JP5092092B2 - Ink ribbon for metallic glossy thermal transfer - Google Patents
Ink ribbon for metallic glossy thermal transfer Download PDFInfo
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- JP5092092B2 JP5092092B2 JP2008169730A JP2008169730A JP5092092B2 JP 5092092 B2 JP5092092 B2 JP 5092092B2 JP 2008169730 A JP2008169730 A JP 2008169730A JP 2008169730 A JP2008169730 A JP 2008169730A JP 5092092 B2 JP5092092 B2 JP 5092092B2
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- 238000012546 transfer Methods 0.000 title claims description 62
- 239000010410 layer Substances 0.000 claims description 77
- 238000007740 vapor deposition Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000008119 colloidal silica Substances 0.000 claims description 10
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- 238000000034 method Methods 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 10
- 238000005034 decoration Methods 0.000 description 7
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
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- 239000011859 microparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Decoration By Transfer Pictures (AREA)
Description
成型同時加飾法（インモールド転写）、ホットスタンピング加飾法に使用される転写フィルムに金属光沢パターンを印刷するための金属光沢熱転写用インクリボンに関する。 The present invention relates to an ink ribbon for metallic gloss thermal transfer for printing a metallic gloss pattern on a transfer film used in a simultaneous molding decoration method (in-mold transfer) and a hot stamping decoration method.
近年、携帯電話、ノートパソコンなどの個人向け電子機器でデザインの差別化を図る傾向がある。これらデザインの加飾工法として、成型同時加飾法（インモールド転写）、ホットスタンピング加飾法が良く知られている。インモールド転写は、射出成型金型内に転写フィルムを送り込み、フィルムの接着側に溶融樹脂を注入することで樹脂の溶融温度と射出圧力を利用して成型と同時に絵柄を転写する技術である。成型と加飾の2つの工程を一括しておこなえるうえに成型後のトリミング等も不要であるなど生産性が高い特徴がある。また、ホットスタンピング加飾法は、樹脂成型完了物へ転写フィルムを重ね合わせ、ホットロール等にて加熱、加圧し、転写フィルムから絵柄層を樹脂成型物に転写する技術である。また、インモールド転写フィルムおよびホットスタンピング転写フィルムへの絵柄層の印刷は、従来グラビア印刷、シルクスクリーン印刷等を用いていたが、デザインの差別化から小ロット印刷が可能な方法として、熱転写プリンターにより絵柄形成を行う方法が広がりを見せている。本発明は、熱転写プリンターにて絵柄パターンを形成する為に用いるインクリボンであって特に金属光沢パターンを形成する為に用いるインクリボンに関し、特に上述のインモールド転写フィルムおよびホットスタンピング転写フィルムに熱転写プリンターにて金属光沢パターンを形成する為に好ましく用いられるインクリボンに関する。
従来、熱転写プリンターにて金属光沢パターンを形成する為に用いるインクリボンは、裏面に耐熱処理を施したＰＥＴフィルム基材上に離型層、蒸着アンカー層、金属蒸着層、接着層からなる構成をとっている。（特許文献１、２）しかし、従来のインクリボンは、蒸着アンカー層と金属蒸着層との界面における層間強度が弱い為、特にインモールド転写フィルム、ホットスタンピング転写フィルムに熱転写プリンターで金属光沢パターンを熱転写して形成した転写フィルムで、成型物への加飾を行った際、金属光沢パターン部が剥離し、離脱しやすい問題があった。
In recent years, there has been a tendency to differentiate designs in personal electronic devices such as mobile phones and laptop computers. As a design method for these designs, a simultaneous molding method (in-mold transfer) and a hot stamping method are well known. In-mold transfer is a technique in which a transfer film is fed into an injection mold and a molten resin is injected onto the adhesive side of the film to transfer a pattern simultaneously with molding using the melting temperature and injection pressure of the resin. The two processes, molding and decoration, can be performed at once, and trimming after molding is not necessary. The hot stamping decoration method is a technique in which a transfer film is superimposed on a resin molded product, heated and pressurized with a hot roll or the like, and a pattern layer is transferred from the transfer film to the resin molded product. In addition, gravure printing, silk screen printing, etc. were conventionally used to print the image layer on the in-mold transfer film and hot stamping transfer film. However, as a method that enables small lot printing due to design differentiation, a thermal transfer printer can be used. The method of pattern formation is spreading. The present invention relates to an ink ribbon that is used to form a picture pattern in a thermal transfer printer, and particularly to an ink ribbon that is used to form a metallic gloss pattern, and more particularly to the above-described in-mold transfer film and hot stamping transfer film. The present invention relates to an ink ribbon preferably used for forming a metallic gloss pattern.
