JP4606618B2 - Thermal transfer recording medium - Google Patents
Thermal transfer recording medium Download PDFInfo
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- JP4606618B2 JP4606618B2 JP2001062321A JP2001062321A JP4606618B2 JP 4606618 B2 JP4606618 B2 JP 4606618B2 JP 2001062321 A JP2001062321 A JP 2001062321A JP 2001062321 A JP2001062321 A JP 2001062321A JP 4606618 B2 JP4606618 B2 JP 4606618B2
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- thermal transfer
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Description
【0001】
【発明の属する技術分野】
本発明は、耐溶剤性に優れ且つ高濃度の熱転写画像を与える熱転写記録媒体に関する。
【0002】
【従来の技術】
近年、サーマルヘッドを用いる感熱転写記録法は、無騒音であること、装置が比較的安価で、かつ小型化できること、保守が容易であること、転写画像が安定であること等の利点から多く用いられるようになってきている。このような感熱転写記録法に用いる熱転写記録媒体は、例えばコンデンサー紙やポリエステルフィルム等の熱伝導性及び耐熱性の優れた基材の一方の面に着色剤と熱可塑性樹脂類等からなるインク層を設けてなるものである。しかしながら従来の熱転写記録媒体はインク層中の着色剤の分散が悪く、そのため記録画像の濃度が十分でないという問題があった。着色剤の分散性を良くするために種々の分散剤が提案されている。例えば、ロジン、ロジンエステル、ポリアクリル酸、ポリアミンなどの酸性又は塩基性の官能基を持つ分散剤が提案されているが、このものは、耐溶剤性、特にメタノール、エタノールに対する耐アルコール性が悪いため、転写画像が溶剤に触れると消えてしまうといった欠点がある。特開平1−110188号公報には、熱転写記録媒体のカーボンブラックの分散剤としてアルミニウム系カップリング剤を用いることが提案されている。アルミニウムカップリング剤はカーボンブラック表面に化学的に結合され、分散性が向上する。この場合、未反応官能基が多く残存し、そのため塗工液が経時増粘したり、熱転写性能が低下するなどの問題がある。
【0003】
【発明が解決しようとする課題】
本発明は、熱転写記録媒体のインク層を構成する着色剤、特にカーボンブラックの分散性を向上させるとともに、インク層形成塗工液の経時安定性に優れ、しかも転写画像の耐溶剤性が優れる、熱転写記録媒体を提供することをその課題とする。
【0004】
【課題を解決するための手段】
本発明者は、上記した従来技術の問題点を解決すべく鋭意研究を重ねた結果、特定のマグネシウムキレート化合物を熱転写性インク層に含有させることにより上記課題が解決できることを見出し本発明を完成させるに至った。
即ち、本発明によれば、耐熱性基材上の片面に着色剤と熱可塑性樹脂からなる熱転写性インク層を設けてなる熱転写記録媒体において、該インク層に下記式(1)
Mg(R1O)(CH3COCHCOOR2) (1)
(但し、R1及びR2はそれぞれ独立にアルキルまたはアルケニル基を表す)で表わされるマグネシウムキレート化合物を含有させたことを特徴とする熱転写記録媒体が提供される。
【0005】
【発明の実施の形態】
以下本発明を詳細に説明する。
