JP5215132B2 - Sublimation type inkjet printing transfer paper - Google Patents
Sublimation type inkjet printing transfer paper Download PDFInfo
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- JP5215132B2 JP5215132B2 JP2008284781A JP2008284781A JP5215132B2 JP 5215132 B2 JP5215132 B2 JP 5215132B2 JP 2008284781 A JP2008284781 A JP 2008284781A JP 2008284781 A JP2008284781 A JP 2008284781A JP 5215132 B2 JP5215132 B2 JP 5215132B2
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- sublimation
- printing
- printing ink
- transfer
- paper
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- 238000000859 sublimation Methods 0.000 title claims description 215
- 230000008022 sublimation Effects 0.000 title claims description 215
- 238000012546 transfer Methods 0.000 title claims description 151
- 238000007641 inkjet printing Methods 0.000 title claims description 42
- 238000007639 printing Methods 0.000 claims description 210
- 239000010410 layer Substances 0.000 claims description 72
- 239000010419 fine particle Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 42
- 239000011247 coating layer Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000007789 sealing Methods 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 20
- 229920006174 synthetic rubber latex Polymers 0.000 claims description 6
- 239000000976 ink Substances 0.000 description 191
- 239000000123 paper Substances 0.000 description 120
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 82
- 238000001035 drying Methods 0.000 description 40
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 32
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 32
- 238000000034 method Methods 0.000 description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 22
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- -1 satin white Chemical compound 0.000 description 16
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、昇華型インクジェット捺染転写紙に関し、具体的には、インクジェット記録方式により転写紙に昇華型捺染インクを用いた印刷を行い、この転写紙上の印刷された画像をポリエステル等の布帛に転写して昇華転写捺染する際に使用する昇華型インクジェット捺染転写紙に関する。 The present invention relates to a sublimation type ink jet printing transfer paper. Specifically, the sublimation type printing ink is printed on a transfer paper by an ink jet recording method, and the printed image on the transfer paper is transferred to a cloth such as polyester. The present invention relates to a sublimation type ink jet printing transfer paper used for sublimation transfer printing.
転写捺染法には、ワックスや樹脂等の熱軟化性固着剤と顔料からなるインクを用いた溶融型転写捺染法、ポリ塩化ビニル等の粉末及び可塑剤及び顔料からなるプラスチゾルインキを用いたラバープリント型転写捺染法、熱昇華性染料を用いた昇華型捺染転写法がある。 For transfer printing methods, melt-type transfer printing methods using heat softening fixatives such as waxes and resins and inks made of pigments, rubber prints using powders such as polyvinyl chloride and plasticizers and pigments There are a type transfer printing method and a sublimation type printing transfer method using a heat sublimation dye.
溶融型転写捺染法では捺染物の風合いや伸縮性が不十分であり、ラバープリント型転写捺染法による捺染物は通気性や感触が良くない。昇華型捺染転写法は、捺染物の風合いを損なわず、他の転写法では出せないシャープな図柄をプリントできることから、現在主に行われている転写捺染法である。従来、熱転写捺染シートはその形成に際してスクリーン版、グラビア版などの印刷版とそれに応じた印刷機が必要であったが、個性の多様化により、小ロットに対応したインクジェット印字用の転写捺染シートの報告がなされ、小ロットに対応した昇華型捺染転写が広まり、需要が伸びてきている。 In the melt type transfer printing method, the texture and stretchability of the printed material are insufficient, and the printed material by the rubber print type transfer printing method does not have good air permeability and feel. The sublimation printing transfer method is a transfer printing method that is mainly performed at present because it can print a sharp pattern that cannot be produced by other transfer methods without impairing the texture of the printed matter. Conventionally, a thermal transfer printing sheet has required a printing plate such as a screen plate and a gravure plate and a printing machine corresponding to the thermal transfer printing sheet. However, due to the diversification of individuality, a transfer printing sheet for inkjet printing corresponding to a small lot is required. There has been a report, and sublimation printing transfer corresponding to small lots has become widespread, and demand is increasing.
昇華型捺染転写法とは、ポリエステル生地等の被転写物と昇華型捺染転写紙とを重ね合わせたものを１８０〜２２０℃に加熱されたドライヤーに密着させて、昇華型捺染転写紙に印刷された印刷インクを熱にて昇華させ、被転写物に転写捺染を行うものである。 The sublimation printing transfer method is a method of printing on a sublimation printing transfer paper by bringing a transfer material such as polyester fabric and a sublimation printing transfer paper into close contact with a dryer heated to 180 to 220 ° C. The printed ink is sublimated with heat to perform transfer printing on the transfer object.
