sheet is generally added with a stabilizer such as zinc or barium in order to promote foaming. Due to the action of the stabilizer, a polyvinyl chloride resin which normally foams at a high temperature can be foamed at or below that temperature.
そこで、転写シートの転写層としての転写インキ中に発泡抑制剤としてトリアジンを用いると、トリアジンは安定剤の働きを阻害し、転写されたインキの有る部分の熱発泡性のポリ塩化ビニル樹脂基材は高温でなければ発泡できなくなる。 Therefore, when triazine is used as a foaming inhibitor in the transfer ink as the transfer layer of the transfer sheet, the triazine inhibits the function of the stabilizer, and the thermally foamable polyvinyl chloride resin base material where the transferred ink is present. Cannot foam unless it is hot.
したがって、発泡抑制剤にトリアジンを用いた転写シートでは、発泡温度を低くすることによって、転写された熱発泡性のポリ塩化ビニル樹脂基材を、発泡する部分と発泡しない部分とに分けることができ、そのために発泡抑制効果を得ることができる。 Therefore, in a transfer sheet using triazine as a foam inhibitor, the transferred heat-foamable polyvinyl chloride resin substrate can be divided into a foaming part and a non-foaming part by lowering the foaming temperature. Therefore, the foaming suppression effect can be obtained.
このような熱発泡性のポリ塩化ビニル樹脂基材を、発泡する部分と発泡しない部分とに分けるための良好な発泡抑制効果を得るためには、発泡が始まる前に、発泡抑制剤を被転写材であるポリ塩化ビニル樹脂層に迅速に浸透させる必要がある。 In order to obtain a good foam suppression effect for dividing such a heat-foamable polyvinyl chloride resin substrate into a foaming part and a non-foaming part, a foam inhibitor is transferred before foaming starts. It is necessary to rapidly penetrate the polyvinyl chloride resin layer as a material.
しかし、発泡抑制剤としてのトリアジンは融点が３００℃以上と高温であるため、発泡が始まる前にポリ塩化ビニル樹脂層に浸透させることは困難であり、良好な発泡抑制効果を得ることができないものであった。 However, since triazine as a foaming inhibitor has a high melting point of 300 ° C. or higher, it is difficult to infiltrate the polyvinyl chloride resin layer before foaming starts, and a good foaming inhibiting effect cannot be obtained. Met.
そこで、発泡抑制剤として、１６０℃以下の低い融点を示すベンゾトリアゾール、トリアゾール等を用いた転写シートでは、発泡が始まる前に、発泡抑制剤を被転写材であるポリ塩化ビニル樹脂層内に迅速に浸透させることができ、高融点のトリアジンを用いた場合と比較して大きな発泡抑制効果を得ることができる。 Therefore, in a transfer sheet using benzotriazole, triazole or the like having a low melting point of 160 ° C. or less as a foaming inhibitor, the foaming inhibitor is quickly put into the polyvinyl chloride resin layer as a transfer material before foaming starts. Compared with the case where a high melting point triazine is used, a large foam suppression effect can be obtained.
しかしながら、融点が低い発泡抑制剤を使用した場合には、転写シートの印刷形成後にブロッキングが発生し易く、転写シートの安定した品質での提供が困難であり、また発泡抑制効果が経時的に低下するため、転写シートとしての長期保存が困難であった。
本発明の課題は、安定して熱転写ができ、且つ被転写材としての発泡性樹脂の発泡時に、良好な発泡効果と、発泡する部分と発泡しない部分とに分ける十分な発泡抑制効果とを得ることができ、さらに長期保存が可能な転写シートを安定して提供することにある。 An object of the present invention is to obtain a satisfactory foaming effect and a sufficient foaming suppression effect that can be divided into a foaming part and a non-foaming part at the time of foaming of a foamable resin as a transfer material. Therefore, it is desirable to stably provide a transfer sheet that can be stored for a long period of time.
