JP4192242B2 - Protective layer transfer sheet - Google Patents
Protective layer transfer sheet Download PDFInfo
- Publication number
- JP4192242B2 JP4192242B2 JP2004079436A JP2004079436A JP4192242B2 JP 4192242 B2 JP4192242 B2 JP 4192242B2 JP 2004079436 A JP2004079436 A JP 2004079436A JP 2004079436 A JP2004079436 A JP 2004079436A JP 4192242 B2 JP4192242 B2 JP 4192242B2
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- Prior art keywords
- protective layer
- resin
- transfer sheet
- acrylic
- transfer
- 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
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- 239000011241 protective layer Substances 0.000 title claims description 122
- 238000012546 transfer Methods 0.000 title claims description 84
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000012790 adhesive layer Substances 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 230000005865 ionizing radiation Effects 0.000 claims description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 230000000704 physical effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 46
- 239000011248 coating agent Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000758 substrate Substances 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 238000001723 curing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000011888 foil Substances 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000007756 gravure coating Methods 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
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Laminated Bodies (AREA)
Description
本発明は保護層転写シートに関し、さらに詳しくは熱転写方式により、プラスチック成形物や画像等に優れた耐久性を与える保護層転写シートに関する。
The present invention relates to a protective layer transfer sheet, and more particularly to a protective layer transfer sheet that gives excellent durability to a plastic molded product, an image, and the like by a thermal transfer method.
従来より、電子写真方式、インクジェット方式や熱転写方式等によって階調画像や文字、記号等の単調画像を形成することが行われている。このようにして得られた画像は、用いられる用途によっては耐傷性や耐溶剤性が必要とされることが多い。そこでこれらの画像を形成した後、保護層を画像の上から熱転写によりベタ印刷する（以後オーバープリントと呼ぶ）ことで堅牢性を向上させる手法により、低コストで簡便に画像を保護することができる。該オーバープリントは保護層を硬化させることによりさらに堅牢性を向上させることができる。保護層を硬化させるには熱もしくは電離放射線による硬化が一般的である（特許文献１）。熱硬化の場合は、転写フィルム状態において保護層をあらかじめ硬化させる。なぜなら熱硬化は一般的に時間がかかるため、転写後での熱処理はシステムの簡便性に劣るからである。また、画像形成物の熱変形等による不具合が生じることもある。 Conventionally, a monotonous image such as a gradation image, a character, or a symbol has been formed by an electrophotographic method, an inkjet method, a thermal transfer method, or the like. The image obtained in this way often requires scratch resistance and solvent resistance depending on the intended use. Therefore, after these images are formed, the protective layer is solid-printed by thermal transfer from the top of the image (hereinafter referred to as overprinting), whereby the image can be easily protected at a low cost by a technique for improving the robustness. . The overprint can be further improved in toughness by curing the protective layer. In order to cure the protective layer, curing by heat or ionizing radiation is generally used (Patent Document 1). In the case of heat curing, the protective layer is cured in advance in the transfer film state. This is because heat curing generally takes time, and heat treatment after transfer is inferior in system simplicity. In addition, a defect due to thermal deformation of the image formed product may occur.
一方、電離放射線硬化の場合は保護層を転写前に硬化させても転写後に硬化させてもよい。ところで上述のごとく、堅牢性を向上させるため、転写フィルム状態で保護層をあらかじめ硬化した場合、保護層の熱溶融性は著しく低下し箔切れ性が悪化する。その結果、エッジ部分等での保護層のキレ性が悪くなる（この現象を面状剥離と呼ぶ）。箔切れ性を良好に維持するためには、膜厚を薄くする必要があり、保護層の厚みはかなり制限される。よって高い堅牢性を得ることは困難である。 On the other hand, in the case of ionizing radiation curing, the protective layer may be cured before transfer or after transfer. By the way, as mentioned above, in order to improve the fastness, when the protective layer is previously cured in the transfer film state, the heat melting property of the protective layer is remarkably lowered and the foil breakability is deteriorated. As a result, the sharpness of the protective layer at the edge portion or the like deteriorates (this phenomenon is called planar peeling). In order to maintain the foil cutting property well, it is necessary to reduce the film thickness, and the thickness of the protective layer is considerably limited. Therefore, it is difficult to obtain high robustness.
転写後に電離放射線の照射によって保護層を硬化させる手法においては上記のような問題はないが、別の問題がある。電離放射線硬化樹脂は硬化前は通常タックがあり、熱転写シートのような巻物にはできない。このためセパレーターが必要になり（特許文献２）コストアップにつながる。また、このタックのため保護層の上にさらに接着層を積層することは困難となり、結局、保護層と接着のよい被着体にしか用いることができず汎用性に欠ける。 Although there is no problem as described above in the method of curing the protective layer by irradiation with ionizing radiation after transfer, there is another problem. The ionizing radiation curable resin usually has a tack before curing, and cannot be a roll like a thermal transfer sheet. For this reason, a separator is required (Patent Document 2), leading to an increase in cost. Further, due to this tack, it is difficult to further laminate an adhesive layer on the protective layer. Eventually, it can be used only for an adherend having good adhesion to the protective layer and lacks versatility.
本発明の課題は箔切れ性がよく、しかも硬化前にはタックがなくかつ、被接着体に対する接着性が高く、保護層が転写された被転写体は、耐溶剤性、耐水性、耐傷性、碁盤目テスト（ＪＩＳ Ｋ５４００）の密着性の優れたものとすることができる保護層転写シートを提供することである。 The subject of the present invention is good foil cutting property, and has no tack before curing, has high adhesion to the adherend, and the transfer subject to which the protective layer has been transferred has solvent resistance, water resistance and scratch resistance. An object of the present invention is to provide a protective layer transfer sheet that can have excellent adhesion in a cross-cut test (JIS K5400).
