JP4344570B2 - Fused thermal transfer recording paper - Google Patents
Fused thermal transfer recording paper Download PDFInfo
- Publication number
- JP4344570B2 JP4344570B2 JP2003317738A JP2003317738A JP4344570B2 JP 4344570 B2 JP4344570 B2 JP 4344570B2 JP 2003317738 A JP2003317738 A JP 2003317738A JP 2003317738 A JP2003317738 A JP 2003317738A JP 4344570 B2 JP4344570 B2 JP 4344570B2
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- JP
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- Prior art keywords
- thermal transfer
- transfer recording
- weight
- recording sheet
- melt
- Prior art date
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Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は溶融熱転写記録用紙に関するものである。より詳細には、種々の印刷方式においてインクの転移性、密着性に優れ、特に溶融熱転写記録装置を用いたときの熱溶融性インクの転写性、密着性、耐水性、耐溶剤性に優れた溶融熱転写記録用紙に関するものである。 The present invention relates to a melt thermal transfer recording sheet. More specifically, the transferability and adhesion of the ink are excellent in various printing methods, and particularly the transferability, adhesion, water resistance, and solvent resistance of the hot melt ink when using a melt thermal transfer recording apparatus. The present invention relates to a melt thermal transfer recording sheet.
画像記録方法としては、昇華熱転写方式、溶融熱転写方式、電子写真方式、静電記録方式等があり、画像や情報記録に幅広く利用されている。これらは転写や画像の定着および密着に熱エネルギーを用いるもので、例えばインクリボンを介して記録媒体に押し付けて色材をインクリボンより記録媒体に転写したり、トナーを記録媒体に転写した後に高温のロールや光により加熱して密着させたりするものである。 As the image recording method, there are a sublimation thermal transfer method, a melt thermal transfer method, an electrophotographic method, an electrostatic recording method, and the like, which are widely used for image and information recording. These use thermal energy for transfer and image fixing and adhesion. For example, the color material is transferred from the ink ribbon to the recording medium by pressing the ink medium via the ink ribbon, or the toner is transferred to the recording medium at a high temperature. It is heated and adhered by a roll or light.
これらの中でバーコード等の情報記録に一般的に使用される溶融熱転写方式は、熱溶融性インクおよびそれを支持する基体からなる熱転写インクリボンと、記録用紙とを、熱源であるサーマルヘッド等を備えた印字ヘッドとドラムとの間に挟着させて、サーマルヘッドを電気信号にて制御することによって熱転写インクリボン中の熱溶融性インクを加熱して溶解されたインクを直接記録用紙に転写するものである。 Among them, the heat transfer method generally used for recording information such as a barcode is a heat transfer ink ribbon composed of a heat-meltable ink and a substrate that supports the ink and a recording paper, a thermal head that is a heat source, etc. The heat-meltable ink in the thermal transfer ink ribbon is heated to transfer the dissolved ink directly to the recording paper by sandwiching it between the print head equipped with the drum and the drum and controlling the thermal head with an electrical signal To do.
この様な溶融熱転写方式に用いる記録用紙は、熱溶融性インクに対する密着性の良好なポリエステル樹脂やエポキシ樹脂からなる層やプライマー層を表面に有することが多い。 The recording paper used for such a melt heat transfer system often has a layer or primer layer made of a polyester resin or epoxy resin having good adhesion to the heat melt ink on the surface.
これら記録用紙は、一般に、焼成クレイまたは炭酸カルシウム等の無機微細粉末を含有するプロピレン系樹脂の延伸フィルムよりなる合成紙(たとえば特許文献1〜15参照)や、ポリエチレンテレフタレート延伸フィルム、或いはポリオレフィン系樹脂フィルム等である。更にこれらのフィルムの表面に画像受容層としてシリカや炭酸カルシウム等の無機微細粉末とバインダーとを含有するピグメント塗工剤を塗工することによって白色度、染色性および印刷適性を高めたものが用いられている(たとえば特許文献16〜23)。 These recording papers are generally synthetic paper (for example, see Patent Documents 1 to 15) made of a stretched film of a propylene-based resin containing inorganic fine powder such as calcined clay or calcium carbonate, a stretched polyethylene terephthalate film, or a polyolefin-based resin. Film. In addition, the surface of these films is coated with a pigment coating agent containing an inorganic fine powder such as silica or calcium carbonate and a binder as an image receiving layer, so that the whiteness, dyeability and printability are improved. (For example, Patent Documents 16 to 23).
また、記録用紙として、無機微細粉末含有ポリオレフィン系樹脂の延伸フィルムであって、画像受容層として各種印刷適性および帯電防止性能を付与させるために窒素含有高分子化合物の水溶性プライマーを塗布したものも提案されている(例えば特許文献24)。しかし、この記録用紙を用いた場合は、高温高湿環境下において、吸湿性を有する水性プライマー層が水分を吸湿するために熱溶融性インクの転写が妨害され、その結果バーコード等の印字に線切れが生じたり、画像が不鮮明になったりする等の問題があった。 In addition, as a recording paper, a stretched film of a polyolefin resin containing inorganic fine powder, which is coated with a water-soluble primer of a nitrogen-containing polymer compound for imparting various printability and antistatic performance as an image receiving layer. It has been proposed (for example, Patent Document 24). However, when this recording paper is used, the water-based primer layer that absorbs moisture absorbs moisture in a high-temperature and high-humidity environment. There have been problems such as line breakage and image blurring.
この問題を改良するために、より微細な無機微細粉末を含有するポリオレフィン系樹脂フィルムの延伸物よりなる微多孔性のフィルムを成形したものに、窒素含有高分子化合物の水溶性プライマーを塗布した記録用紙を用いることで、高温、高湿環境下においても鮮明な画像が得られることが報告されている(例えば特許文献25〜27)。しかしながら、これらの記録材料に印字した印字物には、高温高湿環境下に長時間置いた後にインク密着不良の問題が発生することが判明している。 In order to remedy this problem, a recording was made by applying a water-soluble primer of a nitrogen-containing polymer compound to a molded microporous film made of a stretched polyolefin resin film containing finer inorganic fine powder. It has been reported that a clear image can be obtained even in a high temperature and high humidity environment by using paper (for example, Patent Documents 25 to 27). However, it has been found that printed matter printed on these recording materials has a problem of poor ink adhesion after being placed in a high temperature and high humidity environment for a long time.
この問題を更に改良するために、特定の画像受容層を設けることにより、高温高湿環境下に長時間置かれた印字物であっても、インクの密着性が向上することが報告されている(例えば特許文献28)。 In order to further improve this problem, it has been reported that by providing a specific image-receiving layer, the adhesion of ink is improved even for a printed matter placed for a long time in a high temperature and high humidity environment. (For example, patent document 28).
しかし、特許文献28に記載の記録用紙に溶融熱転写記録装置を用いてバーコード印字などを行ったうえで、有機溶剤などの入ったドラム缶や容器の情報管理に使用すると、内容物の有機溶剤が漏れるなどにより、熱溶融性インクあるいは画像受容層が有機溶剤によって溶解し印字情報が剥がれ落ち、情報管理に支障をきたすなどの問題があった。このため、市場からの改善要望が高かった。
そこで本発明は、特に有機溶剤にさらされた状態で擦過されても情報管理に支障をきたさず、種々の印刷性にも優れた溶融熱転写記録用紙を提供することを解決すべき課題とした。 Accordingly, the present invention has been made to solve the problem of providing a melt thermal transfer recording sheet that does not interfere with information management even when it is rubbed in a state exposed to an organic solvent and is excellent in various printability.
本発明者らはこのような従来技術の問題に鑑み検討を続けた結果、少なくとも一方向に延伸された樹脂延伸フィルムからなる溶融熱転写記録用紙であって、JIS−B−0601−2001による樹脂延伸フィルムの表面の中心線平均粗さ(Ra)が0.4〜2.5μmであり、該樹脂延伸フィルムの最外層は、無機微細粉末および/または有機フィラーを30〜75重量%、JIS−K−7206−1999で測定したビカット軟化点が140℃以下である熱可塑性樹脂とJIS−K−7206−1999で測定したビカット軟化点が140℃を超えるポリオレフィン系樹脂を合計で70〜25重量%含み、該樹脂延伸フィルムの最外層は、該ポリオレフィン系樹脂100重量部に対して、該熱可塑性樹脂を75重量部より多く900重量部以下の量で含むことを特徴とする本発明の溶融熱転写記録用紙が、前記課題を克服することを見いだした。 As a result of continuing investigations in view of such problems of the prior art, the inventors of the present invention are melt thermal transfer recording sheets made of a stretched resin film stretched in at least one direction, and are resin stretched according to JIS-B-0601-2001. The center line average roughness (Ra) of the surface of the film is 0.4 to 2.5 μm, and the outermost layer of the stretched resin film is 30 to 75% by weight of inorganic fine powder and / or organic filler, JIS-K Includes a total of 70 to 25% by weight of a thermoplastic resin having a Vicat softening point of 140 ° C. or less as measured in −7206-1999 and a polyolefin resin having a Vicat softening point of 140 ° C. or more as measured in JIS-K-7206-1999 , outermost layer, with respect to the polyolefin-based resin 100 parts by weight, more 900 wt than 75 parts by weight of thermoplastic resin of the resin stretched film Melt thermal transfer recording sheet of the present invention which comprises in the following amounts were found to overcome the problems.
無機微細粉末および/または有機フィラーをポリオレフィン系樹脂に含有させ、少なくとも一方向に延伸することで表面には微細な凹凸を生じ、また内部にも微細な空隙(ミクロボイド)が生じる。さらにビカット軟化点が140℃以下の熱可塑性樹脂を含有することで、溶融熱転写印字する際にサーマルヘッドの熱と圧力により溶融した熱転写インクがこれら凹凸や空隙に入り込み、続いて表面の熱可塑性樹脂が可塑化変形しこれら凹凸や空隙の表層を被覆することで熱転写インクが内部に封じ込められ、その結果有機溶剤にさらされた状態で擦過した後もインキの溶けだしが少なくなる。 By incorporating an inorganic fine powder and / or an organic filler into a polyolefin resin and stretching in at least one direction, fine irregularities are produced on the surface, and fine voids (microvoids) are also produced inside. Further, by containing a thermoplastic resin having a Vicat softening point of 140 ° C. or lower, the thermal transfer ink melted by the heat and pressure of the thermal head enters the irregularities and voids when performing melt thermal transfer printing, and then the surface thermoplastic resin However, the thermal transfer ink is contained inside by plasticizing and deforming and covering the surface layer of these irregularities and voids, and as a result, the ink does not melt even after being rubbed in an exposed state to an organic solvent.
これらの現象は、溶融熱転写記録装置を用いて温度110℃、印字速度3インチ/秒の条件で本発明の上記樹脂延伸フィルムの表面を加熱後に、該樹脂延伸フィルムの表面が被覆された面積比率が35%以上になっていることからも確かめることができる。 These phenomena are the ratio of the area where the surface of the stretched resin film of the present invention was coated after heating the surface of the stretched resin film of the present invention at a temperature of 110 ° C. and a printing speed of 3 inches / second using a melt thermal transfer recording apparatus. It can be confirmed from the fact that is 35% or more.
ポリオレフィン系樹脂はビカット軟化点が140℃を超えるプロピレン系樹脂であることが好ましい。 The polyolefin resin is preferably a propylene resin having a Vicat softening point exceeding 140 ° C.
さらにこれらフィルムには、フィラーの分散剤を含有することが好ましく、分散剤を0重量%を超えて20重量%以下含有することが好ましい。 Further, these films preferably contain a filler dispersant, and preferably contain more than 0% by weight and 20% by weight or less of the dispersant.
また、フィルム表面には各種印刷適性を向上させるために、下記一般式(a)で表されるポリイミン共重合体またはポリアミンポリアミドのエチレンイミン付加物よりなる塗布層を設けることが好ましい。 Moreover, in order to improve various printability on the film surface, it is preferable to provide a coating layer made of an ethyleneimine adduct of a polyimine copolymer represented by the following general formula (a) or polyamine polyamide.