Conventionally, an ink ribbon used to form a metallic gloss pattern with a thermal transfer printer has a structure comprising a release layer, a vapor deposition anchor layer, a metal vapor deposition layer, and an adhesive layer on a heat resistant PET film substrate on the back surface. I'm taking it. (Patent Documents 1 and 2) However, since conventional ink ribbons have weak interlayer strength at the interface between the vapor deposition anchor layer and the metal vapor deposition layer, the metallic gloss pattern is applied to the in-mold transfer film and hot stamping transfer film by a thermal transfer printer. When a decorative film was decorated with a transfer film formed by thermal transfer, there was a problem that the metallic gloss pattern part was peeled off and easily detached.
インモールド転写フィルムやホットスタンピング転写フィルムへ熱転写プリンターにて金属光沢パターンを形成し、転写フィルムから成型物へ金属パターンを転写した際の金属光沢パターンの離脱が無い加飾を可能とする。
A metallic gloss pattern is formed on an in-mold transfer film or a hot stamping transfer film with a thermal transfer printer, and decoration without the separation of the metallic gloss pattern when the metal pattern is transferred from the transfer film to a molded product is enabled.
金属光沢熱転写用インクリボンを基材から、離型層、熱硬化性樹脂と熱可塑性樹脂の混合物を主成分とする蒸着アンカー層、金属蒸着層、粒子径が５〜５０ｎｍの範囲にあるコロイダルシリカを主成分とする中間層、接着層の構成とする。
前記中間層がオルガノシリカゾルを塗布乾燥して形成する。
より好ましくは、中間層のコロイダルシリカの配合比率が７０重量％以上であることを特徴とする。
Metal gloss thermal transfer ink ribbon from base material, release layer, vapor deposition anchor layer composed mainly of a mixture of thermosetting resin and thermoplastic resin , metal vapor deposition layer, colloidal silica with particle diameter in the range of 5-50 nm It is set as the structure of the intermediate | middle layer and adhesive layer which have as a main component.
The intermediate layer is formed by applying and drying an organosilica sol.
More preferably, the compounding ratio of the colloidal silica in the intermediate layer is 70% by weight or more.
本発明の金属光沢熱転写用インクリボンを用いることによって、インモールド転写フィルムやホットスタンピング転写フィルムへ熱転写プリンターにて金属光沢パターンを形成し、転写フィルムから成型物へ金属パターンを転写した際の金属光沢パターンの離脱が無い加飾が得られた。 By using the metallic gloss thermal transfer ink ribbon of the present invention, a metallic gloss pattern is formed on an in-mold transfer film or a hot stamping transfer film with a thermal transfer printer, and the metallic gloss is transferred from the transfer film to a molded product. A decoration without pattern separation was obtained.
本発明の金属光沢熱転写用インクリボンは、その構成を少なくとも基材から、離型層、蒸着アンカー層、金属蒸着層、コロイダルシリカを主成分とする中間層、接着層とする。
基材としては、裏面に耐熱処理を施した基材を用いる。基材材料としては各種耐熱フィルムが使用できるが、コスト、強度のバランスからＰＥＴフィルムが好ましい。基材厚みとしては、２〜１２μｍの範囲のものが使用でき、特に２．５〜６μｍが強度と熱伝導性から好ましい。
The metallic gloss thermal transfer ink ribbon of the present invention is composed of at least a base material, a release layer, a vapor deposition anchor layer, a metal vapor deposition layer, an intermediate layer mainly composed of colloidal silica, and an adhesive layer.