本発明の請求項１に係る発明は、紙若しくはオレフィン又は紙とオレフィンとを積層したシートからなる転写シート用の基材シート表面に、転写性を有し且つ被転写材の発泡に対する発泡抑制剤を添加した適宜パターンの発泡抑制インキ層を少なくとも１層具備し、前記発泡抑制剤として融点が１６０℃以上３００℃未満のカルボキシベンゾトリアゾール発泡抑制剤が添加されていることを特徴とする転写シートである。
The invention according to claim 1 of the present invention is a foam inhibitor for foaming of a transfer material having transferability on the surface of a base sheet for a transfer sheet made of paper or olefin or a sheet in which paper and olefin are laminated. A transfer sheet comprising at least one foam-reducing ink layer having an appropriate pattern to which a carboxybenzotriazole foaming inhibitor having a melting point of 160 ° C. or higher and lower than 300 ° C. is added as the foaming inhibitor. is there.
本発明の請求項２に係る発明は、上記請求項１に係る転写シートにおいて、前記発泡抑制インキ層中に、ポリビニルアルコール樹脂を含有する塩化ビニル−酢酸ビニル共重合体樹脂を含有することを特徴とする転写シートである。
The invention according to claim 2 of the present invention is the transfer sheet according to claim 1 , wherein the foaming suppression ink layer contains a vinyl chloride-vinyl acetate copolymer resin containing a polyvinyl alcohol resin. And a transfer sheet.
本発明の請求項３に係る発明は、上記請求項１又は２に係る転写シートにおいて、前記発泡抑制剤がアミンで中和されてアルコール溶解されていることを特徴とする転写シートである。
The invention according to claim 3 of the present invention is the transfer sheet according to claim 1 or 2 , wherein the foaming inhibitor is neutralized with an amine and dissolved in alcohol.
本発明の請求項４に係る発明は、上記請求項３に係る転写シートにおいて、前記アミンの沸点が、２００℃以下であることを特徴とする転写シートである。
The invention according to claim 4 of the present invention is the transfer sheet according to claim 3 , wherein the amine has a boiling point of 200 ° C. or less.
本発明の請求項５に係る発明は、上記請求項１乃至４のいずれか１項に係る転写シートにおいて、前記発泡抑制インキ層中に体質顔料が添加されていることを特徴とする転写シートである。
The invention according to claim 5 of the present invention is the transfer sheet according to any one of claims 1 to 4 , wherein an extender pigment is added to the foam suppression ink layer. is there.
本発明の請求項６に係る発明は、上記請求項５に係る転写シートにおいて、前記体質顔料がシリカであることを特徴とする転写シートである。
The invention according to claim 6 of the present invention is the transfer sheet according to claim 5 , wherein the extender pigment is silica.
本発明の請求項７に係る発明は、上記請求項１乃至６のいずれか１項に係る転写シートにおいて、前記発泡抑制剤が、発泡抑制インキ層中に５〜５０重量％の範囲で添加されていることを特徴とする転写シートである。
The invention according to claim 7 of the present invention is the transfer sheet according to any one of claims 1 to 6 , wherein the foaming inhibitor is added in a range of 5 to 50% by weight in the foaming suppression ink layer. It is the transfer sheet characterized by the above-mentioned.
本発明の請求項８に係る発明は、上記請求項１乃至７のいずれか１項に係る転写シートにおける発泡抑制インキ層の形成に用いられる発泡抑制インキとしてのインキ組成物であって、熱転写性のあるインキ中に発泡抑制剤が添加されていることを特徴とするインキ組成物である。 The invention according to claim 8 of the present invention is an ink composition as a foam suppression ink used for forming a foam suppression ink layer in the transfer sheet according to any one of claims 1 to 7 , wherein the thermal transferability An ink composition characterized in that a foaming inhibitor is added to a certain ink.
本発明の転写シートは、安定して熱転写ができ、且つ被転写材としての熱発泡性のポリ塩化ビニル樹脂の熱発泡時における発泡抑制インキの影響しない部分の良好な発泡効果と、発泡抑制インキの影響する部分における十分な発泡抑制効果とを得ることができ、発泡する部分と発泡しない部分とによる良好な凹凸発泡成形が可能になり、さらに本発明によって改良された発泡抑制インキの使用により、耐ブロッキング性のある、しかも長期保存が可能な転写シートを安定して提供することが可能になる。 The transfer sheet of the present invention is capable of stable thermal transfer, and has a good foaming effect at a portion not affected by the foam-suppressing ink at the time of thermal foaming of a heat-foamable polyvinyl chloride resin as a transfer material, and a foam-suppressing ink Sufficient foam suppression effect in the part affected by, can be good uneven foam molding by the foaming part and non-foaming part, and further by using the foam suppression ink improved by the present invention, It is possible to stably provide a transfer sheet having anti-blocking properties and capable of long-term storage.