さらに上記塗布層が水溶性のエポキシ系架橋剤、イソシアネート系架橋剤、ホルマリン系架橋剤、オキサゾリン系架橋剤、ポリアミンポリアミドのエピクロルヒドリン付加物の架橋剤、およびポリマー型帯電防止剤を含有することが好ましい。
Further, the coating layer preferably contains a water-soluble epoxy crosslinking agent, an isocyanate crosslinking agent, a formalin crosslinking agent, an oxazoline crosslinking agent, a crosslinking agent of an epichlorohydrin addition product of polyamine polyamide, and a polymer type antistatic agent. .
これら溶融熱転写記録用紙には各種印刷を行うことが可能であり、また他の樹脂フィルムや樹脂フィルム以外の材料と積層したり、粘着剤を介して剥離紙と積層したりして、ラベル用原紙として使用することもできる。 These melt heat transfer recording papers can be printed in various ways, and can be laminated with other resin films or materials other than resin films, or laminated with release paper via an adhesive to produce a base paper for labels It can also be used as
更に本発明は、上記溶融熱転写記録用紙、積層体またはラベル用原紙を用いた記録物も含む。 Furthermore, the present invention also includes a recorded matter using the above-described melt thermal transfer recording paper, laminated body, or label base paper.
本発明の溶融熱転写記録用紙は、熱溶融インクの転写性、密着性、耐水性が優れるだけでなく、更に耐溶剤擦過性にも優れている。特に有機溶剤にさらされた状態で擦過されても情報管理に支障をきたさず、種々の印刷性にも優れている。このような特徴を有することから、本発明の溶融熱転写記録用紙は広範な用途に供しうるものである。 The melt thermal transfer recording paper of the present invention is excellent not only in transferability, adhesion and water resistance of the hot melt ink, but also in solvent abrasion resistance. In particular, even if it is rubbed in a state exposed to an organic solvent, information management is not hindered and various printability is excellent. Because of such characteristics, the melt thermal transfer recording paper of the present invention can be used in a wide range of applications.
以下に本発明の溶融熱転写記録用紙について更に詳細に説明する。なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 The melt thermal transfer recording paper of the present invention will be described in detail below. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
[1]溶融熱転写記録用紙
(1)層構成
本発明の溶融熱転写記録用紙は単層であっても多層であっても良く、ベース層と表面層の2層構造であっても、ベース層の表裏面に表面層が存在する3層構造であっても、ベース層と表面層間に他の樹脂フィルム層が存在する多層構造であっても良い。また、延伸軸数は、3層構造では1軸/1軸/1軸、1軸/1軸/2軸、1軸/2軸/1軸、2軸/1軸/1軸、1軸/2軸/2軸、2軸/2軸/1軸、2軸/2軸/2軸等が挙げられ、それ以上の層構造の場合、延伸軸数は任意に組み合わせることが可能である。
[1] Melt Thermal Transfer Recording Paper (1) Layer Configuration The melt thermal transfer recording paper of the present invention may be a single layer or a multilayer, and may have a base layer and a surface layer, or a two-layer structure. Even a three-layer structure in which a surface layer exists on the front and back surfaces may be a multilayer structure in which another resin film layer exists between the base layer and the surface layer. In the three-layer structure, the number of stretching axes is 1 axis / 1 axis / 1 axis, 1 axis / 1 axis / 2 axis, 1 axis / 2 axis / 1 axis, 2 axis / 1 axis / 1 axis, 1 axis / Two axes / 2 axes, 2 axes / 2 axes / 1 axis, 2 axes / 2 axes / 2 axes, and the like can be mentioned. In the case of a layer structure having more than that, the number of stretching axes can be arbitrarily combined.
また本発明の溶融熱転写記録用紙は、他の熱可塑性樹脂フィルム、パルプ抄造紙、平織織布(ポンジー)または不織布(スパンボンド)と積層して積層品にしてもよく、必要により粘着剤層、離型紙を設けてもよい。その場合は樹脂延伸フィルムが最外層になるようにすればよい。 The melt thermal transfer recording paper of the present invention may be laminated with other thermoplastic resin film, pulp paper, plain woven fabric (pongy) or non-woven fabric (spunbond), and if necessary, an adhesive layer, Release paper may be provided. In that case, the stretched resin film may be the outermost layer.
(2)ビカット軟化点が140℃以下である熱可塑性樹脂
本発明に用いるJIS−K−7206−1999で測定したビカット軟化点が140℃以下である熱可塑性樹脂は、ビカット軟化点が好ましくは50〜130℃、更に好ましくは60〜125℃である。本発明の溶融熱転写記録用紙を構成する樹脂延伸フィルムは、該熱可塑性樹脂をポリオレフィン系樹脂100重量部に対して75重量部を超えて900重量部以下含有し、好ましくは100重量部〜700重量部含有し、更に好ましくは100重量部を超えて400重量部以下含有する。
(2) Thermoplastic resin having a Vicat softening point of 140 ° C. or lower The thermoplastic resin having a Vicat softening point of 140 ° C. or lower measured according to JIS-K-7206-1999 used in the present invention preferably has a Vicat softening point of 50 It is -130 degreeC, More preferably, it is 60-125 degreeC. The stretched resin film constituting the melt thermal transfer recording paper of the present invention contains the thermoplastic resin in an amount of more than 75 parts by weight and not more than 900 parts by weight, preferably 100 parts by weight to 700 parts by weight, based on 100 parts by weight of the polyolefin resin. Contained, more preferably more than 100 parts by weight and 400 parts by weight or less.
ビカット軟化点が140℃を超えると、溶融熱転写印字した際にサーマルヘッドの熱によるフィルム表面の可塑化変形が十分ではないので、延伸フィルムの表面の被覆面積比率が小さくなってしまう。このため、溶剤で擦過した後に容易に熱転写インクが溶け出してしまい、本発明の目的を達し得ない。 When the Vicat softening point exceeds 140 ° C., the plastic surface deformation of the film surface due to the heat of the thermal head is not sufficient when performing melt thermal transfer printing, and the ratio of the coated area of the stretched film surface becomes small. For this reason, the thermal transfer ink is easily dissolved after rubbing with a solvent, and the object of the present invention cannot be achieved.
また、これら熱可塑性樹脂の含有量が、ポリオレフィン系樹脂100重量部に対して75重量部未満では、同様に可塑化変形する樹脂分が少なく、フィルムの表面被覆面積比率が小さく、従って溶剤で擦過した後に熱転写インクが溶け出しやすい。また、熱可塑性樹脂の含有量がポリオレフィン系樹脂100重量部に対して900重量部を超えると、延伸時に、ロールやテンターなどの製造機器に貼り付いたり、シートの破断が起きるため延伸フィルムの成形が困難になる。 Further, when the content of these thermoplastic resins is less than 75 parts by weight with respect to 100 parts by weight of the polyolefin-based resin, the amount of the resin that is similarly plastically deformed is small, and the ratio of the surface coverage area of the film is small. After that, the thermal transfer ink is likely to melt. In addition, when the thermoplastic resin content exceeds 900 parts by weight with respect to 100 parts by weight of the polyolefin resin, a stretched film is formed because it sticks to a manufacturing device such as a roll or a tenter or the sheet breaks during stretching. Becomes difficult.
ビカット軟化点が140℃以下である熱可塑性樹脂としては、エチレンやブテンをコモノマーとして含有するランダムプロピレン共重合体、密度が0.940〜0.970g/cm3の高密度ポリエチレン、密度が0.900〜0.935g/cm3の低密度ポリエチレン、密度が0.880〜0.940g/cm3の直鎖状低密度ポリエチレン、エチレン・酢酸ビニル共重合体等のポリエチレン系樹脂、エチレン・アクリル酸共重合体、エチレン・アクリル酸アルキルエステル共重合体、エチレン・メタクリル酸アルキルエステル共重合体、エチレン・メタクリル酸共重合体の金属塩(Zn、Al、Li、K、Naなど)等のアクリル酸系樹脂、アイオノマー、ポリブテン−1、ポリブタジエン、メタクリル樹脂などを使用することができる。これらのなかでも耐薬品性およびコスト等の面から高密度ポリエチレン、低密度ポリエチレン、ランダムポリプロピレン共重合体、アクリル酸系樹脂が好ましく、特に高密度ポリエチレン、低密度ポリエチレンが好ましい。 As a thermoplastic resin having a Vicat softening point of 140 ° C. or less, a random propylene copolymer containing ethylene or butene as a comonomer, a high density polyethylene having a density of 0.940 to 0.970 g / cm 3 , and a density of 0.8. 900~0.935g / cm 3 low-density polyethylene, linear low density polyethylene having a density of 0.880~0.940g / cm 3, a polyethylene-based resins such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid Acrylic acids such as copolymers, ethylene / acrylic acid alkyl ester copolymers, ethylene / methacrylic acid alkyl ester copolymers, metal salts of ethylene / methacrylic acid copolymers (Zn, Al, Li, K, Na, etc.) Resin, ionomer, polybutene-1, polybutadiene, methacrylic resin, etc. can be used. Among these, high-density polyethylene, low-density polyethylene, random polypropylene copolymer, and acrylic resin are preferable from the viewpoint of chemical resistance and cost, and high-density polyethylene and low-density polyethylene are particularly preferable.
(3)ポリオレフィン系樹脂
本発明に用いるポリオレフィン系樹脂としては、JIS−K−7206−1999で測定したビカット軟化点が140℃を超えるプロピレン系樹脂を用いることが好ましい。 ビカット軟化点が140℃を超えるプロピレン系樹脂を用いることによって、延伸後のフィルム表面に凸凹や空隙が形成されやすくなり、表面粗さが適度に大きくなって、サーマルヘッドの加熱により溶融した熱転写インクが入り込む部分が多くなるという利点がある。
(3) Polyolefin-based resin As the polyolefin-based resin used in the present invention, it is preferable to use a propylene-based resin having a Vicat softening point exceeding 140 ° C. measured according to JIS-K-7206-1999. By using a propylene-based resin having a Vicat softening point exceeding 140 ° C., irregularities and voids are easily formed on the stretched film surface, the surface roughness becomes moderately large, and the thermal transfer ink is melted by heating the thermal head. There is an advantage that there are more parts to enter.
プロピレン系樹脂としては、プロピレンを単独重合させたアイソタクティック重合体およびシンジオタクティック重合体が好ましい。また、エチレン、1−ブテン、1−ヘキセン、1−ヘプテン、4−メチル−1−ペンテン等のα−オレフィンとプロピレンとを共重合体させた、様々な立体規則性を有するポリプロピレンを主成分とする共重合体を使用することもできる。共重合体は2元系でも3元系以上の多元系でもよい。上記のポリオレフィン系樹脂の中から1種を選択して単独で使用してもよいし、2種以上を選択して組み合わせて使用してもよい。 As the propylene-based resin, an isotactic polymer and a syndiotactic polymer obtained by homopolymerizing propylene are preferable. In addition, the main component is polypropylene having various stereoregularities obtained by copolymerizing propylene with an α-olefin such as ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene. Copolymers can also be used. The copolymer may be a binary system or a multi-system of ternary system or higher. One of these polyolefin resins may be selected and used alone, or two or more may be selected and used in combination.
(4)無機微細粉末
本発明に用いる無機微細粉末としては、平均粒径が通常0.05〜10μm、好ましくは0.1〜7μm、より好ましくは0.3μm〜5μm、特に好ましくは0.4μm〜2.5μm、最も好ましくは0.5μm〜1.5μmのものが使用できる。平均粒径が0.05μm未満ではビカット軟化点が140℃以下である熱可塑性樹脂およびポリオレフィン系樹脂との溶融混練時に均一に無機微細粉末が分散しなかったり、無機微細粉末が二次凝集したり、吸着水分の影響により水分発泡を起こす場合がある。また平均粒径が10μmを超えるとフィルムの強度が低下し易い傾向があり、さらに印刷インキや熱溶融性インクの転移濃度が低くなる傾向もある。無機微細粉末としては、具体的には、炭酸カルシウム、アルミノシリケート、アルミナ、焼成クレイ、シリカ、けいそう土、タルク、酸化チタン、硫酸バリウムなどを使用することができる。これらの中でも、コストの面から炭酸カルシウムを使用することが好ましい。炭酸カルシウムの中でも、平均粒径が小さく、かつ粒度分布が小さく、さらに粗大粒子が除去されたもの(例えば、丸尾カルシウム(株)製の「カルテックス7」を例示できる)は印刷インキの転移濃度が向上する点で好ましい。
(4) Inorganic fine powder The inorganic fine powder used in the present invention has an average particle size of usually 0.05 to 10 μm, preferably 0.1 to 7 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.4 μm. One having a thickness of ˜2.5 μm, most preferably 0.5 μm to 1.5 μm can be used. When the average particle size is less than 0.05 μm, the inorganic fine powder does not uniformly disperse during the melt-kneading with the thermoplastic resin and the polyolefin resin having a Vicat softening point of 140 ° C. or less, or the inorganic fine powder is secondary agglomerated. In some cases, moisture foaming may occur due to the influence of adsorbed moisture. On the other hand, if the average particle size exceeds 10 μm, the strength of the film tends to be lowered, and the transfer concentration of the printing ink or the hot-melt ink tends to be lowered. Specifically, calcium carbonate, aluminosilicate, alumina, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, etc. can be used as the inorganic fine powder. Among these, it is preferable to use calcium carbonate from the viewpoint of cost. Among calcium carbonates, those having a small average particle size and a small particle size distribution and having coarse particles removed (for example, “Caltex 7” manufactured by Maruo Calcium Co., Ltd.) have a transfer concentration of printing ink. It is preferable in terms of improvement.