As a base material, the base material which heat-processed on the back surface is used. Various heat-resistant films can be used as the base material, but a PET film is preferred from the balance of cost and strength. As the thickness of the base material, those in the range of 2 to 12 μm can be used, and 2.5 to 6 μm is particularly preferable from the viewpoint of strength and thermal conductivity.
次に離型層としては、例えば、エポキシ樹脂、アクリル系樹脂、セルロース系樹脂、ポリエステル系樹脂、熱可塑性ウレタン系樹脂、或いは、塩素化ポリエチレン、塩素化ポリプロピレン、等の変性オレフィン系樹脂、或いは、酢酸ビニル樹脂、塩化ビニル−酢酸ビニル共重合体、ブチラール樹脂等のビニル系樹脂を、１種又は２種以上混合使用することができる。
なお、例えば上記アクリル系樹脂は、そのモノマーとして、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸−ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸−ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸−ｎ−アミル、（メタ）アクリル酸−ｎ−ヘキシル、（メタ）アクリル酸−ｎ−オクチル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸−２−クロルエチル、（メタ）アクリル酸−３−クロルプロピル等の（メタ）アクリル酸ハロゲン化アルキル、（メタ）アクルル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル等の水酸基を持つ（メタ）アクリル酸エステル、α−クロル（メタ）アクリル酸メチル、α−クロル（メタ）アクリル酸エチルなどのハロゲン化（メタ）アクリル酸エステル、（メタ）アクルル酸−１−クロル−２−ヒドロキシエチルなどの水酸基を持つα−アルキル（メタ）アクリル酸エステル、及び（メタ）アクリル酸グリシジル等の（メタ）アクリル系モノマーの１種又は２種以上からなる単独重合体又は共重合体である。なお、（メタ）アクリルとはアクリル又はメタクリルを意味する。離型層の厚みとしては、０．１〜２μｍの範囲が好ましい。
Next, as the release layer, for example, epoxy resin, acrylic resin, cellulose resin, polyester resin, thermoplastic urethane resin, modified olefin resin such as chlorinated polyethylene, chlorinated polypropylene, or the like, or One or a mixture of two or more vinyl resins such as vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, butyral resin can be used.
In addition, for example, the acrylic resin has, as its monomer, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (Meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-n-amyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-octyl, (meth) (Meth) acrylic acid alkyl esters such as lauryl acrylate, (meth) acrylic acid-2-chloroethyl, (meth) acrylic acid alkyl halides such as 3-chloropropyl, (meth) acrylic acid- (Meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, -Halogenated (meth) acrylates such as methyl chloro (meth) acrylate and α-chloro (meth) ethyl acrylate, and α-having hydroxyl groups such as (meth) acrylic acid-1-chloro-2-hydroxyethyl It is a homopolymer or copolymer composed of one or more of (meth) acrylic monomers such as alkyl (meth) acrylic acid esters and glycidyl (meth) acrylate. In addition, (meth) acryl means acryl or methacryl. The thickness of the release layer is preferably in the range of 0.1 to 2 μm.