前記インクジェット印字用の昇華型捺染転写紙としては、基材上に、シリカ等の顔料や、ポリビニルアルコールや水溶性セルロース誘導体等の結着剤等を含有するインク受容層を設けてなるものが知られている（特許文献１〜５を参照）。
昇華型インクジェット捺染転写紙にインクジェット印刷をする際には、高速印刷をしつつ印刷後の転写紙を高速で巻き取る必要が生じるために、昇華型インクジェット捺染転写紙のインク受容層がきわめて急速に昇華型捺染インクを吸収、乾燥させる性能を有する必要がある。特に近年、印刷速度が１ｍ／分を超える高速印刷が要求されるようになっていることから、格別に優れたインク吸収乾燥性が求められるようになっている。 When ink-jet printing is performed on sublimation inkjet printing transfer paper, it is necessary to wind up the transfer paper after printing at high speed while performing high-speed printing. It must have the ability to absorb and dry sublimation printing inks. Particularly in recent years, since high-speed printing with a printing speed exceeding 1 m / min has been required, exceptionally excellent ink absorption drying properties have been demanded.
しかしながら、従来の昇華型インクジェット捺染転写紙においては、このような高速印刷時におけるインク吸収乾燥性が十分ではないという問題があった。昇華型捺染インクの吸収乾燥が不十分であると、印刷後の巻き取りの際に、裏写りや、汚れ、コスレの問題が発生する。さらには、印刷後の転写工程で、前記の裏写りや、汚れ、コスレの原因となった不要なインクが転写設備や被転写物に付着して、最終転写物の品質低下や汚れも生じやすくなる。このような場合、印刷時及び転写時の作業性が著しく低下してしまうため、従来品よりもさらに優れたインク吸収乾燥性を持つ昇華型インクジェット捺染転写紙が求められている。 However, the conventional sublimation type ink jet textile transfer paper has a problem that the ink absorption drying property at the time of such high speed printing is not sufficient. If the absorption drying of the sublimation printing ink is insufficient, problems such as show-through, stains, and cosmetization occur during winding after printing. Furthermore, in the transfer process after printing, unnecessary ink that causes the above-mentioned show-through, dirt, and scumming adheres to the transfer equipment and the transfer object, and the quality of the final transfer product is likely to deteriorate and become dirty. Become. In such a case, workability at the time of printing and transfer is remarkably lowered, and therefore, there is a demand for sublimation type ink jet textile transfer paper having ink absorption and drying properties superior to those of conventional products.
一方、被転写物に転写捺染する際においては、昇華型捺染インクが昇華捺染型転写紙の昇華型捺染インク受容層とは異なる裏面側に裏抜けを生じたり、被転写物である布帛等を通過（裏抜け）し、転写用プレス機等に昇華型捺染インクが付着してしまう問題があった。しかしながら、この昇華型捺染インクの吸収乾燥性と昇華型捺染インク裏抜け防止性は相反する性質であり、これを両立させた、すなわち印刷時には昇華型捺染インクを速やかに吸収乾燥させ、かつ転写時には裏抜けをさせない昇華捺染型転写紙を製造することは困難であった。さらに、昇華捺染型転写紙における画像の再現性や、被転写物への転写効率（転写画像の解像性や、転写画像濃度レベルと、その均一性等）についても十分なレベルのものとする必要があった。 On the other hand, when transfer printing is performed on the transfer object, the sublimation printing ink causes a back-through on the back side different from the sublimation printing ink receiving layer of the sublimation printing transfer paper, or a cloth or the like to be transferred is used. There is a problem that the dye passes through (behind) and the sublimation printing ink adheres to a transfer press or the like. However, the absorption drying property of this sublimation printing ink and the prevention of reverse exposure of the sublimation printing ink are contradictory properties, and this is compatible, that is, the sublimation printing ink is quickly absorbed and dried during printing, and at the time of transfer. It has been difficult to produce a sublimation printing type transfer paper that does not cause back-through. Furthermore, the image reproducibility on the sublimation printing type transfer paper and the transfer efficiency (transfer image resolution level, transfer image density level and uniformity thereof, etc.) to the transfer object are of a sufficient level. There was a need.