本発明で分散剤として用いる上記一般式(1)のマグネシウムキレート化合物において、R1のアルキル、アルケニル基としては炭素数1〜30のものが通常用いられ、特にメチル基、エチル基、n−プロピル基等の炭素数1〜8の低級アルキル基が好ましく用いられる。一方、R2のアルキル基、アルケニル基としては炭素数1〜30のものが通常用いられ、その例としては、n−ブチル基、ヘキシル基、オクチル基、ラウリル基、オレイル基、ステアリル基が挙げられる。本発明で用いるマグネシウムキレート化合物は単独でも数種の混合でも使用可能である。即ち、R1及びR2のアルキル、アルケニル基が異なる種類の混合物が使用でき、例えば、R2が天然物由来の複数種の脂肪酸アルキルでも良い。R1、R2の炭素数に応じてマグネシウムキレート化合物分散剤の融点、粘度が調整可能である。塗工液溶剤への溶解性、調製された塗工液の安定性に特に優れる点で、R1がエチル基、R2がオレイル基であるオレイルアセトアセテートマグネシウムエチレートとの使用が特に好ましい。
【0006】
マグネシウムキレート化合物分散剤の使用量は、使用される着色剤の種類、量によって適宜調製可能で特に制限は受けないが、着色剤に対して通常0.01〜30重量%の範囲であり、0.1〜10重量%が好ましい。少なすぎると分散性の向上が不十分となり、多すぎると塗工液の経時増粘を起こし易い傾向がある。
【0007】
本発明で用いられる着色剤としては、要求される色調などに応じ、カーボンブラック、有機顔料、無機顔料又は各種染料から適当なものを選択して用いることができる。カーボンブラックのように親水性表面を持ち分散剤として従来高極性のイオン性活性剤、高分子分散剤を使用せざるをえなかった用途に特に効果が大きい。着色剤のインク層中の含有量は通常5〜30%の範囲である。
【0008】
インク層に使用する熱可塑性樹脂としては、酸価が9mgKOH/g以下の顔料分散性に乏しい飽和共重合ポリエステル樹脂を用いる。これにより、画像の耐溶剤性(アルコール性)、耐スクラッチ性、受容体への定着性に優れた熱転写画像を得ることが可能となる。
熱可塑性樹脂の使用量はインク層重量に基づき通常90%以下、好ましくは1〜80%の範囲である。
【0009】
本発明のインク層には、着色剤、熱可塑性樹脂、マグネシウムキレート化合物以外に熱感度向上を目的にワックス、低分子量オリゴマー等からなる熱溶融性材料を添加しても良い。熱溶融性材料の添加量はインク層重量に基づき0〜90%の範囲である。
【0010】
さらに、ブロッキング防止等を目的に有機・無機フィラー等を含有させても良い。但し、これらフィラーは着色剤がマグネシウムキレート化合物で分散されてから後に塗工液中に添加処理されることが必要である。
【0011】
インク層は、上記の着色剤、熱可塑性樹脂、マグネシウムキレート化合物、及び必要に応じて熱溶融性材料、その他添加剤をトルエン、メチルエチルケトン、テトラヒドロフラン、イソプロピルアルコール等の塗工液溶剤に混合させ、サンドミル、ビーズミル、ボールミル、超音波ミル等で分散混合処理し、得られた塗工液を支持体に従来公知の方法(例えばホットメルト塗布法、水性塗工法、有機溶剤を使用する塗工法等)で形成することができる。インク層の厚みは通常0.5〜4μm、好ましくは0.8〜2μmである。支持体は公知のフィルムや紙をそのまま使用すればよく、例えばポリエチレンテレフタレート(PET)等のポリエステル、ポリカーボネート、トリアセチルセルロース、ナイロン、ポリイミド等のように比較的耐熱性のよいプラスチックフィルム;セロハン;硫酸紙等が好ましく使用される。
【0012】
熱感度、解像度付与を目的に熱溶融性材料を主体とした剥離性の中間層を支持体とインク層の間に設けても良い。又、画像受容体との接着性を高める目的で熱可塑性樹脂、熱溶融性材料を主体とする表面層をインク層の上に設けても良い。さらに、必要に応じて支持体の裏面に保護層(バック層)を設けてもよい。保護層はサーマルヘッドによる熱印加時に支持体を高温から保護するための層であり、耐熱性の高い熱可塑性樹脂や熱硬化性樹脂のほか、紫外線硬化性樹脂や電子線硬化性樹脂も使用可能である。保護層形成に好適な樹脂はフッ素樹脂、シリコーン樹脂、ポリイミド樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂等であり、これらの樹脂を薄膜状で使用すればよい。また、保護層の設置によって支持体の耐熱性を著しく向上させることができるため、該層の設置によって従来は不適とされていた材料を支持体にすることも可能になる。