次に蒸着アンカー層は、耐熱性の高い樹脂が好ましく使用でき、熱硬化性樹脂と熱可塑性樹脂の混合物を主成分とすることが特に好ましく、熱硬化性樹脂としては、ポリイソシアネートを用いることが好ましく、樹脂中に反応基を有する熱可塑性樹脂とポリイソシアネートとの反応硬化物としても、反応基を有さない熱可塑性樹脂との混合物としてもよい。熱可塑性樹脂としては、例えば、エポキシ樹脂、アクリル系樹脂、セルロース系樹脂、ポリエステル系樹脂、熱可塑性ウレタン系樹脂、或いは、塩素化ポリエチレン、塩素化ポリプロピレン、等の変性オレフィン系樹脂、或いは、酢酸ビニル樹脂、塩化ビニル−酢酸ビニル共重合体、ブチラール樹脂等のビニル系樹脂を、１種又は２種以上混合使用することができる。 Next, as the vapor deposition anchor layer, a resin having high heat resistance can be preferably used, and it is particularly preferable to use a mixture of a thermosetting resin and a thermoplastic resin as a main component, and polyisocyanate is used as the thermosetting resin. Preferably, it may be a reaction cured product of a thermoplastic resin having a reactive group in the resin and a polyisocyanate, or a mixture of a thermoplastic resin having no reactive group. Examples of the thermoplastic resin include epoxy resins, acrylic resins, cellulose resins, polyester resins, thermoplastic urethane resins, modified olefin resins such as chlorinated polyethylene and chlorinated polypropylene, or vinyl acetate. One or a mixture of two or more vinyl resins such as a resin, vinyl chloride-vinyl acetate copolymer, butyral resin can be used.
なお、例えば上記アクリル系樹脂は、そのモノマーとして、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸−ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸−ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸−ｎ−アミル、（メタ）アクリル酸−ｎ−ヘキシル、（メタ）アクリル酸−ｎ−オクチル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸−２−クロルエチル、（メタ）アクリル酸−３−クロルプロピル等の（メタ）アクリル酸ハロゲン化アルキル、（メタ）アクルル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピル等の水酸基を持つ（メタ）アクリル酸エステル、α−クロル（メタ）アクリル酸メチル、α−クロル（メタ）アクリル酸エチルなどのハロゲン化（メタ）アクリル酸エステル、（メタ）アクルル酸−１−クロル−２−ヒドロキシエチルなどの水酸基を持つα−アルキル（メタ）アクリル酸エステル、及び（メタ）アクリル酸グリシジル等の（メタ）アクリル系モノマーの１種又は２種以上からなる単独重合体又は共重合体である。なお、（メタ）アクリルとはアクリル又はメタクリルを意味する。蒸着アンカー層の厚みとしては、０．１〜２μｍの範囲が好ましい。 In addition, for example, the acrylic resin has, as its monomer, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (Meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-n-amyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-octyl, (meth) (Meth) acrylic acid alkyl esters such as lauryl acrylate, (meth) acrylic acid-2-chloroethyl, (meth) acrylic acid alkyl halides such as 3-chloropropyl, (meth) acrylic acid- (Meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, -Halogenated (meth) acrylates such as methyl chloro (meth) acrylate and α-chloro (meth) ethyl acrylate, and α-having hydroxyl groups such as (meth) acrylic acid-1-chloro-2-hydroxyethyl It is a homopolymer or copolymer composed of one or more of (meth) acrylic monomers such as alkyl (meth) acrylic acid esters and glycidyl (meth) acrylate. In addition, (meth) acryl means acryl or methacryl. As a thickness of a vapor deposition anchor layer, the range of 0.1-2 micrometers is preferable.
次に金属蒸着層の金属としてはアルミニウム、亜鉛、錫、ニッケル、クロム、インジュウム、銅、金、銀、チタン、などが、単体、混合物、合金として使用できる。なかでアルミニウム、錫、銅、インジュウムが特に好ましく使用できる。金属蒸着層は、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理蒸着法や化学蒸着法により形成できる。金属蒸着層の厚みは、１０〜１，０００Åの範囲が好ましい。 Next, as a metal of a metal vapor deposition layer, aluminum, zinc, tin, nickel, chromium, indium, copper, gold, silver, titanium, etc. can be used as a simple substance, a mixture, or an alloy. Of these, aluminum, tin, copper, and indium can be particularly preferably used. The metal vapor deposition layer can be formed by physical vapor deposition such as vacuum vapor deposition, sputtering, or ion plating, or chemical vapor deposition. The thickness of the metal vapor deposition layer is preferably in the range of 10 to 1,000 mm.