本発明は、上記現状に鑑み、昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク吸収乾燥性と画像再現性と裏抜け防止性を有するとともに、転写による被転写物の画像再現性や転写効率の点でも良好な特性を有する昇華型インクジェット捺染転写紙を提供することを課題とするものである。 In view of the above situation, the present invention has excellent sublimation printing ink absorption drying property, image reproducibility and anti-through-through prevention property when printing onto sublimation inkjet printing transfer paper using sublimation printing ink. It is an object of the present invention to provide a sublimation type ink jet printing transfer paper having good characteristics in terms of image reproducibility and transfer efficiency of a transfer object.
本発明は、基材と昇華型捺染インク受容層とを有する昇華型インクジェット捺染転写紙であって、前記基材上に目止め塗工層が設けられ、前記目止め塗工層上に前記昇華型捺染インク受容層が設けられており、前記昇華型捺染インク受容層は、水溶性樹脂と微細粒子を含有し、前記目止め塗工層は、非水溶性樹脂と無機微粒子を含有し、ＪＩＳ Ｐ ８１２２に準拠したステキヒトサイズが６０秒〜１２０秒であることを特徴とする昇華型インクジェット捺染転写紙に関する。 The present invention is a sublimation type ink jet printing transfer paper having a base material and a sublimation type printing ink receiving layer, wherein a sealing coating layer is provided on the base material, and the sublimation is provided on the sealing coating layer. The sublimation type printing ink receiving layer contains a water-soluble resin and fine particles, and the sealing coating layer contains a water-insoluble resin and inorganic fine particles. The present invention relates to a sublimation type ink-jet printing / transferring paper characterized in that the Stethich size according to P 8122 is 60 seconds to 120 seconds.
本発明では、前記基材は、片面が艶面であるクラフト紙であり、前記目止め塗工層は、前記艶面上に設けられ、前記昇華型捺染インク受容層は、前記微細粒子を２０〜８０質量％含有することが好ましい。 In the present invention, the base material is craft paper having a glossy surface on one side, the sealing coating layer is provided on the glossy surface, and the sublimation printing ink receiving layer has 20 fine particles. It is preferable to contain -80 mass%.
さらに本発明では、前記目止め塗工層は、体積平均粒径が１．０〜２５．０μｍの無機微粒子を目止め塗工層固形分のうち６０〜９０質量％、前記非水溶性樹脂として合成ゴムラテックスを含有することが好ましい。 Further, in the present invention, the sealing coating layer comprises inorganic fine particles having a volume average particle size of 1.0 to 25.0 μm in 60 to 90% by mass of the solid content of the sealing coating layer as the water-insoluble resin. It is preferable to contain a synthetic rubber latex.
本発明の昇華型捺染転写紙は、昇華型捺染インクを用いたインクジェット印刷において優れたインク吸収乾燥性を有しており、印刷時及び転写時の作業性が良好であるとともに、転写紙表面での画像再現性、転写後の被転写物表面での画像再現性や転写効率の点でも良好な特性を有する。特に、インクジェット印刷で高速印刷をしつつ、印刷後の転写紙を高速で巻き取る際において発生しやすい裏写りや、汚れ、コスレの問題を回避することができる。 The sublimation printing transfer paper of the present invention has excellent ink absorption and drying properties in ink jet printing using sublimation printing ink, has good workability at the time of printing and transfer, and on the surface of the transfer paper. The image reproducibility, image reproducibility on the surface of the transferred material after transfer, and transfer efficiency are also good. In particular, while performing high-speed printing by ink jet printing, it is possible to avoid problems of show-through, dirt, and blurring that tend to occur when the printed transfer paper is wound at high speed.
本発明の実施に用いられる基材としては、昇華型捺染インク受容層が設けられる基材であればその素材は限定されない。即ち、木材パルプを主成分とする紙や、無機微粒子を含有する熱可塑性樹脂からなる多孔性樹脂フィルム、更には不織布、布帛、樹脂被覆紙、合成紙等が挙げられる。本発明の効果が顕著に現れる基材としては、昇華型インクジェット捺染転写紙の裏面への加熱により、昇華型捺染インクが昇華しやすい多孔質な素材であり、具体的には、木材パルプを主成分とする紙や、不織布、布帛である。 The base material used in the practice of the present invention is not limited as long as the base material is provided with a sublimation printing ink receiving layer. That is, paper mainly composed of wood pulp, a porous resin film made of a thermoplastic resin containing inorganic fine particles, non-woven fabric, fabric, resin-coated paper, synthetic paper, and the like can be given. The substrate in which the effect of the present invention is remarkably exhibited is a porous material in which the sublimation type printing ink is easily sublimated by heating to the back surface of the sublimation type ink jet printing transfer paper. Specifically, wood pulp is mainly used. It is paper, a nonwoven fabric, or a fabric as a component.