本発明に使用する無機微細粉末の粒径は、粒子計測装置、レーザー回折式粒子計測装置「マイクロトラック」((株)日機装製、商品名)により測定した累積で50%にあたる粒子径(累積50%粒径)により測定した。 The particle size of the inorganic fine powder used in the present invention is 50% of the cumulative particle size measured by a particle measuring device, a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Nikkiso Co., Ltd.). % Particle size).
(5)有機フィラー
本発明に用いる有機フィラーとしては、分散後の平均粒径が通常0.05〜10μm、好ましくは0.1〜7μm、より好ましくは0.3〜5μmのものが使用できる。
(5) Organic filler As the organic filler used in the present invention, those having an average particle diameter after dispersion of usually 0.05 to 10 μm, preferably 0.1 to 7 μm, more preferably 0.3 to 5 μm can be used.
具体的にはポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ナイロン−6、ナイロン−6,6、環状オレフィンの単独重合体および環状オレフィンとエチレンの共重合体等の融点が160℃〜300℃、ないしはガラス転移温度が160℃〜280℃を有するものを挙げることができる。 Specifically, the melting points of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic olefin homopolymers and copolymers of cyclic olefin and ethylene, etc. are 160 ° C. to 300 ° C. or glass. Mention may be made of those having a transition temperature of 160 ° C. to 280 ° C.
これら無機微細粉末および有機フィラーはそれぞれ単独でもまた組み合わせて使用することもできる。樹脂延伸フィルムにおけるこれらの含有量は30〜75重量%、より好ましくは40〜65重量%である。30重量%未満ではフィルム表面に凹凸や空隙が形成されにくく、表面粗さが小さく、サーマルヘッドの加熱により溶融した熱転写インクが入り込む部分が少なく、表面が被覆されても封じ込められるインク量が少なくて、本発明の目的を達し得ない。また75重量%を超えると、溶融熱転写記録用紙表面の強度が低下し、もろく傷つきやすい表面となり、本発明の目的を達し得ない。 These inorganic fine powders and organic fillers can be used alone or in combination. These contents in the stretched resin film are 30 to 75% by weight, more preferably 40 to 65% by weight. If it is less than 30% by weight, unevenness and voids are hardly formed on the film surface, the surface roughness is small, there are few portions where the thermal transfer ink melted by heating of the thermal head enters, and the amount of ink that can be contained is small even if the surface is covered. The object of the present invention cannot be achieved. On the other hand, if it exceeds 75% by weight, the strength of the surface of the melt thermal transfer recording paper is lowered and the surface becomes brittle and easily damaged, and the object of the present invention cannot be achieved.
(6)分散剤
本発明で用いることができる分散剤としては、例えば酸変性ポリオレフィン、シラノール変性ポリオレフィンなどが挙げられる。この中でも酸変性ポリオレフィンが好ましい。酸変性ポリオレフィンとしては、無水マレイン酸をランダム共重合もしくはグラフト共重合した無水酸基含有ポリオレフィン、あるいはメタクリル酸、アクリル酸などの不飽和カルボン酸をランダム共重合もしくはグラフト共重合したカルボン酸基含有ポリオレフィン、グリシジルメタクリレートをランダム共重合もしくはグラフト共重合したエポキシ基含有ポリオレフィンなどが挙げられる。具体例としては、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリエチレン、アクリル酸変性ポリプロピレン、エチレン・メタクリル酸ランダム共重合体、エチレン・グリシジルメタクリレートランダム共重合体、エチレン・グリシジルメタクリレートグラフト共重合体、グリシジルメタクリレート変性ポリプロピレンなどが挙げられ、なかでも好ましくは無水マレイン酸変性ポリプロピレンおよび無水マレイン酸変性ポリエチレンである。
(6) Dispersant Examples of the dispersant that can be used in the present invention include acid-modified polyolefin and silanol-modified polyolefin. Among these, acid-modified polyolefin is preferable. Examples of the acid-modified polyolefin include a hydroxyl-free polyolefin containing a random copolymerization or graft copolymerization of maleic anhydride, or a carboxylic acid group-containing polyolefin obtained by a random copolymerization or graft copolymerization of an unsaturated carboxylic acid such as methacrylic acid or acrylic acid, Examples thereof include an epoxy group-containing polyolefin obtained by random copolymerization or graft copolymerization of glycidyl methacrylate. Specific examples include maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, acrylic acid modified polypropylene, ethylene / methacrylic acid random copolymer, ethylene / glycidyl methacrylate random copolymer, ethylene / glycidyl methacrylate graft copolymer, glycidyl. Examples include methacrylate-modified polypropylene, among which maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene are preferable.
分散剤を配合することにより、無機微細粉末または有機フィラーの分散性が向上するためか特に溶融熱転写インクの耐溶剤擦過性が向上する。 By blending a dispersant, the dispersibility of the inorganic fine powder or the organic filler is improved, and in particular, the solvent scuff resistance of the melt thermal transfer ink is improved.
無水マレイン酸変性ポリプロピレンおよび無水マレイン酸変性ポリエチレンの具体例としては、三菱化学(株)のモディックAP[P513V]、AP[M513](商品名)、三洋化成(株)のYumex1001、1010(商品名)やYumex2000(商品名)、三井・デュポンポリケミカル(株)のHPR[VR101](商品名)が挙げられる。 Specific examples of maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene include Mitsubishi Chemical's Modic AP [P513V], AP [M513] (trade name), and Sanyo Chemical Co., Ltd. Yumex1001, 1010 (trade name) ), Yumex2000 (trade name), and Mitsui DuPont Polychemical Co., Ltd. HPR [VR101] (trade name).
酸変性ポリオレフィンの酸変性率としては、0.01〜20%が好ましく、さらには0.05〜15%がより好ましく、0.1〜10%がさらに好ましい。 The acid modification rate of the acid-modified polyolefin is preferably 0.01 to 20%, more preferably 0.05 to 15%, and further preferably 0.1 to 10%.
酸変性率が0.01%未満では、無機微細粉末の熱可塑性樹脂中への分散効果が不十分になる傾向があり、20%を超えると酸変性ポリオレフィンの耐熱性が低くなりすぎるため、熱成形時に着色しやすくなる傾向がある。 If the acid modification rate is less than 0.01%, the dispersion effect of the inorganic fine powder in the thermoplastic resin tends to be insufficient, and if it exceeds 20%, the heat resistance of the acid-modified polyolefin becomes too low. There is a tendency to be easily colored during molding.
分散剤の含有量としては、好ましくは0重量%を超えて20重量%以下であり、より好ましくは0重量%を超えて10重量%以下であり、更に好ましくは0.1〜5重量%、特に好ましくは0.15〜2重量%未満、最も好ましくは0.2〜1.7重量%である。 The content of the dispersant is preferably more than 0% by weight and 20% by weight or less, more preferably more than 0% by weight and 10% by weight or less, still more preferably 0.1 to 5% by weight, Particularly preferred is 0.15 to less than 2% by weight, and most preferred is 0.2 to 1.7% by weight.
分散剤の含有量が20重量%を超えては、成形時メヤニ(樹脂組成物の熱劣化物など)の発生が多くなり、また延伸性が大きく低下して成形時における延伸切れが多くなる傾向がある。 When the content of the dispersant exceeds 20% by weight, the occurrence of sag (such as thermally deteriorated resin composition) at the time of molding increases, and the stretchability tends to greatly decrease and the number of stretch breaks at the time of molding tends to increase. There is.
(7)滑剤
滑剤は、本発明の樹脂延伸フィルムの成形性を高める目的で使用する。押出機内で溶融樹脂の分子間摩擦力あるいは押出機の内壁と溶融樹脂間の摩擦力を減少させて流動性を高める効果を有する。使用量は通常0.01〜4重量%の範囲内である。具体的には、オレイン酸やステアリン酸等の高級脂肪酸、およびそれらの金属塩、高級アルコール、多価アルコール、ポリグリコール、ポリグリセロール等のアルコール類、脂肪酸と脂肪族アルコール、芳香族アルコール、ポリグリコール等とのエステル類、天然ワックス、脂肪酸アミド等を使用することができる。
(7) Lubricant A lubricant is used for the purpose of improving the moldability of the stretched resin film of the present invention. It has the effect of increasing fluidity by reducing the intermolecular frictional force of the molten resin in the extruder or the frictional force between the inner wall of the extruder and the molten resin. The amount used is usually in the range of 0.01 to 4% by weight. Specifically, higher fatty acids such as oleic acid and stearic acid, and metal salts thereof, alcohols such as higher alcohols, polyhydric alcohols, polyglycols, polyglycerols, fatty acids and aliphatic alcohols, aromatic alcohols, polyglycols Etc., natural waxes, fatty acid amides and the like can be used.
(8)その他の助剤
本発明の溶融熱転写記録用紙を構成する樹脂延伸フィルムには、必要に応じて安定剤、光安定剤などを添加することができる。
(8) Other auxiliaries A stabilizer, a light stabilizer, etc. can be added to the stretched resin film constituting the melt thermal transfer recording paper of the present invention as required.
安定剤を添加する場合は、通常0.001〜1重量%の範囲内で添加する。具体的には、立体障害フェノール系、リン系、アミン系の安定剤などを使用することができる。 When a stabilizer is added, it is usually added within a range of 0.001 to 1% by weight. Specifically, sterically hindered phenol-based, phosphorus-based, amine-based stabilizers and the like can be used.
光安定剤を添加する場合は、通常0.001〜1重量%の範囲内で添加する。光安定剤としては、具体的には、立体障害アミン系、ベンゾトリアゾール系、ベンゾフェノン系の光安定剤などを使用することができる。 When a light stabilizer is added, it is usually added within a range of 0.001 to 1% by weight. As the light stabilizer, specifically, a sterically hindered amine-based, benzotriazole-based, benzophenone-based light stabilizer, or the like can be used.
(9)成形方法
本発明の溶融熱転写記録用紙の成形方法は特に限定されないため、公知の方法の中から適宜選択して成形することができる。例えば、スクリュー型押出機に接続された単層または積層のTダイやIダイを使用して溶融樹脂をシート状に押し出すキャスト成形、カレンダー成形、圧延成形、インフレーション成形、熱可塑性樹脂と有機溶媒やオイルとの混合物をキャスト成形またはカレンダー成形した後に溶媒やオイルを除去する方法などを用いて成形することができる。
(9) Forming Method The forming method of the melt thermal transfer recording paper of the present invention is not particularly limited, and can be suitably selected from known methods and formed. For example, cast molding, calender molding, rolling molding, inflation molding, thermoplastic resin and organic solvent, which extrude molten resin into a sheet using a single layer or laminated T die or I die connected to a screw type extruder After the mixture with oil is cast or calendered, it can be molded using a method of removing the solvent or oil.
延伸方法は、通常用いられている種々の方法のいずれかによって行う。 The stretching method is performed by any of various methods that are usually used.
具体例としては、ロール群の周速差を利用した縦延伸、テンターオーブンを使用した横延伸、圧延、テンターオーブンとリニアモーターの組み合わせによる同時二軸延伸などを用いることができる。 As specific examples, longitudinal stretching using a difference in peripheral speed between rolls, transverse stretching using a tenter oven, rolling, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor, and the like can be used.