次に本発明の特徴である中間層について詳しく説明する。
中間層はコロイダルシリカを主成分とするものである。主成分とは、中間層中に５０重量％含有することを意味する。好ましくは、７０重量％以上とする。コロイダルシリカの粒子径は、５〜５０ｎｍ特に好ましくは、５〜２０ｎｍの範囲とする。基材上にコロイダルシリカを溶液に分散されたシリカゾルを塗布、乾燥させて中間層を形成することができる。シリカゾルの溶液には、塗布適正の観点から、有機溶媒にコロイダルシリカが分散されたオルガノシリカゾルを用いることがより好ましい。
Next, the intermediate layer, which is a feature of the present invention, will be described in detail.
The intermediate layer is mainly composed of colloidal silica. The main component means 50% by weight in the intermediate layer. Preferably, it is 70% by weight or more. The particle diameter of colloidal silica is 5 to 50 nm, particularly preferably 5 to 20 nm. An intermediate layer can be formed by applying a silica sol in which colloidal silica is dispersed in a solution onto a base material and drying it. For the silica sol solution, it is more preferable to use an organosilica sol in which colloidal silica is dispersed in an organic solvent from the viewpoint of proper coating.
オルガノシリカゾルとしては、有機溶剤の種類によりメタノールシリカゾル、イソプロパノールシリカゾル、ｎーブタノールシリカゾル、イソブタノールシリカゾル、エチレングリコールシリカゾル、キシレン・ブタノールシリカゾル、エチルセロソルブシリカゾル、ジメチルアセトアミドシリカゾル、メチルエチルケトンゾル等がある。 Examples of the organosilica sol include methanol silica sol, isopropanol silica sol, n-butanol silica sol, isobutanol silica sol, ethylene glycol silica sol, xylene / butanol silica sol, ethyl cellosolve silica sol, dimethylacetamide silica sol, and methyl ethyl ketone sol.
中間層には、適宜熱可塑性樹脂を少量加え、塗膜強度、レベリング性、塗布適正を調整しても良い。熱可塑性樹脂の添加量は、５０重量％未満とし、好ましくは３０％未満とする。 A small amount of a thermoplastic resin may be appropriately added to the intermediate layer to adjust the coating strength, leveling properties, and coating suitability. The addition amount of the thermoplastic resin is less than 50% by weight, preferably less than 30%.
中間層の厚みとしては、０．０５〜１．０μｍ程度が好ましい。０．０５μｍ未満では、アンカー層と金属蒸着層との層間強度が得られにくく、１．０μｍを超えると、感熱転写性が低下する。特に好ましい厚みとしては、０．０５〜０．５μｍ範囲とする。ここで、金属蒸着層の上にコロイダルシリカを主成分とする中間層を設けることにより、蒸着アンカー層と金属蒸着層との界面の層間強度が高くなる理由は、定かでない。しかし、転写フィルムに金属光沢パターンを本発明のインクリボンを使用して熱転写で形成したものをホットスタンプ機で成型樹脂（被転写体）に転写フィルムをあてがって転写層を転写して、基材フィルムを剥がしたときに、従来のインクリボンでは、金属蒸着層が剥がれるものが、本発明のインクリボンをした場合は金属蒸着層が剥がれることがないものである。 The thickness of the intermediate layer is preferably about 0.05 to 1.0 μm. If it is less than 0.05 μm, it is difficult to obtain an interlayer strength between the anchor layer and the metal vapor deposition layer, and if it exceeds 1.0 μm, the thermal transferability is lowered. A particularly preferable thickness is in the range of 0.05 to 0.5 μm. Here, the reason why the interlayer strength at the interface between the vapor deposition anchor layer and the metal vapor deposition layer is increased by providing an intermediate layer mainly composed of colloidal silica on the metal vapor deposition layer is not clear. However, a metallic gloss pattern formed on the transfer film by thermal transfer using the ink ribbon of the present invention is applied to the molding resin (transfer object) with a hot stamp machine, and the transfer layer is transferred to the substrate. When the film is peeled off, the conventional ink ribbon peels off the metal vapor-deposited layer, but when the ink ribbon of the present invention is used, the metal vapor-deposited layer does not peel off.