基材として、木材パルプを主成分とする紙を使用することが好ましく、ヤンキードライヤーを用いて乾燥工程を行うことで片面を艶面とした片艶紙を使用することが特に好ましい。片艶紙は従来の紙と異なり、寸法安定性に優れ、フィルムと異なりリサイクルが可能であり、昇華型捺染インクの吸収乾燥性に優れる特徴を有する。 As a base material, it is preferable to use paper mainly composed of wood pulp, and it is particularly preferable to use single glossy paper having a glossy surface on one side by performing a drying step using a Yankee dryer. Unlike glossy paper, single glossy paper has excellent dimensional stability, and unlike film, it can be recycled, and has excellent absorption and drying properties of sublimation printing ink.
本発明の昇華型インクジェット捺染転写紙における基材は、昇華型捺染インク受容層が設けられる支持体であれば、その素材は限定されないが、本発明者が最も好適として見出した片艶紙を基材として以下に説明する。 The substrate of the sublimation type ink jet printing transfer paper of the present invention is not limited as long as it is a support provided with a sublimation type printing ink receiving layer, but is based on single glossy paper that the present inventors have found most suitable. The material will be described below.
本発明者が最も好適として見出した片艶紙を基材として以下に説明する。 The glossy paper that the present inventors have found most suitable will be described below as a base material.
片艶紙の艶面は表面の平坦性が高いので、ここに昇華型捺染インク受容層を設けることによって均質性の高い昇華型捺染インク受容層を得ることが可能になり、画像再現性や作業性に優れているとともに、昇華捺染のための加温転写時に被転写物の画像再現性や、転写効率の点においても優れた特性を有することができ、本発明における昇華型インクジェット捺染転写紙に特に優れた基材として好適に用いられ、さらに、バックコート層を非艶面に設けることで、より伸縮率を低い数値とすることができる。 Since the glossy surface of single glossy paper has a high surface flatness, it is possible to obtain a sublimation printing ink receiving layer with high homogeneity by providing a sublimation printing ink receiving layer here. It has excellent properties and can also have excellent image reproducibility and transfer efficiency at the time of warm transfer for sublimation printing. It is suitably used as a particularly excellent substrate, and further, by providing a back coat layer on the non-glossy surface, the expansion / contraction rate can be made a lower value.
片艶紙は、ヤンキードライヤーを用いて乾燥工程を行うことでヤンキードライヤー面を艶面とした紙である。片艶紙は、湿紙をヤンキードライヤーに貼り付けて乾燥させるため、多筒式ドライヤーを用いる湿紙の乾燥方式に比べ、寸法安定性に優れ、艶面が高平滑であるので、優れた画像再現性を達成することができる。更に、艶面に比べ裏面が粗面であり空隙を多く有するため、加熱時に熱保持効果が高く、均等且つ効果的に昇華型捺染インクの昇華を促す事ができる。これに用いる片艶紙は、米坪が６０〜１５０ｇ／ｍ２であることが好ましく、９０〜１１０ｇ／ｍ２がより好ましい。片艶紙の米坪が６０ｇ／ｍ２未満であると、引張強度と引裂強度の低下により紙切れや昇華型捺染インク受容層への記録時に、基材に波うちや加熱時に伸縮変動が起きやすくなるとともに、作業性が低下する問題が生じ易い。片艶紙の米坪が１５０ｇ／ｍ２を超えると被転写物への昇華型捺染インクの加熱転写時に熱伝達が悪くなり、転写効率が低下する傾向がある。 Single glossy paper is paper that has a Yankee dryer surface as a glossy surface by performing a drying process using a Yankee dryer. Single glossy paper is made by attaching wet paper to a Yankee dryer and drying it. Compared to wet paper drying using a multi-cylinder dryer, it has superior dimensional stability and a glossy surface that is highly smooth. Reproducibility can be achieved. Furthermore, since the back surface is rougher than the glossy surface and has many voids, the heat retention effect is high during heating, and the sublimation printing ink can be sublimated evenly and effectively. Katatsuyashi used therefor is preferably a basis weight is 60 to 150 g / m 2, more preferably 90~110g / m 2. If the glossy surface of the glossy paper is less than 60 g / m 2 , the tensile strength and tear strength will decrease, and when the paper is cut or recorded on the sublimation printing ink receiving layer, the substrate tends to undergo stretching fluctuations when wavy or heated. At the same time, there is a tendency for the workability to deteriorate. If the plain weight of the glossy paper exceeds 150 g / m 2 , heat transfer is deteriorated at the time of heat transfer of the sublimation printing ink to the transfer object, and the transfer efficiency tends to be lowered.