本発明の転写シートを、発明の実施の形態に沿って以下に詳細に説明すれば、図１は本発明の転写シートの積層断面図であり、転写シート用の基材シート３の表面に、該印刷基材シート３面に対して熱転写性（熱剥離性）の発泡抑制インキ層４が凹凸パターンに対応する適宜パターン状に形成されている。 The transfer sheet of the present invention will be described in detail below according to an embodiment of the present invention. FIG. 1 is a cross-sectional view of the transfer sheet of the present invention, on the surface of the substrate sheet 3 for transfer sheet, A thermal transferable (thermally peelable) foam-suppressing ink layer 4 is formed in an appropriate pattern corresponding to the uneven pattern on the surface of the printing substrate sheet 3.
該発泡抑制インキ層４の表面には、化粧柄や彩色などの柄インキ層５が形成され、該柄インキ層５の表面の全面には、隠蔽層６が形成されている。 A pattern ink layer 5 such as a decorative pattern or a color is formed on the surface of the foam suppression ink layer 4, and a concealing layer 6 is formed on the entire surface of the pattern ink layer 5.
前記基材シート３は、図１に示すように用紙層１の表面にオレフィンとしてオレフィン系樹脂層２をラミネート又はコーティングした積層材料であってもよいし、用紙層１単体あるいはオレフィン系樹脂層２単体であってもよい。 The base sheet 3 may be a laminated material obtained by laminating or coating an olefin resin layer 2 as an olefin on the surface of the paper layer 1 as shown in FIG. 1, or the paper layer 1 alone or the olefin resin layer 2. It may be a simple substance.
発泡抑制インキ層４は、基材シート３の表面（用紙層１表面、又はオレフィン系樹脂層２表面）に対して、熱転写性を有するインキを用いて形成されており、このインキ中には、被転写材である発泡性のポリ塩化ビニル樹脂の発泡に対する発泡抑制効果を得るための発泡抑制剤が添加されている。
発泡に対する発泡抑制剤としては、融点が１６０℃以上３００℃未満のカルボキシベンゾトリアゾールが用いられ、カルボキシベンゾトリアゾールの添加量としては、当該発泡抑制インキ中５〜５０重量％であることが好ましい。
The foam suppression ink layer 4 is formed using an ink having a thermal transfer property with respect to the surface of the base sheet 3 (the surface of the paper layer 1 or the surface of the olefin resin layer 2). A foaming inhibitor is added to obtain a foaming inhibiting effect on foaming of the foamable polyvinyl chloride resin that is the transfer material.
As the foaming inhibitor for foaming, carboxybenzotriazole having a melting point of 160 ° C. or more and less than 300 ° C. is used, and the addition amount of carboxybenzotriazole is preferably 5 to 50% by weight in the foaming suppression ink.
さらに、当該発泡抑制インキ中のカルボキシベンゾトリアゾールは、溶解性を向上させるためにアミン中和し、アルコールで溶解させることが好ましく、当該アミンの沸点は２００℃以下であることがさらに好ましい。 Furthermore, the carboxybenzotriazole in the foam-suppressing ink is preferably neutralized with an amine to improve the solubility and dissolved with an alcohol, and the boiling point of the amine is more preferably 200 ° C. or lower.
また、発泡抑制インキ中には、被転写剤であるポリ塩化ビニル樹脂への熱転写性を確保するために、塩化ビニル−酢酸ビニル共重合体樹脂とアクリル樹脂を主成分としたインキを使用することが好ましく、アクリル樹脂の添加量は、当該発泡抑制インキ中１〜３０重量％、塩化ビニル−酢酸ビニル共重合体樹脂の添加量は、当該発泡抑制インキ中１〜３０重量％であることが好ましい。 In addition, in the foam suppression ink, in order to ensure thermal transfer to the polyvinyl chloride resin, which is the transfer agent, use an ink mainly composed of vinyl chloride-vinyl acetate copolymer resin and acrylic resin. The addition amount of the acrylic resin is preferably 1 to 30% by weight in the foam suppression ink, and the addition amount of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by weight in the foam suppression ink. .