延伸の際の温度は、用いるビカット軟化点が140℃以下である熱可塑性樹脂のビカット軟化点以上でポリオレフィン系樹脂の融点以下(好ましくは融点の2〜20℃低い温度)の温度範囲内で行うことができる。また延伸速度は20〜350m/分にするのが好ましい。 The temperature during stretching is within the temperature range of the Vicat softening point of the thermoplastic resin having a Vicat softening point of 140 ° C. or lower and below the melting point of the polyolefin resin (preferably 2-20 ° C. lower than the melting point). be able to. The stretching speed is preferably 20 to 350 m / min.
延伸倍率は用いるポリオレフィン系樹脂およびビカット軟化点が140℃以下である熱可塑性樹脂の特性等を考慮して適宜決定する。一方向に延伸する場合は2〜12倍、好ましくは3〜10倍、より好ましくは4〜8倍であり、二軸延伸の場合は面積倍率で4〜80倍、好ましくは10〜65倍、より好ましくは20〜50倍である。 The draw ratio is appropriately determined in consideration of the characteristics of the polyolefin resin used and the thermoplastic resin having a Vicat softening point of 140 ° C. or lower. In the case of stretching in one direction, it is 2 to 12 times, preferably 3 to 10 times, more preferably 4 to 8 times. In the case of biaxial stretching, the area magnification is 4 to 80 times, preferably 10 to 65 times, More preferably, it is 20 to 50 times.
(10)肉厚
本発明の溶融熱転写記録用紙の肉厚は、0.5μm〜1000μm、好ましくは1μm〜500μmである。
(10) Thickness The thickness of the melt thermal transfer recording paper of the present invention is 0.5 μm to 1000 μm, preferably 1 μm to 500 μm.
これらを成形と同時に共押出しや押出しラミネートにより積層したり、また成形後に他の樹脂フィルムや樹脂フィルム以外の材料と積層したりして得た積層体の肉厚は、好ましくは20μm〜3000μm、より好ましくは30μm〜2000μmである。 The thickness of the laminate obtained by laminating these by co-extrusion or extrusion laminating at the same time as molding, or by laminating with other resin films or materials other than resin films after molding, is preferably 20 μm to 3000 μm, more Preferably it is 30 micrometers-2000 micrometers.
[2]塗布剤
(1)構成素材
(i)成分
本発明の溶融熱転写記録用紙に(i)成分であるポリイミン系重合体またはポリアミンポリアミドのエチレンイミン付加物からなる塗布剤層を設けると印刷インクの密着性、特に紫外線硬化型インクの密着性を改良することができる。このような化合物としては、ポリエチレンイミン、ポリ(エチレンイミン−尿素)およびポリアミンポリアミドのエチレンイミン付加物、又はこれらのアルキル変性体、シクロアルキル変性体、アリール変性体、アリル変性体、アラルキル変性体、アルキラル変性体、ベンジル変性体、シクロペンチル変性体、もしくは脂肪族環状炭化水素変性体、ないしはこれらの水酸化物であり、これらを単独または数種類複合させたものを挙げることができる。
[2] Coating Agent (1) Constituent Material (i) Component Printing ink when a coating layer made of an ethyleneimine adduct of polyimine polymer or polyamine polyamide as component (i) is provided on the melt thermal transfer recording paper of the present invention. In particular, the adhesiveness of the ultraviolet curable ink can be improved. Examples of such compounds include polyethyleneimine, poly (ethyleneimine-urea) and polyamine polyamide ethyleneimine adducts, or alkyl-modified products, cycloalkyl-modified products, aryl-modified products, allyl-modified products, aralkyl-modified products, Alchiral modified products, benzyl modified products, cyclopentyl modified products, aliphatic cyclic hydrocarbon modified products, or hydroxides thereof may be used alone or in combination of several kinds.
これらの中でも、上記一般式(a)で表されるポリイミン系重合体を使用することが、オフセットインクとの密着性、転移性の向上の観点から好ましい。ここで、ポリエチレンイミンの重合度は任意のものが使用されるが、好ましくは20〜3,000のものである。 Among these, it is preferable to use the polyimine-based polymer represented by the general formula (a) from the viewpoint of improving the adhesion to the offset ink and the transferability. Here, any degree of polymerization of polyethyleneimine is used, but it is preferably 20 to 3,000.
(ii)成分
上記(i)成分に、(ii)成分である架橋剤としてエポキシ系、イソシアネート系、ホルマリン系、オキサゾリン系の水溶性の樹脂を加えると印刷インクとの耐水密着性を更に改良することができる。架橋剤としては、特にビスフェノールA−エピクロルヒドリン樹脂、ポリアミンポリアミドのエピクロルヒドリン樹脂、脂肪族エポキシ樹脂、エポキシノボラック樹脂、脂環式エポキシ樹脂、臭素化エポキシ樹脂が好ましく、最も好ましくは、ポリアミンポリアミドのエピクロルヒドリン付加物、あるいは単官能乃至多官能のグリシジルエーテル、グリシジルエステル類が挙げられる。
(Ii) Component Addition of an epoxy-based, isocyanate-based, formalin-based, or oxazoline-based water-soluble resin to the above-mentioned component (i) as a crosslinking agent that is the component (ii) further improves the water-resistant adhesion to the printing ink. be able to. As the crosslinking agent, bisphenol A-epichlorohydrin resin, polyamine polyamide epichlorohydrin resin, aliphatic epoxy resin, epoxy novolac resin, alicyclic epoxy resin, brominated epoxy resin are preferable, and most preferably, epiamine hydrin adduct of polyamine polyamide Or monofunctional to polyfunctional glycidyl ethers and glycidyl esters.
(iii)成分
上記(i)、(ii)成分に、(iii)成分であるポリマー型帯電防止剤を加えることにより、埃の付着や印字および印刷時の帯電によるトラブルを軽減することができる。ポリマー型帯電防止剤としては、カチオン型、アニオン型、両性型、ノニオン型などが使用可能である。カチオン型としては、アンモニウム塩構造やホスホニウム塩構造を有するものが挙げられる。アニオン型としては、スルホン酸、リン酸、カルボン酸等のアルカリ金属塩、例えば、アクリル酸、メタクリル酸、(無水)マレイン酸などのアルカリ金属塩(例としてはリチウム塩、ナトリウム塩、カリウム塩等)構造を分子構造中に有するものが挙げられる。
(Iii) Component By adding the polymer type antistatic agent as the component (iii) to the above components (i) and (ii), troubles due to dust adhesion and charging during printing and printing can be reduced. As the polymer type antistatic agent, a cation type, an anion type, an amphoteric type, a nonionic type and the like can be used. Examples of the cationic type include those having an ammonium salt structure or a phosphonium salt structure. Anionic types include alkali metal salts such as sulfonic acid, phosphoric acid and carboxylic acid, for example, alkali metal salts such as acrylic acid, methacrylic acid and (anhydrous) maleic acid (for example, lithium salt, sodium salt, potassium salt, etc. ) Having a structure in the molecular structure.
両性型としては、上記のカチオン型とアニオン型の両方の構造を同一分子中に含有するもので、例としてはベタイン型が挙げられる。ノニオン型としては、アルキレンオキシド構造を有するエチレンオキシド重合体や、エチレンオキシド重合成分を分子鎖中に有する重合体が挙げられる。その他、ホウ素を分子構造中に有するポリマー型帯電防止剤も例として挙げることができる。これらの中で好ましくは窒素含有ポリマー型帯電防止剤であり、より好ましくは第三級窒素または第四級窒素含有アクリル系ポリマーである。 尚、本発明の塗布剤には、必要に応じて消泡剤、その他の助剤等を印刷および熱転写特性を損なわない範囲で添加しても良い。 The amphoteric type contains both the cation type and the anion type structures in the same molecule, and examples thereof include a betaine type. Examples of the nonionic type include an ethylene oxide polymer having an alkylene oxide structure and a polymer having an ethylene oxide polymerization component in a molecular chain. In addition, a polymer type antistatic agent having boron in the molecular structure can be given as an example. Among these, nitrogen-containing polymer type antistatic agents are preferable, and tertiary nitrogen or quaternary nitrogen-containing acrylic polymers are more preferable. In addition, you may add to a coating agent of this invention in the range which does not impair printing and a thermal transfer characteristic as needed, such as an antifoamer and another adjuvant.
(2)量比
本発明に使用する塗布剤は(i)成分100重量部に対し、(ii)、(iii)成分は下記の割合である。
(ii)成分 通常0〜400重量部、好ましくは50〜300重量部
(iii)成分 通常0〜800重量部、好ましくは25〜500重量部
(2) Quantity ratio The coating agent used for this invention is the following ratio of (ii) and (iii) component with respect to 100 weight part of (i) component.
Component (ii) Usually 0 to 400 parts by weight, preferably 50 to 300 parts by weight (iii) Component Usually 0 to 800 parts by weight, preferably 25 to 500 parts by weight
(3)塗布剤の形態
上記塗布剤の各成分は、水或いはメチルアルコール、エチルアルコール、イソプロピルアルコール、アセトン、メチルエチルケトン、酢酸エチル、トルエン、キシレン等の溶媒に溶解させてから用いるものであるが、中でも水溶液の形態で用いるのが一般的である。溶液濃度は通常0.5〜40重量%、好ましくは1〜20重量%である。
(3) Form of coating agent Each component of the coating agent is used after being dissolved in water or a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, xylene, In particular, it is generally used in the form of an aqueous solution. The solution concentration is usually 0.5 to 40% by weight, preferably 1 to 20% by weight.
(4)塗布
(a)塗布量
塗布剤の溶融熱転写記録用紙への塗布量は、固形分量で通常0.01〜3g/m2、好ましくは0.01〜1g/m2、より好ましくは0.02〜0.3g/m2である。0.01g/m2未満では充分な帯電防止性能が得られず印刷時のフィードトラブルが懸念されるだけでなく、印刷インキの密着性も得られなくなる傾向がある。また3g/m2超では乾燥性が劣るばかりでなく、3g/m2で既に十分な性能が得られるためコストアップになる傾向がある。
(4) Coating (a) Coating amount The coating amount of the coating agent on the melt thermal transfer recording paper is usually 0.01 to 3 g / m 2 , preferably 0.01 to 1 g / m 2 , more preferably 0 in terms of solid content. 0.02 to 0.3 g / m 2 . If it is less than 0.01 g / m 2 , sufficient antistatic performance cannot be obtained and there is a concern not only about feed troubles during printing, but also there is a tendency that adhesion of printing ink cannot be obtained. In the 3 g / m 2 exceeds not only the drying property is inferior, is already sufficient performance in 3 g / m 2 tend to be cost for the resulting.
(b)塗布装置
塗布装置としては、ロールコーター、ブレードコーター、バーコーター、エアーナイフコーター、サイズプレスコーター、グラビアコーター、ダイコーター、リップコーター、スプレーコーター等を利用した塗布装置を使用することができる。
(B) Coating device As the coating device, a coating device using a roll coater, blade coater, bar coater, air knife coater, size press coater, gravure coater, die coater, lip coater, spray coater or the like can be used. .
本発明の溶融熱転写記録用紙には、その表面に塗布層を形成する前に、表面酸化処理としてフィルムに一般的に使用されるコロナ放電処理、フレーム処理、プラズマ処理、グロー放電処理、オゾン処理などを単独または組み合わせて使用する。これらのうちで好ましくはコロナ処理、フレーム処理であり、処理量はコロナ処理の場合、600〜12,000J/m2(10〜200W・分/m2)、好ましくは1,200〜9,000J/m2(20〜180W・分/m2)、フレーム処理の場合、8,000〜200,000J/m2、好ましくは20,000〜100,000J/m2が用いられる。 The melt thermal transfer recording paper of the present invention has a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, an ozone treatment and the like that are generally used for a film as a surface oxidation treatment before forming a coating layer on the surface. Are used alone or in combination. Of these, corona treatment and frame treatment are preferred, and in the case of corona treatment, the treatment amount is 600 to 12,000 J / m 2 (10 to 200 W · min / m 2 ), preferably 1,200 to 9,000 J. / m 2 (20~180W · min / m 2), when the frame processing, 8,000~200,000J / m 2, preferably 20,000~100,000J / m 2 is used.