上記の説明では、問題視する剥がれは蒸着アンカー層と金属蒸着層の界面と述べたが、転写フィルムの層の構成や転写条件等によっては、剥がれる箇所が異なることがまれに出てくる。例えば、Ａ：離型層と蒸着アンカー層間や、Ｂ：従来インクリボンにおける接着層と金属蒸着層間がある。Ａの場合は、やはり金属蒸着層が剥がれる問題は、同じである。Ｂの場合は、金属蒸着層は、被転写体側に残るものの金属蒸着層の上に載っている層である接着層及び転写フィルムに元々備わっており、被転写体への転写時に転写された受像兼接着層、剥離保護層等の層が無くなり耐擦過性等が低下する問題が発生する。本発明のインクリボンを使用すればこのような問題が解消される。つまり、層間強度の向上は、蒸着アンカー層と金属蒸着層間のみならず他の層間強度の向上も可能とするものである。
本発明における接着層用の接着剤は、感熱接着剤であれば特に制限無く使用できる。たとえば、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、熱可塑性ウレタン系樹脂、アクリル系樹脂、塩化ビニル系樹脂、ポリビニルアルコール系樹脂、フェノール樹脂、エチレン-酢酸ビニル共重合体、スチレン−ブタジエンゴム、イソプレンゴムなどの樹脂やエラストマー類の１種又は２種以上を主成分とし、必要に応じてロジンやその誘導体、テルペン樹脂、石油系樹脂などのタッキファイヤー、可塑剤、酸化防止剤などを配合したものが使用できる。接着層のきれ向上や、耐ブロッキング性向上の為に、微粒子を配合しても良い。微粒子としては、シリカ、タルク、炭酸カルシウム、アルミナ、カーボンブラック、酸化チタン等が使用できる。接着層の厚みとしては、０．０５〜２．０μｍ程度が好ましい。
In the above description, the problem peeling is described as the interface between the vapor deposition anchor layer and the metal vapor deposition layer. However, depending on the configuration of the transfer film layer, the transfer conditions, and the like, the peeled portion is rarely different. For example, there are A: release layer and vapor deposition anchor layer, and B: adhesion layer and metal vapor deposition layer in the conventional ink ribbon. In the case of A, the problem that the metal deposition layer is peeled off is the same. In the case of B, the metal vapor deposition layer is originally provided in the adhesive layer and the transfer film, which are layers on the metal vapor deposition layer that remain on the transfer material side, and the image receiving image transferred at the time of transfer to the transfer material. There arises a problem that the layers such as the cum-adhesive layer and the peeling protective layer are lost and the scratch resistance is lowered. Such a problem can be solved by using the ink ribbon of the present invention. In other words, the improvement of the interlayer strength enables the improvement of not only the deposition anchor layer and the metal deposition layer but also the other interlayer strength.
If the adhesive for adhesive layers in this invention is a heat sensitive adhesive, it can be especially used without a restriction | limiting. For example, polyester resin, polyamide resin, epoxy resin, thermoplastic urethane resin, acrylic resin, vinyl chloride resin, polyvinyl alcohol resin, phenol resin, ethylene-vinyl acetate copolymer, styrene-butadiene rubber, isoprene rubber, etc. Mainly composed of one or more of these resins and elastomers, and if necessary, blended with rosin, derivatives thereof, terpene resins, petroleum resins and other tackifiers, plasticizers, antioxidants, etc. it can. You may mix | blend microparticles | fine-particles in order to improve the crack of an adhesive layer, and to improve blocking resistance. As fine particles, silica, talc, calcium carbonate, alumina, carbon black, titanium oxide and the like can be used. The thickness of the adhesive layer is preferably about 0.05 to 2.0 μm.