さらに、発泡抑制インキ中の体質顔料シリカの含有量は、当該発泡抑制インキ中１〜１０％であることが好ましい。 Furthermore, the content of the extender silica in the foam suppression ink is preferably 1 to 10% in the foam suppression ink.
柄インキ層５は、例えば住宅、店舗等の建築物や、電車、自動車等の車両や、飛行機、船舶等の内装材や外装材、床材等の表面を化粧するための化粧柄や、模様、彩色、木目柄、目地、木目導管柄等が印刷により施されている。 The pattern ink layer 5 is, for example, a decorative pattern or pattern for making up the surface of a building such as a house or a store, a vehicle such as a train or an automobile, an interior material or exterior material such as an airplane or a ship, or a floor material. Coloring, wood grain pattern, joints, wood grain conduit pattern, etc. are printed.
隠蔽ベタ層６は、被転写材の被転写面を隠蔽するための隠蔽性のあるインキを用いて、柄インキ層５の上から印刷形成されている。 The concealing solid layer 6 is printed from above the pattern ink layer 5 using concealing ink for concealing the transfer surface of the transfer material.
本発明の転写シートの具体的実施例を、以下に詳細に説明する。 Specific examples of the transfer sheet of the present invention will be described in detail below.
用紙層１として、坪量５２．３ｇ／ｍ2 のフォーム印刷用紙（コンピュータ出力用紙）と、オレフィン系樹脂層２として厚さ２０μｍのポリプロピレン樹脂シートとを貼り合わせて、基材シート３を作成した。 A base sheet 3 was prepared by laminating a form printing paper (computer output paper) having a basis weight of 52.3 g / m 2 as the paper layer 1 and a polypropylene resin sheet having a thickness of 20 μm as the olefin resin layer 2. .
次に、前記基材シート３のポリプロピレン樹脂シート２上に、グラビアインキ中に発泡抑制剤を添加した熱転写性を有する発泡抑制インキを用いて、発泡抑制インキ層４として、グラビア印刷法にて１μｍ程度の印刷膜厚の目地導管柄のパターン印刷を施した。 Next, on the polypropylene resin sheet 2 of the base sheet 3, the foam suppression ink layer 4 is formed by using a gravure printing method using a foam suppression ink having a thermal transfer property in which a foam inhibitor is added to the gravure ink. The pattern printing of the joint conduit pattern with a printing film thickness of about a degree was performed.
発泡抑制インキ層４の形成に使用した上記発泡抑制インキは、被転写材であるポリ塩化ビニル樹脂への熱転写性を確保するために、塩化ビニル−酢酸ビニル共重合耐樹脂とアクリル樹脂を主成分としたインキを使用し、該インキ中に発泡抑制剤として融点が２６８℃
のカルボキシルベンゾトリアゾール１０重量％を添加した。
The foam suppression ink used for forming the foam suppression ink layer 4 is mainly composed of a vinyl chloride-vinyl acetate copolymer-resistant resin and an acrylic resin in order to ensure thermal transfer to a polyvinyl chloride resin as a transfer material. The melting point is 268 ° C. as a foam inhibitor in the ink.
10% by weight of carboxylic benzotriazole was added.
また、上記発泡抑制インキには、ポリビニルアルコール樹脂を添加し、水分に対して不安定な発泡抑制インキ中のカルボキシルベンゾトリアゾールの−ＯＨ基を安定化させた。 Moreover, polyvinyl alcohol resin was added to the said foam suppression ink, and -OH group of the carboxyl benzotriazole in the foam suppression ink unstable with respect to moisture was stabilized.
また、発泡抑制インキ中のカルボキシルベンゾトリアゾールは、メチルエチルケトンや酢酸エチル等のグラビアインキ用の有機溶剤（希釈溶剤）に溶け難いため、溶解性を向上させるためにアミンで中和し、アルコールで溶解させた。 In addition, carboxyl benzotriazole in foam suppression ink is difficult to dissolve in organic solvents (dilution solvents) for gravure inks such as methyl ethyl ketone and ethyl acetate, so neutralize with amine and dissolve with alcohol to improve solubility. It was.
使用したアミンは、発泡抑制インキの熱転写性を考慮して、炭素数が短く、沸点が低い（１６２℃）ジエチルエタノールアミンを使用した。さらに、アミン独特のタックを切るために体質顔料としてシリカを添加した。 As the amine used, diethyl ethanolamine having a short carbon number and a low boiling point (162 ° C.) was used in consideration of the thermal transfer properties of the foam-suppressing ink. Further, silica was added as an extender pigment to cut off the tack unique to amines.