そこで、上記課題を解決するために下記に示す発明をするに至った。すなわち本発明の保護層転写シートは、基材上に少なくとも保護層および接着層を順に設けた保護層転写シートにおいて、その保護層が主成分として硬化性可能である樹脂を含有し、接着層の主成分としてアクリル変性ポリエステルウレタン樹脂を含有することを特徴とする。その保護層主成分である硬化可能な樹脂がアクリル系樹脂であり、さらに好ましくは、電離放射線照射による硬化が可能であるアクリル−シリカハイブリッド樹脂であり、該アクリル−シリカハイブリッド樹脂のシリカ成分は１５重量％以上６０重量％以下で、常温において硬化前にタックが無いことを特徴とする。さらに、硬化前のアクリル−シリカハイブリッド樹脂は３０℃以上のＴｇを持つことが好ましい。 Therefore, in order to solve the above-mentioned problems, the inventors have made the invention shown below. That is, the protective layer transfer sheet of the present invention is a protective layer transfer sheet in which at least a protective layer and an adhesive layer are provided in this order on a base material, and the protective layer contains a resin that can be cured as a main component. An acrylic modified polyester urethane resin is contained as a main component. The curable resin that is the main component of the protective layer is an acrylic resin, more preferably an acrylic-silica hybrid resin that can be cured by irradiation with ionizing radiation, and the silica component of the acrylic-silica hybrid resin is 15 It is characterized by having no tack before curing at room temperature and not more than 60% by weight. Furthermore, the acrylic-silica hybrid resin before curing preferably has a Tg of 30 ° C. or higher.
以下に、本発明の詳細についてさらに説明する。
図１は、本発明の保護層転写シートである一つの実施の形態を示す断面図であり、基材１の一方の面に保護層２と、接着層３をこの順に形成した構成である。図２は、本発明の保護層転写シートである他の実施の形態を示す断面図であり、基材１の一方の面に離型層４を設け、その上に保護層２と接着層３が順に設けられており、保護層の離型性をより高めた構成となっている。さらに、図３は、本発明の保護層転写シートである他の実施の形態を示す断面図であり、基材１の一方の面に耐熱滑性層５を有し、基材１の他方の面に離型層４を介して、保護層２と接着層３がこの順に設けられていて、基材への熱ダメージを緩和できる構成となっている。
The details of the present invention will be further described below.
FIG. 1 is a cross-sectional view showing an embodiment of a protective layer transfer sheet of the present invention, in which a protective layer 2 and an adhesive layer 3 are formed in this order on one surface of a substrate 1. FIG. 2 is a cross-sectional view showing another embodiment of the protective layer transfer sheet of the present invention, in which a release layer 4 is provided on one surface of the substrate 1, and the protective layer 2 and the adhesive layer 3 are provided thereon. Are provided in order, and have a structure in which the release property of the protective layer is further improved. Further, FIG. 3 is a cross-sectional view showing another embodiment of the protective layer transfer sheet of the present invention, which has a heat-resistant slipping layer 5 on one surface of the substrate 1 and the other of the substrate 1. The protective layer 2 and the adhesive layer 3 are provided in this order via the release layer 4 on the surface, so that thermal damage to the substrate can be alleviated.
以下に本発明の保護層転写シートを構成する各層の説明を行う。
本発明の保護層転写シートに用いられている基材１としては、従来の熱転写シートに使用されているものと同じ基材をそのまま用いることができると共に、シートの表面に易接着処理のしてあるものや、その他のものも使用することができ、特に制限はされない。
Hereinafter, each layer constituting the protective layer transfer sheet of the present invention will be described.
As the substrate 1 used in the protective layer transfer sheet of the present invention, the same substrate as that used in conventional thermal transfer sheets can be used as it is, and the surface of the sheet is subjected to an easy adhesion treatment. Some and others can be used and are not particularly limited.
好ましい基材の具体例としては、例えば、ポリエチレンテレフタレートを始めとするポリエステル、ポリカーボネート、ポリアミド、ポリイミド、酢酸セルロース、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリスチレン、フッ素樹脂、ポリプロピレン、ポリエチレン、アイオノマー等のプラスチックフィルム、及びグラシン紙、コンデンサー紙、パラフィン紙等の紙類、セロファン等があり、また、これらの２種以上を積層した複合フィルムなども使用できる。さらに、プラスチック成形物への転写を考慮する場合には、転写シートが成形物の形に添うように熱変形することが好ましく、易成形ＰＥＴやアクリルフィルム等、熱変形が容易な基材を使用するのが良い。これらの基材シートの厚さは、その強度及び耐熱性が適切になるように材料に応じて適宜変更しているが、通常は１．０〜１００μｍ程度が好ましい。 Specific examples of preferred substrates include, for example, polyester films such as polyethylene terephthalate, polycarbonate, polyamide, polyimide, cellulose acetate, polyvinylidene chloride, polyvinyl chloride, polystyrene, fluororesin, polypropylene, polyethylene, and ionomer. , And papers such as glassine paper, condenser paper, paraffin paper, cellophane, etc., and composite films in which two or more of these are laminated can also be used. Furthermore, when considering transfer to a plastic molded product, it is preferable that the transfer sheet is thermally deformed so that it conforms to the shape of the molded product, and a substrate that can be easily thermally deformed, such as easily molded PET or acrylic film, is used. Good to do. Although the thickness of these base material sheets is suitably changed according to material so that the intensity | strength and heat resistance may become appropriate, about 1.0-100 micrometers is preferable normally.