（実施例１）
１．金属光沢熱転写用インクリボンの作製
裏面に厚み０．１μｍの耐熱層を形成した厚さ６μｍのＰＥＴフィルムを基材として用いた。
離型層塗工液（重量％）
1. A 6 μm-thick PET film having a heat-resistant layer having a thickness of 0.1 μm formed on the back surface of the metal ribbon thermal transfer ink ribbon was used as a substrate.
Release layer coating liquid (wt%)
上記塗工液を基材に乾燥後塗布厚み０．６μｍにて塗布した。
蒸着アンカー層塗工液（重量％）
Deposition anchor layer coating solution (wt%)
蒸着アンカー層塗工液を離型層上にメイヤバーにて乾燥後塗布厚み０．６μｍにて塗布し、１００℃のオーブンにて１分間加熱し熱硬化させた。
次に真空蒸着法にてアルミニウムをその上に蒸着した。（蒸着厚み５００Å）
中間層塗工液１：オルガノシリカゾル（固形分２０％ＭＥＫ分散液）（日産化学工業製、ＭＥＫ−ＳＴ、以下で使用のオルガノシリカゾルも同じものを使用した。）
中間層塗工液１をアルミ蒸着層の上にメイヤバーにて乾燥後塗布厚み０．２μｍとなるように塗布し、中間層を形成した。
接着層塗工液（重量％）
Next, aluminum was deposited thereon by vacuum deposition. (Deposition thickness 500mm)
Intermediate layer coating solution 1: Organosilica sol (20% solid content MEK dispersion) (manufactured by Nissan Chemical Industries, MEK-ST, the same organosilica sol used below)
The intermediate layer coating solution 1 was applied on the aluminum vapor deposition layer with a Mayer bar so as to have a coating thickness of 0.2 μm, thereby forming an intermediate layer.
Adhesive layer coating solution (wt%)
さらにその上に接着層塗工液をメイヤバーにて乾燥後塗布厚み０．２μｍとなるように塗布し、金属光沢熱転写用インクリボン（１）を完成した。
２．転写フィルムの作製（ホットスタンプ加飾用）
厚さ２０μｍのＰＥＴフィルムを基材フィルムとして用いた。
剥離保護層塗工液（重量％）
Further, the adhesive layer coating solution was dried on a Mayer bar so as to have a coating thickness of 0.2 μm, thereby completing a metal gloss thermal transfer ink ribbon (1).
2. Production of transfer film (for hot stamp decoration)
A PET film having a thickness of 20 μm was used as a base film.
Peeling protective layer coating solution (wt%)
上記塗工液を基材に乾燥後塗布厚み２．０μｍにて塗布した。
受像兼接着層塗工液（重量％）
Image-receiving and adhesive layer coating solution (wt%)
その上に受像兼接着層塗工液をメイヤバーにて乾燥後塗布厚み０．２μｍなるように塗布し、転写フィルムを完成した。
（実施例２）
実施例１で中間層塗工液を中間層塗工液２とした以外は実施例１と同じ構成した。
中間層塗工液２（重量％）
(Example 2)
The configuration was the same as Example 1 except that the intermediate layer coating solution 2 was changed to the intermediate layer coating solution 2 in Example 1.
Intermediate layer coating solution 2 (wt%)
（比較例１）
実施例１で中間層の形成を除外した以外は、実施例１と同様のものとした。
（比較例２）
実施例１で中間層塗工液を中間層塗工液３とした以外は実施例１と同じ構成した。
中間層塗工液３（重量％）
(Comparative Example 1)
Example 1 was the same as Example 1 except that the formation of the intermediate layer was excluded.
(Comparative Example 2)
The configuration was the same as that of Example 1 except that the intermediate layer coating solution 3 was changed to the intermediate layer coating solution 3 in Example 1.