次に、前記発泡抑制インキ層４上に被転写材であるポリ塩化ビニル樹脂への転写性を確保するため、塩化ビニル−酢酸ビニル共重合体樹脂とアクリル樹脂を主成分とした無機顔料を含むインキによる木目柄の印刷層をグラビア印刷法にて施して柄インキ層５を形成した。 Next, in order to ensure transferability to the polyvinyl chloride resin which is a transfer material on the foam suppression ink layer 4, an inorganic pigment mainly composed of a vinyl chloride-vinyl acetate copolymer resin and an acrylic resin is included. The print pattern of the wood grain pattern by ink was given by the gravure printing method, and the pattern ink layer 5 was formed.
そして、最後に、柄インキ層５上に隠蔽層６を施して、図１に示すような本発明の転写シートを作成した。 Finally, a concealing layer 6 was applied on the pattern ink layer 5 to produce a transfer sheet of the present invention as shown in FIG.
作成した本発明の上記転写シートを、被転写材である熱発泡性のポリ塩化ビニル樹脂基材面に被覆して、２００℃の転写ロールを用いて加熱加圧した後、基材シート３を剥離して、目地導管柄の発泡抑制インキ層４、木目柄の柄インキ層５、全面ベタ状の隠蔽層６をポリ塩化ビニル樹脂基材面に熱転写した。 The prepared transfer sheet of the present invention is coated on the surface of a heat-foamable polyvinyl chloride resin base material to be transferred, and heated and pressurized using a 200 ° C. transfer roll, and then the base sheet 3 is After peeling, the joint conduit pattern foam suppression ink layer 4, the wood pattern handle ink layer 5, and the entire solid hiding layer 6 were thermally transferred onto the surface of the polyvinyl chloride resin substrate.
その後、目地導管柄の発泡抑制インキ層４、木目柄の柄インキ層５、全面ベタ状の隠蔽層６を転写したポリ塩化ビニル樹脂基材を、２２０℃のオーブンで１００秒間放置して加熱発泡処理し、発泡抑制インキ層４の形成された部分の発泡の抑制効果を確認したところ、発泡抑制インキ層４の形成されていない部分の発泡厚さに対して発泡抑制インキ層４の形成された部分の発泡厚さは、０．５ｍｍ程度抑制され、発泡抑制効果が確認できた。 After that, the polyvinyl chloride resin base material to which the joint duct pattern foaming suppression ink layer 4, the wood grain pattern ink layer 5, and the entire solid hiding layer 6 were transferred was left in an oven at 220 ° C. for 100 seconds to be heated and foamed. The foaming suppression ink layer 4 was formed with respect to the foaming thickness of the part where the foaming suppression ink layer 4 was not formed. The foam thickness of the part was suppressed by about 0.5 mm, and the foam suppression effect could be confirmed.
作成した本発明の上記転写シートを２〜３枚程度重ね合わせ、そのシート上より、４０℃の環境下で１ｋｇ／ｃｍ2 の荷重を掛け、２４時間放置した後、転写シートのブロッキング発生状態を確認したところ、発泡抑制インキ層４の基材シート３裏面への転移は知見されなかった。 About 2 to 3 of the prepared transfer sheets of the present invention are superposed, and a load of 1 kg / cm 2 is applied to the transfer sheet in an environment of 40 ° C. and left to stand for 24 hours. When confirmed, the transition to the back surface of the base material sheet 3 of the foam suppression ink layer 4 was not found.
作成した本発明の上記転写シートを、６０℃の環境下で７日間放置した後、その転写シートを用いて、熱発泡性のポリ塩化ビニル樹脂基材面に被覆して、２００℃の転写ロールを用いて加熱加圧した後、基材シート３を剥離して、目地導管柄の発泡抑制インキ層４、木目柄の柄インキ層５、全面ベタ状の隠蔽層６をポリ塩化ビニル樹脂基材面に熱転写した。 The prepared transfer sheet of the present invention was allowed to stand for 7 days in an environment of 60 ° C., and then the transfer sheet was used to coat the surface of a heat-foamable polyvinyl chloride resin base material to form a 200 ° C. transfer roll. After heating and pressurizing, the base material sheet 3 is peeled off, and the joint conduit pattern foam suppression ink layer 4, wood grain pattern ink layer 5, and the entire solid hiding layer 6 are coated with a polyvinyl chloride resin base material. Thermally transferred to the surface.