【0013】
【実施例】
以下、実施例、参考例及び比較例に基づいて、本発明を具体的に説明する。なお、部は重量基準である。
【0014】
実施例1
熱転写性着色インク層塗工液の調製
カーボンブラック 14.5部
オレイルアセトアセテートマグネシウムエチレート 0.5部
飽和共重合ポリエステル樹脂 5.0部
(ユニチカ製、UE3216、酸価1mgKOH/g)
メチルエチルケトン 80.0部
以上をビーズミル中で3時間混合し、分散液を得た。この分散液15部に対し、UE3216の20%メチルエチルケトン溶液85部を混合し、実施例1の熱転写性着色インク層塗工液を得た。
【0015】
参考例2
実施例1の飽和共重合ポリエステル樹脂をユニチカ製XA0847(酸価10mgKOH/g)とした以外は実施例1同様にして熱転写性着色インク層塗工液を得た。
【0016】
比較実施例1
実施例1のマグネシウムキレート誘導体に代えて、アルミニウムキレート誘導体(アセトアルコキシアルミニウムジイソプロピレート)とした以外は実施例1同様にして熱転写性着色インク層塗工液を得た。
【0017】
比較実施例2
実施例1のマグネシウムキレート誘導体に代えて、ラノリン酸グリセライド(日本精化製FPGi33)3部、カーボンブラック15部とした以外は実施例1同様にして熱転写性着色インク層塗工液を得た。
【0018】
比較実施例3
実施例1のマグネシウムキレート誘導体の添加量を0重量部とした以外は実施例1同様にして熱転写性着色インク層塗工液を得た。
【0019】
以上5種の熱転写性着色インク層塗工液を、下記の耐熱滑性層及び中間層を持つ支持体の中間層上に塗布、乾燥して熱転写記録媒体を作成した。
【0020】
厚さ4.5μmのポリエチレンテレフタレートフィルムの一方の面にシリコン変性ポリエステル樹脂(大日精化工業製SP3035)を乾燥後膜厚0.3μmとなるように耐熱滑性層を設け、次に他方の面に
カルナウバワックス 9部
エチレン酢酸ビニル共重合体(住友化学製KE−10) 0.5部
スチレンブダジエン樹脂(JSR製TR−2000) 0.5部
トルエン 70部
メチルエチルケトン 20部
からなる塗工液を乾燥後膜厚1.0μmとなるように塗設し、中間層を設けた。
【0021】
この中間層の上に乾燥後膜厚1.0μmとなるように上記の熱転写性着色インク層塗工液を塗設し、5種の熱転写記録媒体を得た。各記録媒体を記録しその画像濃度及び耐溶剤性試験を下記の条件で行った。
評価条件
熱転写プリンター:サトー製ラベルプリンター−M4800RV
印字速度 :100mm/秒
受容体 :リンテック製PETフィルムラベル(ホワイトマットタイプ)
耐溶剤性試験 :熱転写画像を試薬1級エタノールに浸した綿布(かなきん3号)に100g/cm2の荷重を掛け画像をこすりつけ、画像の欠損が発生する回数を記録した。
画像濃度 :マクベス反射濃度計(RD914)で反射濃度を測定した。
さらに5種の熱転写性着色インク層塗工液を常温で24時間保管し液増粘の有無をB型粘度計(60回転/分)で判定した。結果を表1に示す。
【0022】
【表1】
【0023】
【発明の効果】
本発明のマグネシウムキレート化合物で分散されたインク層を持つ記録媒体は、耐溶剤性を損なうことがなく高い画像濃度を持つ画像を与え、かつ塗工液の経時安定性にも優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermal transfer recording medium having excellent solvent resistance and giving a high density thermal transfer image.