本発明の特徴である接着層は、保護層の被転写体への接着性を良好にする為に設け、保護層と被転写体の相方に接着性を示す必要が有る。この課題を解決する材料としてアクリル変性ポリエステルウレタン樹脂が見出された。このことから接着層の主成分としてアクリル変性ポリエステルウレタン樹脂を含有することを特徴とする。 The adhesive layer, which is a feature of the present invention, is provided in order to improve the adhesiveness of the protective layer to the transfer target, and it is necessary to show the adhesiveness between the protective layer and the transfer target. An acrylic-modified polyester urethane resin has been found as a material for solving this problem. From this, it is characterized by containing an acrylic-modified polyester urethane resin as a main component of the adhesive layer.
前記接着層は、被転写体が、アクリル系樹脂で出来た成形物や受像層がアクリル系樹脂で出来た各種プリンタ用の受像シートや、樹脂成形物にアクリル系インクで印刷層が設けられたものにおいて、特に強固に密着することが出きる。 The adhesive layer is a molded product made of an acrylic resin as a transfer target, an image receiving sheet for various printers whose image receiving layer is made of an acrylic resin, or a printing layer provided with an acrylic ink on a resin molded product. In particular, it is possible to make a particularly tight contact.
また、接着感度等を調整する意味で、前記樹脂以外にも熱可塑性樹脂を添加することができる。例えば、アクリル系樹脂、酢酸ビニル系樹脂、エポキシ系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ブチラール系樹脂、ゼラチン、セルロース系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、ウレタン系樹脂等の如く熱時接着性の良好な樹脂から、適当なガラス転移温度を有するものを選択する。又、添加剤として、紫外線吸収剤、着色顔料、白色顔料、体質顔料、充填剤、帯電防止剤、酸化防止剤、蛍光増白剤、染料等も適宜、必要に応じて使用することができる。 In addition, a thermoplastic resin can be added in addition to the above resin in order to adjust adhesion sensitivity and the like. For example, when heated, such as acrylic resin, vinyl acetate resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, gelatin, cellulose resin, polyamide resin, vinyl chloride resin, urethane resin, etc. A resin having an appropriate glass transition temperature is selected from resins having good adhesiveness. As additives, ultraviolet absorbers, colored pigments, white pigments, extender pigments, fillers, antistatic agents, antioxidants, fluorescent whitening agents, dyes, and the like can be used as necessary.
接着層の厚みは、好ましくは０．１〜１０μm、さらに好ましくは０．５〜５μmである。上記範囲未満では接着力が低くすぎるため保護層の接着性が劣り、上記範囲を超えると転写において箔切れ性が低下しやすい。 The thickness of the adhesive layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is less than the above range, the adhesive strength is too low, so the adhesiveness of the protective layer is inferior. If it exceeds the above range, the foil breakage tends to be lowered during transfer.
本発明の保護層転写シートは、基材上に保護層が設けられている。該保護層は、少なくとも１層からなり、電離放射線照射により硬化したり、または熱硬化して、耐溶剤性、耐水性や耐傷性が得られるようになる。上記耐性を得るためには、保護層転写シートの製造時に、保護層をコーティングした後すぐに電離放射線を照射しても良いし、透明基材を使用して保護層転写シートの裏面から電離放射線を照射しても良いし、被着体へ転写後に照射してもよい。いずれの時期に電離放射線を照射しても保護層は硬化して、所望の耐性を得ることができるが、次の理由から転写後に照射することが最も好ましい。すなわち、転写前に保護層を硬化させると、保護層の膜強度が上昇し転写時に箔切れ性が低下する。また、保護層は硬くて脆い層になるため、転写条件によっては保護層に割れが生じ、その割れ目から溶剤が通過してしまい保護すべき画像等へ達してしまう。このように転写前に保護層を硬化させると、不具合が生じやすい。 In the protective layer transfer sheet of the present invention, a protective layer is provided on a substrate. The protective layer is composed of at least one layer, and is cured by irradiation with ionizing radiation or thermally cured to obtain solvent resistance, water resistance and scratch resistance. In order to obtain the above resistance, ionizing radiation may be irradiated immediately after coating the protective layer during the production of the protective layer transfer sheet, or ionizing radiation from the back surface of the protective layer transfer sheet using a transparent substrate. May be irradiated, or may be irradiated after transfer to the adherend. Irradiation with ionizing radiation at any time can cure the protective layer and obtain desired resistance, but it is most preferable to irradiate after transfer for the following reasons. That is, if the protective layer is cured before transfer, the film strength of the protective layer increases and the foil breakage is reduced during transfer. Further, since the protective layer is a hard and brittle layer, the protective layer is cracked depending on the transfer conditions, and the solvent passes through the crack and reaches an image to be protected. If the protective layer is cured before transfer as described above, problems are likely to occur.
一方、転写後に保護層を硬化させると前記のような不具合が生じず、箔切れ性がよく、また転写した保護層の膜には割れもないため、高い耐溶剤性が得られる。 On the other hand, when the protective layer is cured after the transfer, the above-described problems do not occur, the foil breakability is good, and the transferred protective layer film is not cracked, so that high solvent resistance is obtained.