その後、目地導管柄の発泡抑制インキ層４、木目柄の柄インキ層５、全面ベタ状の隠蔽層６を転写したポリ塩化ビニル樹脂基材を、２２０℃のオーブンで１００秒間放置して加熱発泡処理し、発泡抑制インキ層４の形成された部分の発泡の抑制効果を確認したところ、発泡抑制インキ層４の形成されていない部分の発泡厚さに対して発泡抑制インキ層４の形成された部分の発泡厚さは、実施例１の場合と同様に、０．５ｍｍ程度抑制され、経時
的な発泡抑制効果の持続性が確認できた。
After that, the polyvinyl chloride resin base material to which the joint conduit pattern foam suppression ink layer 4, the wood grain pattern ink layer 5 and the solid cover layer 6 are transferred is left in an oven at 220 ° C. for 100 seconds to be heated and foamed. The foaming suppression ink layer 4 was formed with respect to the foaming thickness of the part where the foaming suppression ink layer 4 was not formed. The foam thickness of the part was suppressed by about 0.5 mm as in the case of Example 1, and the sustainability of the foam suppression effect over time could be confirmed.
上記実施例１において、インキ中に発泡抑制剤として融点が２６８℃のカルボキシルベンゾトリアゾール２０重量％を添加した発泡抑制インキを使用した以外は、上記実施例１と同様にして本発明の転写シートを作成し、上記実施例２、３と同様にして、転写シートのブロッキング発生状態と、発泡抑制インキ層４の形成された部分の発泡の抑制効果を確認したところ、同様の耐ブロッキング性と発泡抑制効果を得ることができた。 In Example 1 above, the transfer sheet of the present invention was prepared in the same manner as in Example 1 above, except that the foam-suppressing ink added with 20% by weight of carboxyl benzotriazole having a melting point of 268 ° C. was used as the foam inhibitor in the ink. The same blocking resistance and suppression of foaming were confirmed when the blocking occurrence state of the transfer sheet and the suppression effect of foaming of the portion where the foaming suppression ink layer 4 was formed were confirmed in the same manner as in Examples 2 and 3 above. The effect was able to be acquired.
＜比較例１＞
上記実施例１において、発泡抑制インキに添加する発泡抑制剤として融点が１５１℃のトリアゾールを使用した以外は、上記実施例１と同様にして、比較例１の転写シートを作成し、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、発泡抑制効果の持続性はほとんど知見されなかった。
<Comparative Example 1>
In Example 1, a transfer sheet of Comparative Example 1 was prepared in the same manner as in Example 1 except that triazole having a melting point of 151 ° C. was used as the foam inhibitor added to the foam suppression ink. In the same manner as above, when the persistence of the foaming suppression effect over time was confirmed, the persistence of the foaming suppression effect was hardly found.
＜参考例１＞
上記実施例１において、発泡抑制インキにポリビニルアルコール樹脂を添加しない以外は上記実施例１と同様にして参考例１の転写シートを作成した。この転写シートについて、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、実施例１の転写シートと同等の結果であった。但し、発泡抑制インキ中の発泡抑制剤が、発泡抑制インキの印刷運転中に沈澱し易く、安定してグラビア印刷を行なうことが困難であった。
<Reference Example 1>
In Example 1, a transfer sheet of Reference Example 1 was prepared in the same manner as in Example 1 except that no polyvinyl alcohol resin was added to the foam suppression ink. With respect to this transfer sheet, in the same manner as in Example 3, when the persistence of the foaming suppression effect with time was confirmed, the result was the same as that of the transfer sheet of Example 1. However, the foam inhibitor in the foam suppression ink tends to precipitate during the printing operation of the foam suppression ink, and it has been difficult to stably perform gravure printing.