[0002]
[Prior art]
In recent years, a thermal transfer recording method using a thermal head is often used due to advantages such as noiselessness, relatively inexpensive and small-sized apparatus, easy maintenance, and stable transfer image. It is getting to be. A thermal transfer recording medium used in such a thermal transfer recording method is an ink layer comprising a colorant and thermoplastic resins on one surface of a substrate having excellent thermal conductivity and heat resistance such as condenser paper and polyester film. Is provided. However, the conventional thermal transfer recording medium has a problem that the colorant is not well dispersed in the ink layer, so that the density of the recorded image is not sufficient. In order to improve the dispersibility of the colorant, various dispersants have been proposed. For example, a dispersant having an acidic or basic functional group such as rosin, rosin ester, polyacrylic acid, and polyamine has been proposed, but this has poor solvent resistance, particularly alcohol resistance to methanol and ethanol. Therefore, there is a drawback that the transferred image disappears when it comes into contact with the solvent. Japanese Patent Laid-Open No. 1-110188 proposes using an aluminum coupling agent as a carbon black dispersant for a thermal transfer recording medium. The aluminum coupling agent is chemically bonded to the carbon black surface, and the dispersibility is improved. In this case, many unreacted functional groups remain, which causes problems such as thickening of the coating liquid with time and deterioration of thermal transfer performance.
[0003]
[Problems to be solved by the invention]
The present invention improves the dispersibility of the colorant constituting the ink layer of the thermal transfer recording medium, particularly carbon black, is excellent in the temporal stability of the ink layer forming coating solution, and is excellent in the solvent resistance of the transferred image. An object is to provide a thermal transfer recording medium.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventor has found that the above problems can be solved by including a specific magnesium chelate compound in the thermal transfer ink layer, and completes the present invention. It came to.
That is, according to the present invention, in a thermal transfer recording medium in which a thermal transfer ink layer comprising a colorant and a thermoplastic resin is provided on one side of a heat resistant substrate, the following formula (1) is applied to the ink layer.
Mg (R 1 O) (CH 3 COCHCOOR 2 ) (1)
There is provided a thermal transfer recording medium comprising a magnesium chelate compound represented by the formula (wherein R 1 and R 2 each independently represents an alkyl or alkenyl group).
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
In the magnesium chelate compound of the above general formula (1) used as a dispersant in the present invention, an alkyl or alkenyl group of R 1 is usually used having 1 to 30 carbon atoms, particularly a methyl group, an ethyl group, or n-propyl. A lower alkyl group having 1 to 8 carbon atoms such as a group is preferably used. On the other hand, those having 1 to 30 carbon atoms are usually used as the alkyl group and alkenyl group of R 2 , and examples thereof include n-butyl group, hexyl group, octyl group, lauryl group, oleyl group and stearyl group. It is done. The magnesium chelate compound used in the present invention can be used alone or in combination of several kinds. That is, a mixture of different types of alkyl and alkenyl groups for R 1 and R 2 can be used. For example, R 2 may be a plurality of types of fatty acid alkyls derived from natural products. The melting point and viscosity of the magnesium chelate compound dispersant can be adjusted according to the number of carbon atoms of R 1 and R 2 . In particular, use with oleyl acetoacetate magnesium ethylate in which R 1 is an ethyl group and R 2 is an oleyl group is particularly preferred in terms of solubility in a coating solution solvent and stability of the prepared coating solution.
[0006]
The amount of the magnesium chelate compound dispersant used can be appropriately adjusted depending on the type and amount of the colorant used and is not particularly limited, but is usually in the range of 0.01 to 30% by weight with respect to the colorant. .1 to 10% by weight is preferred. If the amount is too small, the improvement in dispersibility becomes insufficient. If the amount is too large, the coating solution tends to increase in viscosity over time.
[0007]
As the colorant used in the present invention, an appropriate one can be selected from carbon black, organic pigments, inorganic pigments or various dyes according to the required color tone. This is particularly effective for uses such as carbon black, which have had a hydrophilic surface and had to use a high-polarity ionic activator or polymer dispersant as a dispersant. The content of the colorant in the ink layer is usually in the range of 5 to 30%.
[0008]
The thermoplastic resin used in the ink layer, acid value Ru with poor saturated copolymer polyester resin in the following pigment dispersibility 9 mg KOH / g. As a result, it is possible to obtain a thermal transfer image excellent in solvent resistance (alcohol property), scratch resistance and fixability to a receiver .
The amount of the thermoplastic resin used is usually 90% or less, preferably 1 to 80% based on the weight of the ink layer.
[0009]
In addition to the colorant, thermoplastic resin, and magnesium chelate compound, the ink layer of the present invention may contain a heat-meltable material made of wax, low molecular weight oligomer, or the like for the purpose of improving thermal sensitivity. The amount of the heat-meltable material added is in the range of 0 to 90% based on the ink layer weight.