保護層を構成する樹脂としては、電離放射線硬化可能なアクリル−シリカハイブリッド樹脂を主成分として含有しなければならない。 As a resin constituting the protective layer, an ionizing radiation curable acrylic-silica hybrid resin must be contained as a main component.
該アクリル−シリカハイブリッド樹脂は、そのシリカ成分が１５重量％以上６０重量％以下であることが好ましく、さらに好ましくは２０重量％以上３０重量％以下であることが好ましい。上記範囲以外では膜強度が低下し、保護層としての機能が劣化することがある。 The acrylic-silica hybrid resin preferably has a silica component of 15% by weight to 60% by weight, more preferably 20% by weight to 30% by weight. Outside the above range, the film strength is lowered, and the function as a protective layer may be deteriorated.
また、該アクリル−シリカハイブリッド樹脂は硬化前には常温でタックがないことが好ましい。タックがなければ、保護層転写シートとして巻物にした場合に、保護層がシートの反対側の面に貼りついて基材からはがれてしまう、いわゆるブロッキングと呼ばれる不具合が起こりにくくなるだけでなく、保護層の上にさらに接着層を積層する場合においても、積層しやすくなるなど、シート設計が容易になるメリットがある。 The acrylic-silica hybrid resin preferably has no tack at room temperature before curing. Without tack, when the protective layer transfer sheet is rolled up, the protective layer sticks to the opposite surface of the sheet and peels off from the base material. In the case of further laminating an adhesive layer on top, there is an advantage that the sheet design becomes easy, for example, it becomes easier to laminate.
また、該アクリル−シリカハイブリッド樹脂の硬化前のＴｇは３０℃以上であることが好ましい。３０℃未満では常温でタックが出やすくなる傾向がある。 Moreover, it is preferable that Tg before hardening of this acrylic-silica hybrid resin is 30 degreeC or more. If it is less than 30 degreeC, there exists a tendency for tack to come out easily at normal temperature.
さらに保護層の強靱性等を向上させる目的でアクリロイル基やメタクリロイル基を有する、ポリエステルアクリレート、ポリウレタンアクリレート、エポキシアクリレート、シリコーンアクリレート等の各種アクリレート系オリゴマーやプレポリマー、或いはポリエン−チオール系樹脂等にスチレン等の単官能モノマー、トリメチロールプロパントリアクリレート等の多官能モノマーを添加しても良い。ただしこれらのアクリレートのほとんどは、硬化前の性状が液体であったり、粘性物質であるので、保護層にタックを生じさせない範囲での添加に限られる。 Furthermore, for the purpose of improving the toughness of the protective layer, various acrylate oligomers and prepolymers such as polyester acrylate, polyurethane acrylate, epoxy acrylate and silicone acrylate having acryloyl group and methacryloyl group, or polyene-thiol resin styrene. A monofunctional monomer such as trifunctional monomer or a polyfunctional monomer such as trimethylolpropane triacrylate may be added. However, most of these acrylates are limited to addition in a range that does not cause tackiness in the protective layer because the properties before curing are liquid or viscous substances.
また上記電離放射線硬化樹脂以外にも熱可塑性樹脂を添加することができる。該熱可塑性樹脂としては、例えばアクリル系樹脂、酢酸ビニル系樹脂、エポキシ系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ブチラール系樹脂、ゼラチン、セルロース系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、ウレタン系樹脂等が挙げられる。
その他の添加剤として、紫外線吸収剤、着色顔料、白色顔料、体質顔料、充填剤、帯電防止剤、酸化防止剤、蛍光増白剤、染料等も適宜、必要に応じて使用することができる。
保護層の厚みは好ましくは０．1〜１０μm、さらに好ましくは０．５〜５μmである。上記範囲未満では保護層としての硬化が薄く、上記範囲を超えるとコスト高となる。
In addition to the ionizing radiation curable resin, a thermoplastic resin can be added. Examples of the thermoplastic resin include acrylic resins, vinyl acetate resins, epoxy resins, polyester resins, polycarbonate resins, butyral resins, gelatin, cellulose resins, polyamide resins, vinyl chloride resins, urethane resins. Examples thereof include resins.
As other additives, ultraviolet absorbers, colored pigments, white pigments, extender pigments, fillers, antistatic agents, antioxidants, fluorescent whitening agents, dyes, and the like can be used as necessary.
The thickness of the protective layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is less than the said range, hardening as a protective layer will be thin, and if it exceeds the said range, it will become expensive.
本発明の保護層転写シートは、基材の裏面、すなわち保護層の設けてある面と反対面に、サーマルヘッドや熱ローラーなどの熱によるスティッキングやシワなどの悪影響を防止するために、耐熱滑性層を設けてもよい。上記の耐熱滑性層を形成する樹脂としては、従来公知のものであればよく、例えば、ポリビニルブチラール樹脂、ポリビニルアセトアセタール樹脂、ポリエステル樹脂、塩化ビニル−酢酸ビニル共重合体、ポリエーテル樹脂、ポリブタジエン樹脂、スチレン−ブタジエン共重合体、アクリルポリオール、ポリウレタンアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート、エポキシアクリレート、ウレタン又はエポキシのプレポリマー、ニトロセルロース樹脂、セルロースナイトレート樹脂、セルロースアセトプロピオネート樹脂、セルロースアセテートブチレート樹脂、セルロースアセテートヒドロジエンフタレート樹脂、酢酸セルロース樹脂、芳香族ポリアミド樹脂、ポリイミド樹脂、ポリカーボネート樹脂、塩素化ポリオレフィン樹脂等が挙げられる。 The protective layer transfer sheet of the present invention is provided with a heat-resistant slide to prevent adverse effects such as sticking and wrinkles due to heat from a thermal head or a heat roller on the back surface of the substrate, that is, the surface opposite to the surface on which the protective layer is provided. An adhesive layer may be provided. The resin for forming the heat-resistant slipping layer may be any conventionally known resin such as polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene. Resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetopropionate resin, cellulose acetate Butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polycarbonate resin, chlorinated poly Olefin resins.