[3]溶融熱転写印字
(1)溶融型ワックスインクリボン
溶融型ワックスインクリボンは、ベースフィルムとしてサーマルヘッドが接する側の面に耐熱樹脂コート(1〜3μm)を施したポリエステルフィルム(3〜10μm)を使い、反対面に常温では固体、加熱すると急激に粘度が低下する熱溶融インクを3〜8μmの厚さに均一にグラビアまたはロールコーティング法でコートしたものである。
[3] Melting thermal transfer printing (1) Melting wax ink ribbon The melting wax ink ribbon is a polyester film (3 to 10 μm) having a heat-resistant resin coat (1 to 3 μm) applied to the surface on the side contacting the thermal head as a base film. Is used, and the opposite surface is coated with a hot melt ink that is solid at normal temperature and whose viscosity rapidly decreases when heated to a thickness of 3 to 8 μm by gravure or roll coating.
ワックスインクリボンのインクの成分は、一般的に10〜20重量%の顔料、60〜80重量%のワックス系バインダーおよび10〜20重量%の柔軟剤、分散剤などの各種添加剤から構成されている。 The ink component of the wax ink ribbon is generally composed of various additives such as 10 to 20% by weight pigment, 60 to 80% by weight wax-based binder, and 10 to 20% by weight softener and dispersant. Yes.
ワックス系バインダーはブロードな融点と融点以上の温度で急激に粘度が低下する特性を示し、加熱領域に多少の温度ムラがあっても一様なインク転移が可能なものである。具体的にはパラフィンワックス、エステルワックスやカルナバワックス等が挙げられる。 The wax-based binder exhibits a broad melting point and a characteristic that the viscosity rapidly decreases at a temperature equal to or higher than the melting point, and is capable of uniform ink transfer even if there is some temperature unevenness in the heating region. Specific examples include paraffin wax, ester wax and carnauba wax.
(2)印字条件
本発明の溶融熱転写記録用紙に対する印字方法は特に制限されず、一般に溶融熱転写記録装置を使用して行うことができる。具体的な印字条件については、後述する試験例1を参考にすることができる。
(2) Printing conditions The printing method for the melt thermal transfer recording paper of the present invention is not particularly limited, and can generally be performed using a melt thermal transfer recording apparatus. For specific printing conditions, Test Example 1 described later can be referred to.
本発明の溶融熱転写記録用紙は、後述する試験例2に記載の溶剤擦過後のANSI GRADEがA〜Cであり、好ましくはB以上である。 The melt thermal transfer recording paper of the present invention has an ANSI GRADE after solvent rubbing described in Test Example 2 to be described later, A to C, preferably B or more.
[4]表面物性
(1)空印字後の表面被覆面積比率
本明細書における表面被覆面積比率は、以下の手順により測定した値である。すなわち、溶融熱転写記録装置を用い熱転写記録用紙の表面を直接サーマルヘッドで全面空印字した後のフィルムの任意の一部を切り取り、観察試料台に貼り付け、その観察面に金蒸着して日立製作所(株)製の走査型顕微鏡「S−2400」(商品名)を使用して倍率2000倍にて表面を写真撮影し、サーマルヘッドの熱により表面が被覆された部分をトレーシングフィルムにトレースして塗りつぶした図を画像解析装置「型式ルーゼックスIID」(ニレコ(株)製 商品名)で画像処理を行い、樹脂延伸フィルムの表面被覆面積比率を測定する。
[4] Surface physical properties (1) Surface coverage area ratio after blank printing The surface coverage area ratio in the present specification is a value measured by the following procedure. In other words, using a fusion thermal transfer recording device, the surface of the thermal transfer recording paper is directly blank printed with the thermal head, and an arbitrary part of the film is cut out and pasted on the observation sample stage, and gold is deposited on the observation surface. Using a scanning microscope “S-2400” (trade name) manufactured by Co., Ltd., the surface was photographed at a magnification of 2000 times, and the portion of the surface covered by the heat of the thermal head was traced to the tracing film. The image that has been painted is subjected to image processing with an image analysis apparatus “Model Luzex IID” (trade name, manufactured by Nireco Corporation), and the surface coverage area ratio of the stretched resin film is measured.
本発明の溶融熱転写記録用紙を溶融熱転写記録装置にて空印字後の表面被覆面積比率は好ましくは35%以上、より好ましくは40%以上、さらに好ましくは50%〜100%である。 The surface coverage area ratio of the melt thermal transfer recording paper of the present invention after empty printing with the melt thermal transfer recording apparatus is preferably 35% or more, more preferably 40% or more, and further preferably 50% to 100%.
ビカット軟化点が140℃以下である熱可塑性樹脂は、溶融熱転写印字した際にサーマルヘッドの熱によりフィルム表面の可塑化変形がおこり、熱溶融インクと融着する為に有機溶剤にさらされた状態で擦過した後もインクの溶けだしが少なくなる。 A thermoplastic resin with a Vicat softening point of 140 ° C. or lower undergoes plasticization deformation of the film surface due to the heat of the thermal head during fusion thermal transfer printing, and is exposed to an organic solvent for fusing with the hot melt ink Even after rubbing, the ink melts less.
ただし、表面被覆面積比率が35%以上を満たす場合でも、無機微細粉末および/または有機フィラーが30重量%未満では、熱転写前のフィルム表面の凹凸や空隙が十分でないために、熱溶融インクがこれらの凹凸や空隙に入り込みが不十分であり、有機溶剤の擦過性は良くない。 However, even when the surface coating area ratio satisfies 35% or more, if the inorganic fine powder and / or the organic filler is less than 30% by weight, the unevenness and voids on the film surface before thermal transfer are not sufficient, so that the hot-melt ink is used. Insufficient penetration of the irregularities and voids of the organic solvent, and the scratching property of the organic solvent is not good.
(2)中心線平均粗さ(Ra)
本明細書における中心線平均粗さ(Ra)は、JIS−B−0601−2001に準拠し、小坂研究所製の三次元粗さ測定機SE−3AK(商品名)と解析装置Model SPA−11(商品名)により測定される。
(2) Centerline average roughness (Ra)
The centerline average roughness (Ra) in this specification is based on JIS-B-0601-2001, and is a three-dimensional roughness measuring machine SE-3AK (trade name) manufactured by Kosaka Laboratory and an analyzer Model SPA-11. It is measured by (trade name).
本発明の溶融熱転写記録用紙の中心線平均粗さ(Ra)は0.4〜2.5μmであり、0.45〜2.0μmであることが好ましく、0.5〜0.8μmであることが特に好ましい。 The center line average roughness of the melt thermal transfer recording sheet of the present invention (Ra) is Ri 0.4~2.5μm der, it is good Mashiku is 0.45~2.0Myuemu, 0.5 to 0.8 It is particularly preferred that
中心線平均粗さが0.4μm未満では、フィルム表面に微細な凹凸が形成されず、サーマルヘッドの加熱により溶融した熱転写インクが入り込む部分が少なく、封じ込められるインク量が少なく本発明の目的を達し得ない。また鋭利なもので擦った際のスクラッチ性が劣ることもある。また中心線平均粗さが2.5μmを超えると、印刷インキや溶融熱転写インクの転移性が劣り、印字が欠けたりし、目的とする印刷濃度が得られない。 When the average roughness of the center line is less than 0.4 μm, fine irregularities are not formed on the film surface, there are few portions where the thermal transfer ink melted by the heating of the thermal head enters, and the amount of ink contained is small and the object of the present invention is achieved. The resulting stomach. In addition, the scratch property may be inferior when rubbed with a sharp object. Further, when the centerline average roughness exceeds 2.5 [mu] m, poor metastatic printing inks or melt thermal transfer ink, printing was chipped, not be obtained print density of interest.
[5]積層
本発明の積層方法は特に限定されず、公知の種々の方法が使用できる。具体例としては、フィードブロック、マルチマニホールドを使用した多層ダイス方式と、複数のダイスを使用する押出しラミネーション方式等がある。また多層ダイスと押出しラミネーションを組み合わせて使用してもよい。その他に接着剤を用いたドライラミネートやウェットラミネート、ホットメルト接着剤の塗布等、公知のいかなる積層法も用いることができる。
[5] Lamination The lamination method of the present invention is not particularly limited, and various known methods can be used. Specific examples include a multilayer die method using a feed block and a multi-manifold, and an extrusion lamination method using a plurality of dies. A combination of multilayer dies and extrusion lamination may also be used. In addition, any known laminating method such as dry lamination using an adhesive, wet lamination, or application of a hot melt adhesive can be used.
[6]粘着剤
粘着剤としては、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤が代表的であり、ゴム系粘着剤の具体例には、ポリイソブチレンゴム、ブチルゴムとこれらの混合物、或いは、これらゴム系粘着剤にアビエチン酸ロジンエステル、テルペン・フェノール共重合体、テルペン・インデン共重合体などの粘着付与剤を配合したものが挙げられる。アクリル系粘着剤の具体例としては、2−エチルヘキシルアクリレート・アクリル酸n−ブチル共重合体、2−エチルヘキシルアクリレート・アクリル酸エチル・メタクリル酸メチル共重合体などのガラス転移点が−20℃以下のものが挙げられる。
[6] Adhesive The adhesive is typically a rubber adhesive, an acrylic adhesive, or a silicone adhesive. Specific examples of the rubber adhesive include polyisobutylene rubber, butyl rubber and a mixture thereof, Or the thing which mix | blended tackifiers, such as an abietic acid rosin ester, a terpene * phenol copolymer, a terpene * indene copolymer, with these rubber-type adhesives is mentioned. As specific examples of the acrylic pressure-sensitive adhesive, the glass transition point of 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, or the like is −20 ° C. or lower. Things.
これら粘着剤の形態としては、溶剤型、エマルジョン型、ホットメルト型等が使用され、一般的には溶剤型、エマルジョン型のものを塗工することにより積層される。 As a form of these pressure-sensitive adhesives, a solvent type, an emulsion type, a hot melt type, and the like are used, and they are generally laminated by applying a solvent type or an emulsion type.
かかる塗工は、ロールコーター、ブレードコーター、バーコーター、エアーナイフコーター、グラビアコーター、リバースコーター、ダイコーター、リップコーター、スプレーコーター、コンマコーター等により行われ、必要によりスムージングを行ったり、乾燥工程を経て、粘着剤層が形成される。 Such coating is performed by a roll coater, a blade coater, a bar coater, an air knife coater, a gravure coater, a reverse coater, a die coater, a lip coater, a spray coater, a comma coater, etc. Then, an adhesive layer is formed.
粘着剤層の形成は、後述する離型紙へ粘着剤を塗工し、必要により乾燥を行い、粘着剤層を形成したものに、溶融熱転写記録用紙を積層する方法が一般的であるが、場合によっては溶融熱転写記録用紙に直接粘着剤を塗工して形成することもできる。 For the formation of the pressure-sensitive adhesive layer, it is common to apply a pressure-sensitive adhesive to the release paper, which will be described later, and if necessary, dry and then laminate the melt thermal transfer recording paper on the one formed with the pressure-sensitive adhesive layer. Depending on the case, it may be formed by directly applying an adhesive to the melt thermal transfer recording paper.
該粘着剤の塗工量は特に限定されないが、通常は固形分量で3〜60g/m2、好ましくは10〜40g/m2の範囲である。また、この粘着剤層の層間剥離強度は200〜3000g/20mmであることが好ましい。 The coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of 3 to 60 g / m 2 , preferably 10 to 40 g / m 2 in terms of solid content. Moreover, it is preferable that the delamination strength of this adhesive layer is 200-3000 g / 20mm.
溶融熱転写記録用紙と粘着剤との接着力が小さい場合は、上記粘着剤を塗工する前に溶融熱転写記録用紙の裏面にアンカーコート剤を塗布することが好ましい。 When the adhesive force between the melt thermal transfer recording paper and the adhesive is small, it is preferable to apply an anchor coating agent to the back surface of the melt thermal transfer recording paper before applying the adhesive.
該アンカーコート剤としては、ポリウレタン、ポリイソシアネート・ポリエーテルポリオール、ポリイソシアネート・ポリエステルポリオール・ポリエチレンイミン、アルキルチタネートなどが使用でき、これらは一般に、メタノール、酢酸エチル、トルエン、ヘキサンなどの有機溶剤、または水に溶解して使用される。 As the anchor coating agent, polyurethane, polyisocyanate / polyether polyol, polyisocyanate / polyester polyol / polyethyleneimine, alkyl titanate, etc. can be used, and these are generally organic solvents such as methanol, ethyl acetate, toluene, hexane, Used by dissolving in water.