[0010]
Furthermore, an organic / inorganic filler may be contained for the purpose of preventing blocking. However, these fillers need to be added to the coating solution after the colorant is dispersed with the magnesium chelate compound.
[0011]
The ink layer is prepared by mixing the above-mentioned colorant, thermoplastic resin, magnesium chelate compound, and if necessary, a heat-meltable material and other additives in a coating liquid solvent such as toluene, methyl ethyl ketone, tetrahydrofuran, isopropyl alcohol, and the like. , Dispersed and mixed in a bead mill, ball mill, ultrasonic mill, etc., and the obtained coating solution is applied to the support by a conventionally known method (for example, a hot melt coating method, an aqueous coating method, a coating method using an organic solvent, etc.). Can be formed. The thickness of the ink layer is usually from 0.5 to 4 μm, preferably from 0.8 to 2 μm. For the support, a known film or paper may be used as it is. For example, a plastic film having relatively high heat resistance such as polyester such as polyethylene terephthalate (PET), polycarbonate, triacetylcellulose, nylon, polyimide, cellophane, sulfuric acid Paper or the like is preferably used.
[0012]
For the purpose of imparting thermal sensitivity and resolution, a peelable intermediate layer mainly composed of a heat-meltable material may be provided between the support and the ink layer. In addition, a surface layer mainly composed of a thermoplastic resin or a heat-meltable material may be provided on the ink layer for the purpose of improving the adhesion to the image receptor. Furthermore, you may provide a protective layer (back | bag layer) in the back surface of a support body as needed. The protective layer is a layer to protect the support from high temperature when heat is applied by the thermal head. In addition to high heat resistance thermoplastic resin and thermosetting resin, UV curable resin and electron beam curable resin can also be used. It is. Resins suitable for forming the protective layer are fluorine resin, silicone resin, polyimide resin, epoxy resin, phenol resin, melamine resin, and the like, and these resins may be used in a thin film form. In addition, since the heat resistance of the support can be remarkably improved by installing the protective layer, it becomes possible to use a material that has been conventionally unsuitable by installing the layer as the support.
[0013]
【Example】
Hereinafter, based on an Example, a reference example, and a comparative example, this invention is demonstrated concretely. Parts are based on weight.
[0014]
Example 1
Preparation of thermal transfer coloring ink layer coating liquid Carbon black 14.5 parts Oleyl acetoacetate magnesium ethylate 0.5 parts Saturated copolymer polyester resin 5.0 parts (Unitika, UE3216, acid value 1 mgKOH / g)
80.0 parts or more of methyl ethyl ketone was mixed in a bead mill for 3 hours to obtain a dispersion. To 15 parts of this dispersion, 85 parts of a 20% methyl ethyl ketone solution of UE3216 was mixed to obtain a heat transferable colored ink layer coating liquid of Example 1.
[0015]
Reference example 2
A thermally transferable colored ink layer coating solution was obtained in the same manner as in Example 1 except that the saturated copolymerized polyester resin of Example 1 was XA0847 (acid value 10 mgKOH / g) manufactured by Unitika.
[0016]
Comparative Example 1
A thermally transferable colored ink layer coating solution was obtained in the same manner as in Example 1 except that instead of the magnesium chelate derivative of Example 1, an aluminum chelate derivative (acetoalkoxyaluminum diisopropylate) was used.
[0017]
Comparative Example 2
Instead of the magnesium chelate derivative of Example 1, a heat transferable colored ink layer coating solution was obtained in the same manner as in Example 1 except that 3 parts of lanolinic acid glyceride (FPGI33 manufactured by Nippon Seika Co., Ltd.) and 15 parts of carbon black were used.
[0018]
Comparative Example 3
A thermally transferable colored ink layer coating solution was obtained in the same manner as in Example 1 except that the addition amount of the magnesium chelate derivative in Example 1 was changed to 0 part by weight.
[0019]
The above five types of thermal transfer coloring ink layer coating solutions were applied onto an intermediate layer of a support having the following heat-resistant slipping layer and intermediate layer and dried to prepare a thermal transfer recording medium.