また、耐熱滑性層の耐熱性や塗膜強度及び基材シートとの密着性を向上させるために、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や、不飽和結合を有するモノマー、オリゴマーとの反応生成物を用いることができ、硬化方法は加熱したり、電離放射線を照射したり、その硬化手段は特に限定されない。これらの樹脂からなる耐熱滑性層に添加、あるいは上塗りする滑り性付与剤としては、燐酸エステル、シリコーンオイル、グラファイトパウダー、シリコーン系グラフトポリマー、フッ素系グラフトポリマー、アクリルシリコーングラフトポリマー、アクリルシロキサン、アリールシロキサン等のシリコーン重合体が挙げられる。耐熱滑性層は、上記に記載した樹脂、滑り性付与剤、更に充填剤を、適当な溶剤により、溶解又は分散させて、耐熱滑性層形成用インキを調製し、これを、上記の基材シートの裏面に、例えば、バーコーティング法、グラビア印刷法、スクリーン印刷法、グラビア版を用いたリバースコーティング法等の形成手段により塗布し、乾燥して形成することができる。その耐熱滑性層の塗工厚みは、固形分で０．１μｍ〜２．０μｍ程度である。 In addition, in order to improve the heat resistance of the heat resistant slipping layer, the coating film strength and the adhesion to the base sheet, a reaction cured product of a thermoplastic resin having a reactive group in the resin and a polyisocyanate, an unsaturated bond A reaction product with a monomer or an oligomer having a hydrogen atom can be used. The curing method is not particularly limited, and the curing means is not particularly limited by heating or irradiation with ionizing radiation. The slipperiness imparting agent added to or overcoated with the heat resistant slipping layer made of these resins includes phosphate ester, silicone oil, graphite powder, silicone graft polymer, fluorine graft polymer, acrylic silicone graft polymer, acrylic siloxane, aryl Examples thereof include silicone polymers such as siloxane. The heat resistant slipping layer is prepared by dissolving or dispersing the above-described resin, slipperiness imparting agent, and filler with an appropriate solvent to prepare a heat resistant slipping layer forming ink. It can be applied to the back surface of the material sheet by a forming means such as a bar coating method, a gravure printing method, a screen printing method, a reverse coating method using a gravure plate, and then dried. The coating thickness of the heat resistant slipping layer is about 0.1 μm to 2.0 μm in solid content.
保護層が基材から剥離しにくい場合には、基材と保護層との間に離型層を形成することができる。離型層は、例えば、ワックス類、シリコーンワックス、シリコーン樹脂、フッ素樹脂、アクリル樹脂、ポリビニルアルコール樹脂、セルロース誘導体樹脂、ウレタン系樹脂、酢酸系ビニル樹脂、アクリルビニルエーテル系樹脂、無水マレイン酸樹脂、及びこれらの樹脂群の共重合体を少なくとも１種以上含有する塗布液を、従来公知のグラビアコート、グラビアリバースコート等の方法で塗布、乾燥することにより形成することができる。 When the protective layer is difficult to peel from the base material, a release layer can be formed between the base material and the protective layer. The release layer includes, for example, waxes, silicone wax, silicone resin, fluorine resin, acrylic resin, polyvinyl alcohol resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acrylic vinyl ether resin, maleic anhydride resin, and It can be formed by applying and drying a coating solution containing at least one copolymer of these resin groups by a conventionally known method such as gravure coating or gravure reverse coating.
離型層は、熱転写時に被転写体に移行するもの、あるいは基材シート側に残るもの、あるいは凝集破壊するもの等を、適宜選択することができるが、離型層が非転写性であり、熱転写により離型層が基材シート側に残存し、離型層と転写保護層との界面が熱転写された後の保護層表面になるようにすることが、表面光沢性、保護層の転写安定性等の点で優れているために、好ましく行われる。離型層の形成方法は、従来公知の塗工方法で形成でき、その塗工厚みは乾燥状態で０．５μｍ〜５．０μｍ程度で十分である。又、転写後に艶消しの保護層が望ましい場合には、離型層中に各種の粒子を包含させるか、あるいは離型層の保護層側の表面をマット処理することにより、表面マット状にすることも出来る。尚、基材シートと保護層と剥離性が良好であれば、上記の離型層を設けることなく、保護層が熱転写により、基材シートから直接剥離することができる。 The release layer can be appropriately selected from those that move to the transfer target during thermal transfer, those that remain on the base sheet side, or those that cohesively break down, but the release layer is non-transferable, The release layer remains on the base sheet side due to thermal transfer, and the interface between the release layer and the transfer protective layer becomes the surface of the protective layer after the thermal transfer, surface glossiness, transfer stability of the protective layer Since it is excellent in terms of properties and the like, it is preferably performed. The release layer can be formed by a conventionally known coating method, and a coating thickness of about 0.5 μm to 5.0 μm is sufficient in a dry state. If a matte protective layer is desired after transfer, various types of particles are included in the release layer, or the surface of the release layer on the protective layer side is matted to form a surface mat. You can also If the base sheet and the protective layer are peelable, the protective layer can be peeled directly from the base sheet by thermal transfer without providing the release layer.