アンカーコート剤の塗布量は、塗布・乾燥後の固形分量で0.01〜5g/m2、好ましくは0.02〜2g/m2の範囲である。 The coating amount of the anchor coating agent, 0.01-5 g / m 2 by solid content after coating and drying, is preferably in the range of 0.02~2g / m 2.
[7]離型紙
更に必要により粘着剤層の外側に離型紙を設けることも可能である。
溶融熱転写記録用紙に粘着剤層を介し設けられる離型紙は、粘着剤層との剥離性を良好にするため、粘着剤層に接触する面にシリコン処理が施されるのが一般的である。
離型紙は、通常一般的なものが使用でき、上質紙やクラフト紙をそのまま、あるいはカレンダー処理したり樹脂を塗工したりフィルムラミネートしたもの、グラシン紙、コート紙、プラスチックフィルムなどにシリコン処理を施したものが使用できる。
本発明の溶融熱転写記録用紙または積層体に上記の粘着剤を介し剥離紙を設けることによりラベル用原紙として使用できる。
[7] Release paper Further, if necessary, release paper can be provided outside the pressure-sensitive adhesive layer.
The release paper provided on the melt heat transfer recording paper via the pressure-sensitive adhesive layer is generally subjected to silicon treatment on the surface in contact with the pressure-sensitive adhesive layer in order to improve the peelability from the pressure-sensitive adhesive layer.
Release paper can be used for general papers, and high-quality paper and kraft paper can be used as is, or they can be treated with silicon on glassine paper, coated paper, plastic film, etc. that are calendered, resin-coated, or film-laminated. Can be used.
By providing release paper with the above-mentioned pressure-sensitive adhesive on the melt thermal transfer recording paper or laminate of the present invention, it can be used as a base paper for labels.
[8]印刷
本発明の溶融熱転写記録用紙は、昇華熱転写方式、溶融熱転写方式、電子写真方式、静電記録方式等種々の熱転写方式の記録に使用可能である。それらの中で本発明の効果、すなわち転写された印字や画像部の耐溶剤擦過性が良好となる効果を顕著に得るという観点から、溶融熱転写方式での使用が好ましい。
使用するインクリボンの種類としてはワックス型、樹脂型および両者の混合型等が挙げられるが、特にワックス型インクリボンを使用することが好ましい。
[8] Printing The melt thermal transfer recording paper of the present invention can be used for recording by various thermal transfer systems such as a sublimation thermal transfer system, a melt thermal transfer system, an electrophotographic system, and an electrostatic recording system. Among them, the use in the melt thermal transfer system is preferable from the viewpoint of remarkably obtaining the effect of the present invention, that is, the effect of improving the solvent scratch resistance of the transferred print and image portion.
Examples of the type of ink ribbon to be used include a wax type, a resin type, and a mixed type of both, and it is particularly preferable to use a wax type ink ribbon.
更に種々の印刷も可能であり、凸版印刷は勿論、オフセット印刷、グラビア印刷、フレキソ印刷が挙げられる。 Furthermore, various printing is also possible, and offset printing, gravure printing, flexographic printing as well as letterpress printing can be mentioned.
本発明の溶融熱転写記録用紙または積層体またはラベル用原紙に上記のような各種方式で印字/印刷を行うことにより記録物を得ることができる。 A recorded matter can be obtained by performing printing / printing on the melt thermal transfer recording paper or laminate or label base paper of the present invention by various methods as described above.
以下に製造例、実施例、比較例および試験例を記載して、本発明の特徴をさらに具体的に説明する。製造例では樹脂延伸フィルムと(i)〜(iii)成分の製造について記載し、実施例では本発明の条件を満たす溶融熱転写記録用紙の製造について記載し、比較例では本発明の条件を満たさない溶融熱転写記録用紙について記載し、試験例では各溶融熱転写記録用紙の試験と評価について記載する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be described more specifically with reference to production examples, examples, comparative examples and test examples. The production example describes the production of the stretched resin film and the components (i) to (iii), the example describes the production of the melt thermal transfer recording paper that satisfies the conditions of the present invention, and the comparative example does not satisfy the conditions of the present invention. The melt thermal transfer recording paper is described, and the test example describes the test and evaluation of each melt thermal transfer recording paper. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
(製造例1) 樹脂延伸フィルムの製造
(1)プロピレン単独重合体「ノバテックPP EA−8」(日本ポリケム(株)製、商品名、融点164℃)85重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)15重量%を混合した組成物(C)を、270℃に設定した押出機にて混練した後、シート状に押し出し、更に冷却装置により冷却して、無延伸シートを得た。次いで、このシートを150℃の温度にまで再度加熱させた後、縦方向に5倍の延伸を行って縦延伸樹脂フィルムを得た。
(Production Example 1) Production of stretched resin film (1) Propylene homopolymer “Novatech PP EA-8” (trade name, melting point 164 ° C., manufactured by Nippon Polychem Co., Ltd.) 85% by weight with an average particle size of 3.0 μm A composition (C) in which 15% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) was mixed by an extruder set at 270 ° C., and then in sheet form And then cooled by a cooling device to obtain an unstretched sheet. Next, the sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the longitudinal direction to obtain a longitudinally stretched resin film.
(2)ビカット軟化点122℃の高密度ポリエチレン「ノバテックHD、HJ360」(日本ポリケム(株)製、商品名)23重量%、ビカット軟化点145℃のプロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)16.2重量%、平均粒径1.1μmの重質炭酸カルシウム「カルテックス7」(丸尾カルシウム(株)製、商品名)60重量%、滑剤としてステアリン酸アルミニウム0.2重量%、オレイン酸0.6重量%を混合した組成物(A)を調製した。これとは別に、プロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)55重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)45重量%を混合した組成物(B)を調製した。これらの組成物(A)および(B)を、270℃に設定した別個の押出機でそれぞれ溶融混練し、ダイ内部で積層した後、一台のダイより共押出し、これを上記(1)の工程で得られた5倍縦延伸フィルムの表側に(A)層が表層となるように積層した。 (2) High density polyethylene “Novatech HD, HJ360” (trade name) manufactured by Nippon Polychem Co., Ltd., having a Vicat softening point of 122 ° C., 23% by weight, and a propylene homopolymer “Novatech PP MA-3” having a Vicat softening point of 145 ° C. (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 16.2% by weight, heavy calcium carbonate “Caltex 7” (trade name, Maruo Calcium Co., Ltd., trade name) 60% by weight with an average particle size of 1.1 μm A composition (A) in which 0.2% by weight of aluminum stearate and 0.6% by weight of oleic acid were mixed as a lubricant was prepared. Separately, a heavy calcium carbonate “Softon 1800” having an average particle size of 3.0 μm was added to 55% by weight of a propylene homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.). A composition (B) in which 45% by weight (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) was mixed was prepared. These compositions (A) and (B) were melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, and then co-extruded from a single die. It laminated | stacked so that the (A) layer might become a surface layer on the front side of the 5 times longitudinally stretched film obtained at the process.
(3)更にプロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)55重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)45重量%を混合した組成物(D)を、270℃の温度に設定した別の押出機にて溶融混練させた後シート状に押し出し、これを上記(1)の工程で得られた5倍縦延伸フィルムの裏側の面に積層し、四層構造の積層シートを得た。次いで、この四層構造の積層シートを60℃の温度にまで冷却した後、再び155℃の温度にまで加熱してテンターを用いて横方向に8.5倍延伸し、165℃の温度でアニーリング処理して60℃の温度まで冷却した後、耳部をスリットして四層構造(一軸延伸/一軸延伸/二軸延伸/一軸延伸)の肉厚80μm(A/B/C/D=5μm/10μm/50μm/15μm)の樹脂延伸フィルムを得た。 (3) Further, a heavy calcium carbonate “Softon 1800” having an average particle size of 3.0 μm and 55% by weight of a propylene homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.) (Bikoku Flour Industry Co., Ltd., trade name) A composition (D) mixed with 45% by weight was melted and kneaded in another extruder set at a temperature of 270 ° C., and then extruded into a sheet. Was laminated on the back surface of the 5-fold longitudinally stretched film obtained in the step (1) to obtain a laminated sheet having a four-layer structure. Next, the laminated sheet having the four-layer structure was cooled to a temperature of 60 ° C., then heated again to a temperature of 155 ° C., stretched 8.5 times in the transverse direction using a tenter, and annealed at a temperature of 165 ° C. After the treatment and cooling to a temperature of 60 ° C., the ears are slit and the thickness of the four-layer structure (uniaxial stretching / uniaxial stretching / biaxial stretching / uniaxial stretching) is 80 μm (A / B / C / D = 5 μm / 10 μm / 50 μm / 15 μm) stretched resin film was obtained.
(4)該フィルムの両面に、コロナ放電処理装置「HF400F」(春日電気(株)社製、商品名)を用いてコロナ放電処理を行った。コロナ放電処理に際して、長さ0.8mのアルミニウム製電極を用い、トリーターロールにはシリコーン被膜ロールを用い、電極とロールとのギャップを5mmとし、ライン処理速度を15m/分、印加エネルギー密度を4,200J/m2にした。 (4) Corona discharge treatment was performed on both surfaces of the film using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m 2 .
(製造例2) 樹脂延伸フィルムの製造
(1)ビカット軟化点122℃の高密度ポリエチレン「ノバテックHD、HJ360」(日本ポリケム(株)製、商品名)23重量%、ビカット軟化点145℃のプロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)16.2重量%、平均粒径1.1μmの重質炭酸カルシウム「カルテックス7」(丸尾カルシウム(株)製、商品名)60重量%、滑剤としてステアリン酸アルミニウム0.2重量%、オレイン酸0.6重量%を混合した組成物(A)と、プロピレン単独重合体「ノバテックPP EA−8」(日本ポリケム(株)製、商品名、融点165℃)85重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)15重量%を混合した組成物(B)と、プロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)55重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)45重量%を混合した組成物(C)を調製した。これらの組成物(A)、(B)および(C)を270℃に設定した別個の押出機でそれぞれ溶融混練し、ダイ内部で積層した後シート状に共押出し、更に冷却装置により冷却して三層構造の無延伸積層シートを得た。次いで、150℃の温度まで再加熱した後、縦方向に7倍延伸し、155℃でアニーリング処理して肉厚80μm(A/B/C=5μm/70μm/5μm)の樹脂延伸フィルムを得た。
(Production Example 2) Production of stretched resin film (1) High-density polyethylene “Novatech HD, HJ360” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 122 ° C., propylene having a Vicat softening point of 145 ° C. Homopolymer “Novatech PP MA-3” (trade name, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.) 16.2 wt%, heavy calcium carbonate “Caltex 7” (Maruo Calcium Co., Ltd., trade name) 60% by weight, composition (A) in which aluminum stearate 0.2% by weight and oleic acid 0.6% by weight are mixed as a lubricant, and propylene homopolymer "NOVATEC PP EA-8" (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 85% by weight, heavy calcium carbonate “Softon 1800” with an average particle size of 3.0 μm Co., Ltd., trade name: 15% by weight of the composition (B) and propylene homopolymer “Novatec PP MA-3” (manufactured by Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 55% by weight A composition (C) was prepared by mixing 45% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) having an average particle size of 3.0 μm. These compositions (A), (B) and (C) are melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, coextruded into a sheet, and further cooled by a cooling device. A three-layer unstretched laminated sheet was obtained. Next, after reheating to a temperature of 150 ° C., the film was stretched 7 times in the longitudinal direction and annealed at 155 ° C. to obtain a stretched resin film having a thickness of 80 μm (A / B / C = 5 μm / 70 μm / 5 μm). .
(2)該フィルムの表面に、コロナ放電処理装置「HF400F」(春日電気(株)社製、商品名)を用いてコロナ放電処理を行った。コロナ放電処理に際して、長さ0.8mのアルミニウム製電極を用い、トリーターロールにはシリコーン被膜ロールを用い、電極とロールとのギャップを5mmとし、ライン処理速度を15m/分、印加エネルギー密度を4,200J/m2にした。 (2) The surface of the film was subjected to corona discharge treatment using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m 2 .