＜参考例２＞
上記実施例１において、発泡抑制剤をアミンで溶解せず、そのまま添加した発泡抑制インキを使用した以外は、上記実施例１と同様にして、参考例２の転写シートを作成した。この転写シートについて、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、実施例１の転写シートと同等の結果であった。但し、発泡抑制インキ中の発泡抑制剤が、発泡抑制インキの印刷運転中に沈澱し易く、安定してグラビア印刷を行なうことが困難であった。
<Reference Example 2>
In Example 1 above, a transfer sheet of Reference Example 2 was prepared in the same manner as in Example 1 except that the foam inhibitor was not dissolved with an amine, and the foam suppression ink added as it was was used. With respect to this transfer sheet, in the same manner as in Example 3, when the persistence of the foaming suppression effect with time was confirmed, the result was the same as that of the transfer sheet of Example 1. However, the foam inhibitor in the foam suppression ink tends to precipitate during the printing operation of the foam suppression ink, and it has been difficult to stably perform gravure printing.
＜参考例３＞
上記実施例１において、発泡抑制剤をアミンとして炭素数が長く２８１℃の高融点のアルキドアミンで溶解して添加した発泡抑制インキを使用した以外は、上記実施例１と同様にして、参考例３の転写シートを作成した。この転写シートについて、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、実施例１の転写シートと同等の結果であった。但し、熱転写時に発泡抑制インキ層の塗膜にアミンが残留してしまい、結果として発泡抑制インキ層には、アミン独特のタックが残ってしまう結果となったため、安定した熱転写性が得られず、熱転写を安定して行うことが困難であった。
<Reference Example 3>
In Example 1 above, Reference Example was used in the same manner as in Example 1 above, except that the foam inhibitor used as the foam inhibitor was amine and dissolved and added with a high melting point alkydamine having a high melting point of 281 ° C. 3 transfer sheets were prepared. With respect to this transfer sheet, in the same manner as in Example 3, when the persistence of the foaming suppression effect with time was confirmed, the result was the same as that of the transfer sheet of Example 1. However, amine remains in the coating film of the foam suppression ink layer at the time of thermal transfer, and as a result, an amine-specific tack remains in the foam suppression ink layer, so stable thermal transferability cannot be obtained, It was difficult to perform thermal transfer stably.
＜参考例４＞
上記実施例１において、体質顔料を全く添加しない発泡抑制インキを使用した以外は、上記実施例１と同様にして、参考例４の転写シートを作成した。この転写シートについて、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、実施例１の転写シートと同等の結果であった。但し、グラビア印刷直後の発泡抑制インキ層の塗膜表面にタックが発生し、印刷機のロール等への付着が発生し易く、安定して転写シートを印刷作成することが困難であった。
<Reference Example 4>
In Example 1, a transfer sheet of Reference Example 4 was prepared in the same manner as in Example 1 except that the foam suppression ink to which no extender was added was used. With respect to this transfer sheet, in the same manner as in Example 3, when the persistence of the foaming suppression effect with time was confirmed, the result was the same as that of the transfer sheet of Example 1. However, tack is generated on the surface of the coating film of the foam suppression ink layer immediately after gravure printing, and adhesion to a roll or the like of a printing press is likely to occur, making it difficult to stably print and produce a transfer sheet.
＜参考例５＞
上記実施例１において、体質顔料として硫酸バリウムを添加した発泡抑制インキを使用した以外は、上記実施例１と同様にして、参考例５の転写シートを作成した。この転写シ
ートについて、実施例３と同様にして、経時的な発泡抑制効果の持続性を確認したところ、実施例１の転写シートと同等の結果であった。但し、発泡抑制インキのグラビア印刷中に、発泡抑制インキが版のセルに詰まり易く、安定して転写シートを印刷作成することが困難であった。
<Reference Example 5>
In Example 1, a transfer sheet of Reference Example 5 was prepared in the same manner as in Example 1 except that the foam suppression ink added with barium sulfate as the extender was used. With respect to this transfer sheet, in the same manner as in Example 3, when the persistence of the foaming suppression effect with time was confirmed, the result was the same as that of the transfer sheet of Example 1. However, during the gravure printing of the foam-suppressing ink, the foam-suppressing ink easily clogs the plate cells, and it is difficult to stably print and produce a transfer sheet.
１…用紙 ２…オレフィン樹脂 ３…基材シート ４…発泡抑制インキ層
５…柄インキ層 ６…隠蔽層
DESCRIPTION OF SYMBOLS 1 ... Paper 2 ... Olefin resin 3 ... Base material sheet 4 ... Foam suppression ink layer 5 ... Pattern ink layer 6 ... Concealment layer
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