また、本発明の保護層転写シートを用いて、ＩＤカード、身分証明書、免許証等のカード類の作成を行うこともできる。これらのカードは写真等の画像情報の他に、文字情報を含むものである。この場合、例えば文字情報形成は溶融転写方式により行い、写真等の画像形成は昇華転写方式で行うこともできる。更にカードには、エンボス、サイン、ＩＣメモリー、磁気層、ホログラム、その他の印刷等を設けることもでき、保護層転写後にエンボス、サイン、磁気層等を設けることもできる。 In addition, cards such as ID cards, identification cards, and licenses can be created using the protective layer transfer sheet of the present invention. These cards include character information in addition to image information such as photographs. In this case, for example, character information can be formed by a melt transfer method, and an image such as a photograph can be formed by a sublimation transfer method. Furthermore, the card can be provided with embossing, signature, IC memory, magnetic layer, hologram, other printing, etc., and embossing, signature, magnetic layer, etc. can be provided after transfer of the protective layer.
受像シートや、カード等に熱転写シートを用いてサーマルプリンターによってカラー画像及び／又は文字画像を形成し、その上に本発明の保護層転写シートを用いて、転写保護層を転写して保護層を形成するか、同一基材上に熱転写インキ層を有する本発明の保護層転写シートを用いる。転写に際して、熱転写プリンターは、昇華転写用、溶融転写用、保護層転写用というように別々に転写条件を設定してもよいし、また、共通のプリンターでそれぞれ印字エネルギーを適切に調整して行ってもよい。尚、本発明の保護層転写シートでは、加熱手段として熱転写プリンターに限定されず、その他熱板、ホットスタンパー、熱ロール、ラインヒーター、アイロン等でも転写できる。また、保護層は、形成された画像の全面に転写してもよいし、特定の部分のみに転写してもよい。 A color image and / or a character image is formed by a thermal printer using a thermal transfer sheet on an image receiving sheet or a card, and a protective layer is transferred onto the protective layer transfer sheet using the protective layer transfer sheet of the present invention. The protective layer transfer sheet of the present invention that is formed or has a thermal transfer ink layer on the same substrate is used. During transfer, the thermal transfer printer may set transfer conditions such as sublimation transfer, melt transfer, and protective layer transfer separately, or by adjusting the printing energy appropriately with a common printer. May be. In the protective layer transfer sheet of the present invention, the heating means is not limited to a thermal transfer printer, but transfer can also be performed using a hot plate, a hot stamper, a hot roll, a line heater, an iron, or the like. The protective layer may be transferred to the entire surface of the formed image or may be transferred only to a specific portion.
本発明によれば、被転写体に対して保護層を箔切れ性よく転写することができ、保護層を電離放射線で硬化させることにより、耐溶剤性、耐水性、耐傷性、碁盤目テストの密着性が向上する。 According to the present invention, the protective layer can be transferred to the transfer object with good foil cutting properties, and by curing the protective layer with ionizing radiation, solvent resistance, water resistance, scratch resistance, and cross-cut test Adhesion is improved.
次に実施例及び比較例を挙げて本発明を更に具体的に説明する。尚、文中、部又は％とあるのは特に断りの無い限り質量基準である。 Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “part” or “%” is based on mass unless otherwise specified.
裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に保護層用塗工液１を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に接着層用塗工液１を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工して保護層転写シート１を得た。 The protective layer coating solution 1 was applied to the surface of a 25 μm PET film having a heat-resistant slip treatment on the back surface by a bar coater so that the dry coating thickness was 5 μm. Subsequently, the protective layer transfer sheet 1 was obtained by applying the adhesive layer coating liquid 1 on the protective layer with a bar coater so that the dry coating thickness was 0.5 μm.
保護層用塗工液１
ＵＶ硬化性アクリルシリカハイブリッド樹脂 ７０部（固形分３０％、シリカ成分２３％、Ｔｇ４５℃、Ｍｗ２万）
光開始剤 １．０部（ダロキュア１１７３、チバスペシャリティケミカル製）
ＭＥＫ ３０部
接着層用塗工液１
アクリル変性ポリエステルウレタン樹脂 ５０部（サンプレンＩＢ５８２、固形分４２％、三洋化成製）
トルエン ４０部
ＩＰＡ １０部
Coating liquid for protective layer 1
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 23%, Tg 45 ° C., Mw 20,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
MEK 30 parts Adhesive layer coating solution 1
50 parts of acrylic modified polyester urethane resin (Samprene IB582, solid content 42%, manufactured by Sanyo Chemical)
Toluene 40 parts IPA 10 parts
裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に保護層塗工液２を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に実施例１と同様にして、接着層用塗工液１を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工し、保護層転写シート２を得た。 The protective layer coating solution 2 was applied to the surface of a 25 μm PET film having a heat resistant slip treatment on the back surface by a bar coater so that the dry coating thickness was 5 μm. Subsequently, in the same manner as in Example 1 on the protective layer, the adhesive layer coating solution 1 was applied with a bar coater so that the dry coating thickness was 0.5 μm, and a protective layer transfer sheet 2 was obtained. It was.