Intermediate layer coating solution 3 (wt%)
金属光沢熱転写用インクリボンの評価
熱転写プリンター解像度６００ｄｐｉのテストプリンターにて前記の転写フィルム上に上記熱転写用インクリボンをもちいて金属光沢パターンを形成した。
金属光沢がパターンニングされた転写フィルムを、ホットスタンプ機を用いて厚み３ｍｍの透明アクリルプレートにパターンを転写させた。（転写温度２４０℃、転写速度８０ｍｍ／ｓｅｃ）
以上により、アクリルプレートに金属光沢パターンを形成した評価用サンプルを作製した。
評価項目
１）密着性
転写した被転写体の表面をカッターナイフにて１．５ｍｍ角の碁盤目を１００マス刻み、セロテープ（ニチバンＣＴ−２４、セロテープのニチバンの登録商標）にて剥離テストを実施して、碁盤目の残個数を数えた。
２）光沢感
○：良好な金属光沢、△：ややくもりが見られる、×：くもりが見られる
３）印刷適正
２ｄｏｔのへアーラインの印字性能にて評価
○：良好なヘアーラインが得られた、△：ややかすれ部が見られる、×：かすれる
評価結果
Evaluation of Ink Ribbon for Metallic Glossy Thermal Transfer Printer A metallic gloss pattern was formed on the transfer film using the thermal transfer printer using a test printer with a resolution of 600 dpi.
The pattern was transferred to the transparent acrylic plate having a thickness of 3 mm from the transfer film patterned with metallic luster using a hot stamping machine. (Transfer temperature 240 ° C, Transfer speed 80mm / sec)
As described above, an evaluation sample in which a metallic gloss pattern was formed on an acrylic plate was produced.
Evaluation item 1) Adhesion-transferred surface of the transfer object is cut into 100 squares with a 1.5 mm square grid using a cutter knife, and a peel test is performed with cello tape (Nichiban CT-24, registered trademark of Nichiban of Cellotape). Then, the remaining number of grids was counted.
2) Glossiness ○: Good metallic luster, Δ: Slightly cloudy, ×: Cloudy is observed 3) Printability Evaluation by 2 dot hairline printing performance ○: Good hairline was obtained, Δ : Slightly faint part is seen, ×: Faint
Evaluation results
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008169730A JP5092092B2 (en) | 2008-06-30 | 2008-06-30 | Ink ribbon for metallic glossy thermal transfer |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008169730A JP5092092B2 (en) | 2008-06-30 | 2008-06-30 | Ink ribbon for metallic glossy thermal transfer |
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| JP2010005969A JP2010005969A (en) | 2010-01-14 |
| JP5092092B2 true JP5092092B2 (en) | 2012-12-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017057116A (en) * | 2015-09-16 | 2017-03-23 | 日東電工株式会社 | Sol liquid and method for producing the same, method for producing laminate film, laminate film, optical member, and image display device |
| JP6432486B2 (en) | 2015-11-04 | 2018-12-05 | ブラザー工業株式会社 | Thermal transfer ink ribbon, ribbon cartridge, and printing apparatus |
| JP6639293B2 (en) * | 2016-03-22 | 2020-02-05 | アルプスアルパイン株式会社 | Production method of printed matter |
| JP7115020B2 (en) * | 2018-04-27 | 2022-08-09 | 大日本印刷株式会社 | Method for manufacturing transfer sheet, decorative sheet, and method for manufacturing decorative article |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330288A (en) * | 1986-07-25 | 1988-02-08 | Toppan Printing Co Ltd | Metal gloss thermal transfer recording medium |
| JP2965594B2 (en) * | 1989-07-31 | 1999-10-18 | 日本写真印刷株式会社 | Transfer material |
| JP4080077B2 (en) * | 1998-11-19 | 2008-04-23 | フジコピアン株式会社 | Method for forming metallic gloss image |
| JP4139301B2 (en) * | 2003-09-24 | 2008-08-27 | 大日本印刷株式会社 | Thermal transfer sheet and printed matter |
| JP4542458B2 (en) * | 2005-03-30 | 2010-09-15 | 大日本印刷株式会社 | Protective layer thermal transfer sheet |
| JP4788210B2 (en) * | 2005-07-07 | 2011-10-05 | 凸版印刷株式会社 | Transfer foil |
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| JP2010005969A (en) | 2010-01-14 |
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