また、片艶紙の艶面のＪＩＳ Ｐ ８１１９に準拠下したベック平滑度が４０〜２００秒であることが好ましく、５０〜１００秒がより好ましい。艶面のベック平滑度が４０秒未満であると印刷時の昇華型捺染インクの吸収・乾燥性は高くなるももの、画像再現性が低下し、被転写物への昇華型捺染インクの転写時の画像再現性と転写効率が低下する傾向がある。また、２００秒を超えると水溶性樹脂と微細粒子からなる昇華型捺染インク受容層の形成にムラが発生し、画像再現性が低下する傾向がある。 Moreover, it is preferable that the Beck smoothness based on JISP8119 of the glossy surface of single glossy paper is 40 to 200 second, and 50 to 100 second is more preferable. If the glossy surface has a Beck smoothness of less than 40 seconds, the absorption / drying property of the sublimation printing ink at the time of printing increases, but the image reproducibility deteriorates and the sublimation printing ink is transferred to the transfer object. Image reproducibility and transfer efficiency tend to decrease. On the other hand, if it exceeds 200 seconds, unevenness occurs in the formation of the sublimation printing ink receiving layer comprising the water-soluble resin and fine particles, and the image reproducibility tends to be lowered.
片艶紙の艶面は表面の平坦性が高いので、ここに目止め塗工層、さらに昇華型捺染インク受容層を設けることによって均質性の高い昇華型捺染インク受容層を得ることが可能になり、画像再現性や作業性に優れているとともに、昇華捺染のための加温転写時に被転写物の画像再現性や、転写効率の点においても優れた特性を有することができ、本発明における昇華型インクジェット捺染転写紙に特に優れた基材として好適に用いられる。 Because the glossy surface of single glossy paper has a high surface flatness, it is possible to obtain a sublimation printing ink receiving layer with high homogeneity by providing a sealing coating layer and a sublimation printing ink receiving layer here. In addition to being excellent in image reproducibility and workability, it can have excellent characteristics in terms of image reproducibility and transfer efficiency of a transferred material during warm transfer for sublimation printing, and in the present invention. It is suitably used as a particularly excellent substrate for sublimation type ink jet textile transfer paper.
非艶面である裏面の平滑度は、１８秒程度が好ましい。裏面が艶面と同等以上の平滑度を有すると、加熱時の熱保持性が劣り、転写による被転写物の画像再現性や転写効率の点で劣る問題が発現する恐れがある。従って、表裏面とも多筒ドライヤーで乾燥された上質紙などは、片艶紙に比べ転写による被転写物の画像再現性や転写効率の点で劣る場合がある。 The smoothness of the back surface, which is a non-glossy surface, is preferably about 18 seconds. If the back surface has a smoothness equal to or higher than that of the glossy surface, heat retention during heating is inferior, and there may be a problem that inferior in terms of image reproducibility and transfer efficiency of a transfer object by transfer. Therefore, high-quality paper or the like dried with a multi-cylinder dryer on both the front and back surfaces may be inferior in terms of image reproducibility and transfer efficiency of the transferred material by transfer compared to single glossy paper.
更に、片艶紙の裏面にバックコート層を設けることで、艶面に付与されたヤンキードライヤーによる緊張乾燥に近似した、繊維同士の寸法変化の少ない裏面性状を得ることができ、艶面、裏面相俟って寸法変化の少ない性状を醸し出すことが出来る。 Furthermore, by providing a back coat layer on the back side of single glossy paper, it is possible to obtain a back side property with little dimensional change between fibers, similar to tension drying with a Yankee dryer applied to the glossy surface. Together, it can bring out properties with little dimensional change.