保護層用塗工液２
ＵＶ硬化性アクリルシリカハイブリッド樹脂 ７０部（固形分３０％、シリカ成分２０％、Ｔｇ５５℃、Ｍｗ２．５万）
光開始剤 １．０部（ダロキュア１１７３、チバスペシャリティケミカル製）
ＭＥＫ ３０部
接着層用塗工液１
アクリル変性ポリエステルウレタン樹脂 ５０部（サンプレンＩＢ５８２、固形分４２％、三洋化成製）
トルエン ４０部
ＩＰＡ １０部
Protective layer coating solution 2
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 20%, Tg 55 ° C., Mw 25,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
MEK 30 parts Adhesive layer coating solution 1
50 parts of acrylic modified polyester urethane resin (Samprene IB582, solid content 42%, manufactured by Sanyo Chemical)
Toluene 40 parts IPA 10 parts
裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に離型層として融点が７０℃のパラフィンワックスを塗布厚みが０．５μｍとなるようホットメルトコーターで塗布し、その上に保護層用塗工液３を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に実施例１の接着層用塗工液１を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工して保護層転写シート３を得た。得られた保護層転写シートを５０℃で４日間加熱保存して保護層を熱硬化した。 Apply a paraffin wax having a melting point of 70 ° C. as a release layer to the surface of a 25 μm PET film having a heat-resistant slip treatment on the back surface with a hot melt coater to a coating thickness of 0.5 μm, and then apply a protective layer coating thereon. The coating liquid 3 was applied with a bar coater so that the dry coating thickness was 5 μm. Subsequently, the protective layer transfer sheet 3 was obtained by applying the adhesive layer coating liquid 1 of Example 1 on the protective layer with a bar coater so that the dry coating thickness was 0.5 μm. The obtained protective layer transfer sheet was heated and stored at 50 ° C. for 4 days to thermally cure the protective layer.
保護層用塗工液３
ポリエステル樹脂 １５部（バイロン２００、東洋紡績製）
イソシアネート １０部（タケネートＤ−２０４、固形分５０％、武田薬品製）
ＭＥＫ ７５部
接着層用塗工液１
アクリル変性ポリエステルウレタン樹脂 ５０部（サンプレンＩＢ５８２、固形分４２％、三洋化成製）
トルエン ４０部
ＩＰＡ １０部
Protective layer coating solution 3
15 parts of polyester resin (Byron 200, manufactured by Toyobo)
Isocyanate 10 parts (Takenate D-204, solid content 50%, Takeda Pharmaceutical)
MEK 75 parts Adhesive layer coating solution 1
50 parts of acrylic modified polyester urethane resin (Samprene IB582, solid content 42%, manufactured by Sanyo Chemical)
Toluene 40 parts IPA 10 parts
［比較例１］裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に保護層塗工液２を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に実施例１と同様にして、接着層用塗工液２を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工し、保護層転写シート４を得た。
保護層用塗工液２
ＵＶ硬化性アクリルシリカハイブリッド樹脂 ７０部（固形分３０％、シリカ成分２０％、Ｔｇ５５℃、Ｍｗ２．５万）
光開始剤 １．０部（ダロキュア１１７３、チバスペシャリティケミカル製）
ＭＥＫ ３０部
接着層用塗工液２
ポリエステルウレタン樹脂 ５０部（バイロンＵＲ−３２００、固形分３０％、東洋紡積製）
トルエン ５０部
[Comparative Example 1] The protective layer coating solution 2 was applied to the surface of a 25 μm PET film having a heat resistant slip treatment on the back surface by a bar coater so that the dry coating thickness was 5 μm. Subsequently, in the same manner as in Example 1 on the protective layer, the adhesive layer coating solution 2 was applied with a bar coater so that the dry coating thickness was 0.5 μm, and a protective layer transfer sheet 4 was obtained. It was.
Protective layer coating solution 2
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 20%, Tg 55 ° C., Mw 25,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
MEK 30 parts Adhesive layer coating solution 2
50 parts of polyester urethane resin (Byron UR-3200, solid content 30%, manufactured by Toyobo)
50 parts of toluene
［比較例２］裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に保護層塗工液２を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に実施例１と同様にして、接着層用塗工液３を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工し、保護層転写シート５を得た。 [Comparative Example 2] The protective layer coating solution 2 was applied to the surface of a 25 µm PET film having a heat resistant slip treatment on the back surface by a bar coater so that the dry coating thickness was 5 µm. Subsequently, in the same manner as in Example 1 on the protective layer, the adhesive layer coating solution 3 was applied with a bar coater so that the dry coating thickness was 0.5 μm, and a protective layer transfer sheet 5 was obtained. It was.
保護層用塗工液２
ＵＶ硬化性アクリルシリカハイブリッド樹脂 ７０部（固形分３０％、シリカ成分２０％、Ｔｇ５５℃、Ｍｗ２．５万）
光開始剤 １．０部（ダロキュア１１７３、チバスペシャリティケミカル製）
ＭＥＫ ３０部
接着層用塗工液３
ポリエステル樹脂 １５部（バイロンＵＥ−３３００、東洋紡積製）
トルエン ４０部
ＭＥＫ ４０部
Protective layer coating solution 2
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 20%, Tg 55 ° C., Mw 25,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
MEK 30 parts Adhesive layer coating solution 3
15 parts of polyester resin (Byron UE-3300, manufactured by Toyobo)
Toluene 40 parts MEK 40 parts
［比較例３］裏面に耐熱滑性処理された２５μｍのＰＥＴフィルムの表面に保護層塗工液２を乾燥塗布厚みが５μｍとなるようバーコーターにて塗工した。続いて、保護層の上に実施例１と同様にして、接着層用塗工液４を乾燥塗布厚みが０．５μｍとなるようにバーコーターにて塗工し、保護層転写シートを得た。 [Comparative Example 3] The protective layer coating solution 2 was applied to the surface of a 25 μm PET film having a heat resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, the adhesive layer coating solution 4 was applied onto the protective layer with a bar coater so that the dry coating thickness was 0.5 μm in the same manner as in Example 1 to obtain a protective layer transfer sheet. .