(製造例3) 樹脂延伸フィルムの製造
(1)ビカット軟化点122℃の高密度ポリエチレン「ノバテックHD、HJ360」(日本ポリケム(株)製、商品名)35重量%、ビカット軟化点145℃のプロピレン単独重合体「ノバテックPP MA−3」(日本ポリケム(株)製、商品名、融点165℃)24.2重量%、平均粒径1.1μmの重質炭酸カルシウム「カルテックス7」(丸尾カルシウム(株)製、商品名)40重量%、滑剤としてステアリン酸アルミニウム0.2重量%、オレイン酸0.6重量%を混合した組成物(A)と、プロピレン単独重合体「ノバテックPP EA−8」(日本ポリケム(株)製、商品名、融点165℃)85重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)15重量%を混合した組成物(B)と、日本ポリケム(株)製、プロピレン単独重合体「ノバテックPP MA−3」(商品名、融点165℃)55重量%に、平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(備北粉化工業(株)製、商品名)45重量%を混合した組成物(C)を調製した。これらの組成物(A)、(B)および(C)を270℃に設定した別個の押出機でそれぞれ溶融混練し、ダイ内部で積層した後シート状に共押出し、更に冷却装置により冷却して三層構造の無延伸積層シートを得た。
(Production Example 3) Production of stretched resin film (1) High-density polyethylene “Novatech HD, HJ360” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 122 ° C., propylene having a Vicat softening point of 145 ° C. Homopolymer “Novatech PP MA-3” (manufactured by Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 24.2% by weight, heavy calcium carbonate “Cartex 7” (Maruo Calcium Co., Ltd., trade name) 40% by weight, a composition (A) in which aluminum stearate 0.2% by weight and oleic acid 0.6% by weight are mixed as a lubricant, and a propylene homopolymer "Novatec PP EA-8" (Nippon Polychem Co., Ltd., trade name, melting point 165 ° C.) 85% by weight, heavy calcium carbonate “Softon 1800” with an average particle size of 3.0 μm Co., Ltd., trade name: 15% by weight of the composition (B) mixed with Nippon Polychem Co., Ltd., propylene homopolymer “NOVATEC PP MA-3” (trade name, melting point: 165 ° C.) 55% by weight A composition (C) was prepared by mixing 45% by weight of heavy calcium carbonate “Softon 1800” (trade name, manufactured by Bihoku Flour Industry Co., Ltd.) having an average particle size of 3.0 μm. These compositions (A), (B) and (C) are melt-kneaded in separate extruders set at 270 ° C., laminated inside the die, coextruded into a sheet, and further cooled by a cooling device. A three-layer unstretched laminated sheet was obtained.
(2)次いで、この三層構造の積層シートを冷却装置により60℃まで冷却した後、150℃の温度にまで再加熱させた後、縦方向に5倍の延伸を行い、更に155℃の温度にまで加熱してテンターを用いて横方向に6倍延伸し、165℃の温度でアニーリング処理をして60℃の温度にまで冷却し、耳部をスリットして肉厚80μm(A/B/C=5μm/70μm/5μm)の積層樹脂延伸フィルムを得た。 (2) Next, this three-layer laminated sheet was cooled to 60 ° C. by a cooling device, then reheated to a temperature of 150 ° C., then stretched 5 times in the longitudinal direction, and further a temperature of 155 ° C. And then stretched 6 times in the transverse direction using a tenter, annealed at a temperature of 165 ° C., cooled to a temperature of 60 ° C., slitted at the ear, and 80 μm thick (A / B / A laminated resin stretched film of C = 5 μm / 70 μm / 5 μm was obtained.
(3)該フィルムの表面に、コロナ放電処理装置「HF400F」(春日電気(株)社製、商品名)を用いてコロナ放電処理を行った。コロナ放電処理に際して、長さ0.8mのアルミニウム製電極を用い、トリーターロールにはシリコーン被膜ロールを用い、電極とロールとのギャップを5mmとし、ライン処理速度を15m/分、印加エネルギー密度を4,200J/m2にした。 (3) The surface of the film was subjected to corona discharge treatment using a corona discharge treatment apparatus “HF400F” (trade name, manufactured by Kasuga Electric Co., Ltd.). In the corona discharge treatment, an aluminum electrode having a length of 0.8 m was used, a silicone film roll was used as the treater roll, the gap between the electrode and the roll was 5 mm, the line treatment speed was 15 m / min, and the applied energy density was 4 , 200 J / m 2 .
(製造例4) 塗布剤(i)成分の製造
攪拌機、環流冷却器、温度計および窒素ガス導入口を備えた四つ口フラスコに、ポリエチレンイミン「エポミン P−1000(重合度1600)」(日本触媒(株)製、商品名)の25重量%水溶液100部、n−ブチルクロライド10部およびプロピレングリコールモノメチルエーテル10部を入れて窒素気流下で攪拌し、80℃の温度で20時間変性反応を行って20重量%のブチル変性ポリエチレンイミン水溶液を得た。
(Production Example 4) Production of coating agent (i) component In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet, polyethyleneimine “Epomin P-1000 (degree of polymerization 1600)” (Japan) 100 parts of a 25% by weight aqueous solution of a catalyst (trade name), 10 parts of n-butyl chloride and 10 parts of propylene glycol monomethyl ether are added and stirred under a nitrogen stream, and the modification reaction is carried out at a temperature of 80 ° C. for 20 hours. And a 20% by weight butyl-modified polyethyleneimine aqueous solution was obtained.
(製造例5) 塗布剤(ii)成分の準備
ポリアミンポリアミドのエピクロルヒドリン付加物「WS−570(固形分12.5重量%)」(日本PMC(株)製、商品名)を塗布剤(ii)成分として準備した。
(Manufacture example 5) Preparation of coating agent (ii) component Epichlorohydrin adduct "WS-570 (solid content 12.5 weight%)" of polyamine polyamide (Nippon PMC Co., Ltd., brand name) coating agent (ii) Prepared as an ingredient.
(製造例6) 塗布剤(iii)成分の製造
環流冷却器、温度計、窒素置換用ガラス管、および攪拌装置を取り付けた四つ口フラスコに、ジメチルアミノエチルメタクリレート35部、エチルメタアクリレート20部、シクロヘキシルメタアクリレート20部、ステアリルメタアクリレート25部、エチルアルコール150部と、アゾビスイソブチロニトリル1部を添加し、窒素気流下に80℃の温度で6時間重合反応を行った。
(Production Example 6) Production of coating agent (iii) component 35 parts of dimethylaminoethyl methacrylate and 20 parts of ethyl methacrylate are attached to a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer. Then, 20 parts of cyclohexyl methacrylate, 25 parts of stearyl methacrylate, 150 parts of ethyl alcohol and 1 part of azobisisobutyronitrile were added, and a polymerization reaction was performed at a temperature of 80 ° C. for 6 hours in a nitrogen stream.
ついで、3−クロロ−2−ヒドロキシプロピルアンモニウムクロリドの60重量%エチルアルコール溶液70部を加え、更に80℃の温度で15時間反応させた後、水を滴下しながらエチルアルコールを留去し、最終固形分30%の第4級アンモニウム塩型共重合体を得た。 Next, 70 parts of a 60% by weight ethyl alcohol solution of 3-chloro-2-hydroxypropylammonium chloride was added and further reacted at a temperature of 80 ° C. for 15 hours, and then the ethyl alcohol was distilled off while adding water dropwise. A quaternary ammonium salt copolymer having a solid content of 30% was obtained.
この共重合体は、次の一般式で示される基を分子鎖内に含むアクリル酸アルキルエステル系重合体である。 This copolymer is an acrylic acid alkyl ester polymer containing a group represented by the following general formula in the molecular chain.
(実施例1)
製造例1で得た積層樹脂延伸フィルムを溶融熱転写記録用紙とした。なお、下記表1における樹脂などの組成は、A層(最外層)の組成を表す。これは、後述するその他の実施例および比較例においても同様である。
Example 1
The laminated resin stretched film obtained in Production Example 1 was used as a melt thermal transfer recording paper. In addition, composition of resin etc. in following Table 1 represents the composition of A layer (outermost layer). The same applies to other examples and comparative examples described later.
(実施例2〜5)
実施例1でA層のプロピレン単独重合体、高密度ポリエチレンまたは無機微細粉末の配合量を表1のように変更する他は実施例1と同様にして溶融熱転写記録用紙を得た。
(Examples 2 to 5)
A melt thermal transfer recording paper was obtained in the same manner as in Example 1 except that the blending amount of the propylene homopolymer of layer A, high density polyethylene or inorganic fine powder in Example 1 was changed as shown in Table 1.
(実施例6)
実施例1でA層の無機微細粉末を備北粉化工業(株)製平均粒径3.0μmの重質炭酸カルシウム「ソフトン1800」(商品名)に変更する他は実施例1と同様にして溶融熱転写記録用紙を得た。
(Example 6)
The same procedure as in Example 1 was conducted, except that the inorganic fine powder of layer A in Example 1 was changed to heavy calcium carbonate “Softon 1800” (trade name) with an average particle size of 3.0 μm manufactured by Bihoku Flour Industry Co., Ltd. A melt thermal transfer recording sheet was obtained.
(実施例7)
実施例1でA層の高密度ポリエチレンを、ビカット軟化点84℃の低密度ポリエチレン「ノバテックLD、LC604」(日本ポリケム(株)製、商品名)に変更する他は実施例1と同様にして溶融熱転写記録用紙を得た。
(Example 7)
In the same manner as in Example 1, except that the high density polyethylene of layer A in Example 1 is changed to low density polyethylene “Novatech LD, LC604” (trade name, manufactured by Nippon Polychem Co., Ltd.) having a Vicat softening point of 84 ° C. A melt thermal transfer recording sheet was obtained.
(実施例8)
実施例1でA層の高密度ポリエチレンを、ビカット軟化点60℃のエチレン−メチルアクリレート「レクスパールRB5120」(日本ポリオレフィン(株)製、商品名)に変更する他は実施例1と同様にして溶融熱転写記録用紙を得た。
(Example 8)
The high density polyethylene of layer A in Example 1 was changed to ethylene-methyl acrylate “Lex Pearl RB5120” (trade name, manufactured by Nippon Polyolefin Co., Ltd.) having a Vicat softening point of 60 ° C. A melt thermal transfer recording sheet was obtained.
(実施例9)
製造例2で得た積層樹脂延伸フィルムを溶融熱転写記録用紙とした。
Example 9
The laminated resin stretched film obtained in Production Example 2 was used as a melt thermal transfer recording paper.
(実施例10)
製造例3で得た積層樹脂延伸フィルムを溶融熱転写記録用紙とした。
(Example 10)
The laminated resin stretched film obtained in Production Example 3 was used as a melt thermal transfer recording paper.
(実施例11)
製造例1で得た積層樹脂延伸フィルムの両面に、製造例4で得た塗布剤(i)成分100重量部、製造例5で得た塗布剤(ii)成分150重量部、製造例6で得た塗布剤(iii)成分150重量部からなる塗布剤を、ロールコーターを用いて塗膜の肉厚が0.06g/m2となるように塗布・乾燥させ、フィルム状の溶融熱転写記録用紙を得た。
Example 11
On both surfaces of the laminated resin stretched film obtained in Production Example 1, 100 parts by weight of the coating agent (i) component obtained in Production Example 4, 150 parts by weight of the coating agent (ii) component obtained in Production Example 5, and in Production Example 6 The obtained coating agent consisting of 150 parts by weight of the coating agent (iii) component is applied and dried using a roll coater so that the thickness of the coating film becomes 0.06 g / m 2, and the film-like melt thermal transfer recording paper Got.
(実施例12)
実施例1でA層において、プロピレン単独重合体、高密度ポリエチレンの配合を表1に記載の量に変更し、更に分散剤としてマレイン酸変性率5%のマレイン酸変性ポリプロピレン(三洋化成(株)製、商品名:「Yumex1001」)を0.5重量%添加する以外は実施例1と同様にして溶融熱転写記録用紙を得た。
Example 12
In Example 1, in layer A, the blend of propylene homopolymer and high-density polyethylene was changed to the amounts shown in Table 1, and maleic acid-modified polypropylene having a maleic acid modification rate of 5% as a dispersant (Sanyo Chemical Co., Ltd.) Manufactured and trade name: “Yumex1001”) was added in the same manner as in Example 1 except that 0.5% by weight was added to obtain a melt thermal transfer recording sheet.