[0020]
A heat-resistant slipping layer is provided on one surface of a 4.5 μm thick polyethylene terephthalate film so that the film thickness becomes 0.3 μm after drying a silicon-modified polyester resin (SP3035 manufactured by Dainichi Seika Kogyo Co., Ltd.), and then the other surface Carnauba wax 9 parts ethylene vinyl acetate copolymer (KE-10 manufactured by Sumitomo Chemical Co., Ltd.) 0.5 parts styrene budadiene resin (TR-2000 manufactured by JSR) 0.5 parts toluene 70 parts methyl ethyl ketone 20 parts coating solution An intermediate layer was provided by coating so as to have a film thickness of 1.0 μm after drying.
[0021]
On the intermediate layer, the above-described thermal transfer coloring ink layer coating solution was applied so as to have a film thickness of 1.0 μm after drying, and five types of thermal transfer recording media were obtained. Each recording medium was recorded, and its image density and solvent resistance test was conducted under the following conditions.
Evaluation condition Thermal transfer printer: SATO Label Printer-M4800RV
Printing speed: 100 mm / sec Receptor: PET film label manufactured by Lintec (white mat type)
Solvent resistance test: The thermal transfer image was rubbed with a cotton cloth (Kanakin No. 3) soaked in reagent 1 grade ethanol under a load of 100 g / cm 2 , and the number of occurrences of image loss was recorded.
Image density: The reflection density was measured with a Macbeth reflection densitometer (RD914).
Further, five types of thermal transfer coloring ink layer coating liquids were stored at room temperature for 24 hours, and the presence or absence of liquid thickening was determined with a B-type viscometer (60 rotations / minute). The results are shown in Table 1.
[0022]
[Table 1]
[0023]
【The invention's effect】
The recording medium having the ink layer dispersed with the magnesium chelate compound of the present invention gives an image having a high image density without impairing the solvent resistance, and is excellent in the temporal stability of the coating liquid.
Claims (4)
Mg(R1O)(CH3COCHCOOR2) (1)
(但し、R1及びR2は、それぞれ独立にアルキル基又はアルケニル基を表す。)In a thermal transfer recording medium in which a thermal transfer ink layer comprising a colorant and a thermoplastic resin is provided on one side of a heat resistant substrate, a saturated copolymerized polyester resin having an acid value of 9 mgKOH / g or less is used as the thermoplastic resin. A thermal transfer recording medium , wherein the ink layer contains a magnesium chelate compound represented by the following formula (1).
Mg (R 1 O) (CH 3 COCHCOOR 2 ) (1)
(However, R 1 and R 2 each independently represents an alkyl group or an alkenyl group.)
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JP2001062321A JP4606618B2 (en) | 2001-03-06 | 2001-03-06 | Thermal transfer recording medium |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01110188A (en) * | 1987-10-23 | 1989-04-26 | Hitachi Maxell Ltd | Thermal transfer recording medium |
JPH0338381A (en) * | 1989-07-05 | 1991-02-19 | Mitsui Toatsu Chem Inc | Thermal transfer recording material |
JPH0781247A (en) * | 1993-06-29 | 1995-03-28 | Mitsubishi Rayon Co Ltd | Heat-sensitive transferring body |
JPH1025441A (en) * | 1996-07-12 | 1998-01-27 | Kawaken Fine Chem Co Ltd | Dispersing/gelling agent for ink and paint |
-
2001
- 2001-03-06 JP JP2001062321A patent/JP4606618B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01110188A (en) * | 1987-10-23 | 1989-04-26 | Hitachi Maxell Ltd | Thermal transfer recording medium |
JPH0338381A (en) * | 1989-07-05 | 1991-02-19 | Mitsui Toatsu Chem Inc | Thermal transfer recording material |
JPH0781247A (en) * | 1993-06-29 | 1995-03-28 | Mitsubishi Rayon Co Ltd | Heat-sensitive transferring body |
JPH1025441A (en) * | 1996-07-12 | 1998-01-27 | Kawaken Fine Chem Co Ltd | Dispersing/gelling agent for ink and paint |
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