保護層用塗工液２
ＵＶ硬化性アクリルシリカハイブリッド樹脂 ７０部（固形分３０％、シリカ成分２０％、Ｔｇ５５℃、Ｍｗ２．５万）
光開始剤 １．０部（ダロキュア１１７３、チバスペシャリティケミカル製）
ＭＥＫ ３０部
接着層用塗工液４
塩化ビニル酢酸ビニル共重合樹脂 １５部（ＶＹＮＳ−３、ユニオンカーバイド製）
トルエン ４０部
ＭＥＫ ４０部
Protective layer coating solution 2
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 20%, Tg 55 ° C., Mw 25,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
MEK 30 parts Adhesive layer coating solution 4
15 parts of vinyl chloride vinyl acetate copolymer resin (VYNS-3, manufactured by Union Carbide)
Toluene 40 parts MEK 40 parts
以上のようにして得られた保護層転写シートを、縦１０ｃｍ×横１０ｃｍ×厚さ２ミリのアクリル板にホットラミネーター（大成製）を用いて１５０℃で熱ラミし、室温に下がるまで放置した後、基材を剥離した。つづいて実施例３以外は、コンベア式ＵＶ照射装置（ＧＳ製ＣＳ３０）にて、２００ｍｊ/ｃｍ２の積算光量のＵＶ光を照射して保護層を硬化した。 The protective layer transfer sheet obtained as described above was heat-laminated at 150 ° C. using a hot laminator (manufactured by Taisei) on an acrylic plate having a length of 10 cm × width of 10 cm × thickness of 2 mm, and was left until it fell to room temperature. Thereafter, the substrate was peeled off. Subsequently, except for Example 3, the protective layer was cured by irradiating UV light with an integrated light amount of 200 mj / cm 2 with a conveyor-type UV irradiation device (CS30 manufactured by GS).
（評価方法）
１．箔切れ性
○：箔切れ性良好、△：面状剥離傾向あり、×：面状剥離大
２．耐水・耐溶剤性
試料に水、エタノール、ＭＥＫ、トルエンをそれぞれ１滴滴下し、３０分後に拭き取り試料の様子を観察する。
○：変化無し、△：若干侵される、×：完全に侵される
３．耐傷性
試料を２５０ｇ／ｃｍ2の荷重をかけたスチールウール（ボンスター＃００００）で１０回擦る。
：変化無し、△：若干の傷あり、×：キズ大
４．密着性
碁盤目テスト：ＪＩＳ Ｋ５４００に準ずる。
(Evaluation methods)
1. 1. Foil cutting property: good foil cutting property, Δ: planar peeling tendency, x: large planar peeling One drop each of water, ethanol, MEK, and toluene is dropped on the water / solvent resistant sample, and the state of the wiped sample is observed after 30 minutes.
○: No change, Δ: Slightly affected, X: Completely affected The scratch resistant sample is rubbed 10 times with steel wool (Bonster # 0000) loaded at 250 g / cm @ 2.
: No change, Δ: Some scratches, ×: Large scratches Adhesive cross-cut test: According to JIS K5400.
以上の評価結果は下記の通りである。
△は、実用の範囲内である。 Δ is within the practical range.
１基材
２保護層
３接着層
４離型層
５耐熱滑性層
1 base material 2 protective layer 3 adhesive layer 4 release layer 5 heat resistant slipping layer
Claims (4)
4. The silica component of the acrylic-silica hybrid resin is 15% by weight or more and 60% by weight or less, has a Tg of 30 ° C. or more in physical properties before curing, and has no tack before curing at room temperature. Protective layer transfer sheet.
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| JP4489667B2 (en) * | 2004-12-01 | 2010-06-23 | 大日本印刷株式会社 | Method for forming printed matter |
| JP2007098633A (en) * | 2005-09-30 | 2007-04-19 | Dainippon Printing Co Ltd | Protective layer transfer sheet |
| JP4967566B2 (en) * | 2006-09-25 | 2012-07-04 | 凸版印刷株式会社 | Transfer sheet |
| JP5029243B2 (en) * | 2007-09-19 | 2012-09-19 | 凸版印刷株式会社 | Ink composition, transfer sheet using the same, and information recording medium using the same |
| JP4967999B2 (en) * | 2007-11-05 | 2012-07-04 | 三菱化学株式会社 | Transfer sheet and use thereof |
| JP5155645B2 (en) * | 2007-12-10 | 2013-03-06 | 日本写真印刷株式会社 | Transfer material manufacturing method and transfer material excellent in foil burr resistance |
| JP7068607B2 (en) | 2018-03-29 | 2022-05-17 | 大日本印刷株式会社 | Protective layer transfer sheet |
| JP6870781B2 (en) | 2018-06-29 | 2021-05-12 | 大日本印刷株式会社 | Thermal transfer sheet |
| US20220032674A1 (en) | 2018-09-28 | 2022-02-03 | Dai Nippon Printing Co., Ltd. | Thermal transfer sheet and print |
| JP7104461B2 (en) * | 2018-12-28 | 2022-07-21 | フジコピアン株式会社 | Thermal transfer recording medium |
| WO2020203566A1 (en) | 2019-04-04 | 2020-10-08 | 大日本印刷株式会社 | Heat transfer sheet |
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