(実施例13〜17)
実施例12でA層のプロピレン単独重合体、高密度ポリエチレン、無機微細粉末、及び分散剤の配合量を表1のように変更する他は実施例12と同様にして溶融熱転写記録用紙を得た。
(Examples 13 to 17)
In Example 12, a melt thermal transfer recording paper was obtained in the same manner as in Example 12 except that the blending amounts of the propylene homopolymer of layer A, high-density polyethylene, inorganic fine powder, and dispersant were changed as shown in Table 1. .
(比較例1)
特開平8−80684号公報の実施例1に記載の延伸樹脂フィルムを用意した。なお、以下に記載される試験例の評価は、このフィルムの表面層(一軸延伸)について行った。
(Comparative Example 1)
A stretched resin film described in Example 1 of JP-A-8-80684 was prepared. In addition, evaluation of the test example described below was performed about the surface layer (uniaxial stretching) of this film.
(比較例2)
特開2001−219661号公報の実施例1に記載の延伸樹脂フィルムを用意した。なお、以下に記載される試験例の評価は、このフィルムの表面層(一軸延伸)について行った。
(Comparative Example 2)
A stretched resin film described in Example 1 of JP-A No. 2001-219661 was prepared. In addition, evaluation of the test example described below was performed about the surface layer (uniaxial stretching) of this film.
(比較例3〜7)
実施例1のA層におけるプロピレン単独重合体、高密度ポリエチレン、無機微細粉末の配合量を表2に記載のとおりに変更した以外は実施例1と同様にして溶融熱転写記録用紙を得た。
(Comparative Examples 3 to 7)
A melt thermal transfer recording paper was obtained in the same manner as in Example 1 except that the blending amounts of the propylene homopolymer, high-density polyethylene, and inorganic fine powder in layer A of Example 1 were changed as shown in Table 2.
(比較例8)
実施例5でA層のポリプロピレン単独重合体を、ビカット軟化点131℃の「チッソポリプロ F8090」(チッソ(株)製、商品名、融点148℃)に変更する他は実施例5と同様にしてフィルムを得て評価した。結果を表2に示す。
(Comparative Example 8)
In the same manner as in Example 5, except that the polypropylene homopolymer of layer A in Example 5 is changed to “Cisso Polypro F8090” (trade name, melting point: 148 ° C., manufactured by Chisso Corporation) having a Vicat softening point of 131 ° C. A film was obtained and evaluated. The results are shown in Table 2.
実施例および比較例で製造した各溶融熱転写記録用紙について、上記測定法にしたがって空印字後の表面被覆面積比率、中心線平均粗さ(Ra)を測定した結果を表1および表2に示す。さらに、以下の試験を行った。 Tables 1 and 2 show the results of measuring the surface coverage area ratio and the centerline average roughness (Ra) after empty printing according to the measurement method described above for each of the thermal transfer recording sheets manufactured in Examples and Comparative Examples. Further, the following tests were conducted.
(試験例1) 溶融熱転写適性の評価
実施例および比較例で製造した各溶融熱転写記録用紙に印字して、溶融熱転写適性を評価した。印字にはバーコードプリンター「Zebra140 Xi II」(Zebra(株)製、商品名)と溶融型ワックスインクリボン「FTR」((株)フジコピアン製、商品名)を用いた。サーマルヘッドの温度は110℃(サーマルヘッドに熱電対を取り付けて実測した)になるように条件を設定した。
(Test Example 1) Evaluation of melt heat transfer suitability Printing on each melt heat transfer recording paper produced in Examples and Comparative Examples was performed to evaluate melt heat transfer suitability. For printing, a bar code printer “Zebra140 Xi II” (trade name, manufactured by Zebra Corporation) and a melt-type wax ink ribbon “FTR” (trade name, manufactured by Fuji Copian Corporation) were used. Conditions were set so that the temperature of the thermal head was 110 ° C. (measured by attaching a thermocouple to the thermal head).
記録用紙にかかる温度を110℃、印字速度を3インチ/秒にして、上記の溶融型ワックスインクリボンを記録用紙に転写した。溶融熱転写して印字したバーコード(CODE39)を、温度23℃、相対湿度50%の条件下でバーコード検証機「LASERCHEK II」(富士電機冷凍機(株)製、商品名)にて読みとり、読みとり率をANSI(American National Standards Institute) GRADEにて評価した。ANSI GRADEはA〜D、FおよびNo Decodeの6段階で現したもので、Aが最も良好な印字状態を示す。結果は表1および表2に示すとおりであった。 The molten wax ink ribbon was transferred to the recording paper at a temperature of 110 ° C. and a printing speed of 3 inches / second. Bar code (CODE39) printed by melt heat transfer is read with a bar code verifier “LASERCHEK II” (trade name, manufactured by Fuji Electric Refrigerator Co., Ltd.) under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. The reading rate was evaluated by ANSI (American National Standards Institute) GRADE. ANSI GRADE appears in 6 stages of A to D, F and No Decode, and A indicates the best printing state. The results are as shown in Tables 1 and 2.
A :極めて良好(バーコードにかすれが全くみられず、市販のバーコードリ
ーダーを用いて1回のバーコード読みとりで正確に読みとれるレベル)
B :良好(基本的に1回のバーコード読みとりで読みとりが可能であるが、
再度バーコード読みとりが必要な場合もあるレベル)
C :可(バーコードに若干のかすれが見られ、複数回のバーコード読みとり
が必要であるが実用できるレベル)
D、F :不可(バーコードに線切れが生じ、Cレベルより多くのバーコード読み
とり回数が必要であり実用的でないレベル)
No Decord:不可(CODE39のバーコードと認識できないレベル)
A: Extremely good (barcode is not faint at all, and commercially available barcode
(A level that can be read accurately with a single barcode reading using a reader)
B: Good (Basically, it is possible to read a single barcode, but
(A level that may require reading the barcode again)
C: Possible (Slight fading is seen in the barcode, and multiple times of reading the barcode.
Is necessary but practical level)
D, F: Impossible (bar code breaks, reading more bar codes than C level)
The number of times of taking is necessary and is not practical)
No Decord: Impossible (level not recognized as CODE39 barcode)
(試験例2) 耐溶剤擦過性の評価
実施例1で得られた印字物を、JIS−L−0849−1996に準拠した方法にて評価した。具体的には染色堅ろう度試験用摩擦試験機「FR−II型」(スガ試験機(株)製、商品名)を用い、摩擦用白綿布を常に湿潤状態を保つようにエタノールを適宜供給しながら200g荷重にて50回擦過した。耐溶剤擦過性をバーコード検証機にてANSI GRADEを測定することにより行った。ANSI GRADEがA〜C以上のものを実用レベルと判断した。結果は表1および表2に示すとおりであった。
(Test Example 2) Evaluation of solvent abrasion resistance The printed matter obtained in Example 1 was evaluated by a method based on JIS-L-0849-1996. Specifically, using a friction tester “FR-II” (trade name, manufactured by Suga Test Instruments Co., Ltd.) for dyeing fastness test, ethanol is appropriately supplied so that the white cotton cloth for friction is always kept wet. However, it was rubbed 50 times with a load of 200 g. Solvent rub resistance was measured by measuring ANSI GRADE with a bar code verifier. Those having ANSI GRADE of A to C or higher were judged to be practical levels. The results are as shown in Tables 1 and 2.
(試験例3) 印刷適性の評価
評価には印刷機「RI- III型印刷適性試験機」((株)明製作所社製、商品名)と印刷インキ「ベストキュアー161(墨)」((株)T&K TOKA社製、商品名)を用いた。
(Test Example 3) Evaluation of printability For evaluation, the printing machine “RI-III type printability tester” (trade name, manufactured by Meisei Co., Ltd.) and printing ink “Best Cure 161 (black)” ) T & K TOKA, trade name) was used.
各溶融熱転写記録用紙を、温度23℃、相対湿度50%の雰囲気下で3日間保管した後、上記印刷機を用いて溶融熱転写記録用紙の塗布面に上記インクを1.5g/m2の厚さになるように印刷した。印刷面のマクベス濃度を光反射濃度「マクベス濃度計」((株)コルモーゲン社製(米国)、商品名)にて測定した。以下の判定基準でC以上を合格レベルと判定した。結果は表1および表2に示すとおりであった。
A :マクベス濃度1.8以上、転移濃度が極めて良好
B :マクベス濃度1.6以上1.8未満、転移濃度が良好
C :マクベス濃度1.4以上1.6未満、転移濃度がややうすいが実用レベル
D :マクベス濃度1.4未満、転移濃度が低く、絵柄によっては問題となる
Each melt thermal transfer recording sheet was stored for 3 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then the ink was applied to the application surface of the melt thermal transfer recording sheet with a thickness of 1.5 g / m 2 using the printer. It was printed as it was. The Macbeth density of the printed surface was measured with a light reflection density “Macbeth densitometer” (trade name, manufactured by Colmorgen, Inc. (USA)). C or higher was determined as an acceptable level according to the following criteria. The results are as shown in Tables 1 and 2.
A: Macbeth concentration of 1.8 or higher, transition density is extremely good B: Macbeth concentration of 1.6 or higher and lower than 1.8, transfer density is good C: Macbeth concentration of 1.4 or higher and lower than 1.6, transition level is slightly thin Practical level D: Macbeth concentration of less than 1.4, transfer concentration is low, which may be a problem depending on the design
(試験例4)メヤニ評価
実施例1〜17及び比較例1〜8に使用した樹脂フィルムの成形において、成形開始1時間後のダイス先端におけるメヤニの発生状況を目視により判断した。
A :優 (ダイス先端にほとんどメヤニの発生が見られず成形上全く問題な
いレベル)
B :良 (ダイス先端にメヤニの発生が見られるが成形上問題ないレベル)
C :可 (ダイス先端にメヤニの発生が見られ、樹脂フィルムにメヤニが脱
落するが、定期的なダイス先端の清掃により成形が可能なレベル)
D :不可 (ダイス先端にメヤニの発生が非常に多く、樹脂フィルムにメヤニ
が頻繁に脱落し、成形に耐えないレベル)
(Test Example 4) Evaluation of Meani In the molding of the resin films used in Examples 1 to 17 and Comparative Examples 1 to 8, the occurrence state of the meani at the tip of the die 1 hour after the start of molding was judged visually.
A: Excellent (There is almost no scum on the tip of the die, and there is no problem in molding.
Level)
B: Good (Mayani is seen at the tip of the die, but there is no problem in molding)
C: Yes (Mayan is observed at the tip of the die, and it is removed from the resin film.
Although it drops, it is possible to form by regular cleaning of the die tip)
D: Not possible (Mayan on the tip of the die is very large, and it is not on the resin film.
Is a level that often falls off and cannot withstand molding)
Claims (13)
(i)下記一般式(a)で表されるポリイミン系重合体またはポリアミンポリアミドのエチレンイミン付加物。
(I) An ethyleneimine adduct of a polyimine polymer or polyamine polyamide represented by the following general formula (a).
(ii)水溶性のエポキシ系、イソシアネート系架橋剤、ホルマリン系架橋剤、オキサゾリン系架橋剤、ポリアミンポリアミドのエピクロルヒドリン付加物の架橋剤。 The molten thermal transfer recording sheet according to claim 6 , wherein the coating layer contains the following component (ii).
(Ii) Water-soluble epoxy-based, isocyanate-based crosslinking agent, formalin-based crosslinking agent, oxazoline-based crosslinking agent, and crosslinking agent for epichlorohydrin adduct of polyamine polyamide.
(iii)ポリマー型帯電防止剤。 The molten thermal transfer recording sheet according to claim 6 or 7 , wherein the coating layer contains the following component (iii).
(Iii) Polymer type antistatic agent.
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JP5052759B2 (en) * | 2004-04-26 | 2012-10-17 | 株式会社ユポ・コーポレーション | Surface treatment method for thermoplastic resin film and thermoplastic resin film |
JP2006082464A (en) * | 2004-09-17 | 2006-03-30 | Toppan Printing Co Ltd | Laminate and packaging material |
JP6310232B2 (en) | 2013-11-06 | 2018-04-11 | 株式会社ユポ・コーポレーション | Thermoplastic resin film, adhesive sheet, and image receiving sheet for thermal transfer |
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