本発明に係る片艶紙はいわゆる製紙分野で使用される原料より構成される。使用するパルプとしては特に限定されないが、例えば、針葉樹未晒クラフトパルプ（ＮＵＫＰ）や針葉樹晒クラフトパルプ（ＮＢＫＰ）、広葉樹未晒クラフトパルプ（ＬＵＫＰ）や広葉樹晒クラフトパルプ（ＬＢＫＰ）等の化学パルプ；サーモメカニカルパルプ（ＴＭＰ）、ケミサーモメカニカルパルプ（ＣＴＭＰ）、リファイナーメカニカルパルプ（ＲＭＰ）、リファイナーグランドパルプ（ＲＧＰ）、ケミグランドパルプ（ＣＧＰ）、サーモグランドパルプ（ＴＧＰ）、砕木パルプ（ＧＰ）、ストーングランドパルプ（ＳＧＰ）、加圧ストーングランドパルプ（ＰＧＷ）等の機械パルプ；デインキングパルプ（ＤＩＰ）、ウェストパルプ（ＷＰ）等の化学パルプや機械パルプを含む古紙パルプ等が挙げられ、これらの中から１種又は２種以上を選択して用いることができる。これらのうち、針葉樹晒クラフトパルプ、広葉樹晒クラフトパルプを、紙質強度と基材表面の平坦性、昇華型捺染インクの昇華型インクジェット捺染転写紙における品質確認において適宜組合せて用いることが好ましい。 The glossy paper according to the present invention is composed of raw materials used in the so-called papermaking field. Although it does not specifically limit as a pulp to be used, For example, chemical pulps, such as a softwood unbleached kraft pulp (NUKP), a softwood bleached kraft pulp (NBKP), a hardwood unbleached kraft pulp (LUKP), and a hardwood bleached kraft pulp (LBKP); Thermomechanical pulp (TMP), Chemithermomechanical pulp (CTMP), Refiner mechanical pulp (RMP), Refiner ground pulp (RGP), Chemiground pulp (CGP), Thermogrand pulp (TGP), Groundwood pulp (GP), Stone Mechanical pulp such as ground pulp (SGP) and pressed stone grand pulp (PGW); waste paper pulp including chemical pulp and mechanical pulp such as deinking pulp (DIP) and waist pulp (WP). 1 type or 2 types from It can be selected and used above. Of these, softwood bleached kraft pulp and hardwood bleached kraft pulp are preferably used in combination as appropriate in terms of paper strength, flatness of the substrate surface, and quality confirmation of sublimation ink-jet printing paper for sublimation printing ink.
特に基材原料として好ましいパルプは、使用するパルプ原料の平均繊維長が１．０ｍｍ以上１．６ｍｍ未満であり、ＮＢＫＰとＬＢＫＰの配合割合が５０／５０〜１５／８５質量％であり、さらに、ルンケル比が０．８以下のパルプ繊維を用いる事が好ましい。ルンケル比は、繊維のルーメン（内腔）の幅Ｌと細胞壁の厚さｔによって求められる値であり、Ｒ ＝２ ・ｔ ／Ｌ によって表される。このルンケル比は、数値が低いほど同じ径に対して繊維壁の厚みが小さくなり、繊維は柔軟性を持つ。ルンケル比が０．８以下であれば、昇華捺染工程において、被転写物との密着性にすぐれ、昇華型捺染インクにおける溶媒を紙中に吸収しやすくなり、昇華型捺染インクの吸収乾燥性を向上させることができる。ルンケル比が０．８以下のパルプ繊維を得るには、木材として比較的成長の早い植林木等を原料とするのが好ましい。 Particularly preferred pulp as a base material has an average fiber length of 1.0 mm or more and less than 1.6 mm of the pulp material to be used, the blending ratio of NBKP and LBKP is 50/50 to 15/85% by mass, It is preferable to use pulp fibers having a Runkel ratio of 0.8 or less. The Runkel ratio is a value determined by the width L of the fiber lumen (lumen) and the thickness t of the cell wall, and is represented by R = 2 · t 2 / L 2. The lower the value of the Runkel ratio, the smaller the fiber wall thickness with respect to the same diameter, and the more flexible the fiber. If the Runkel ratio is 0.8 or less, in the sublimation printing process, the adhesion to the transfer object is excellent, the solvent in the sublimation printing ink is easily absorbed in the paper, and the absorption drying property of the sublimation printing ink is improved. Can be improved. In order to obtain a pulp fiber having a Runkel ratio of 0.8 or less, it is preferable to use a planted tree or the like that grows relatively quickly as a raw material.
前記基材は、好適にはＪＩＳ Ｐ ８１１７に準拠した昇華型インクジェット捺染転写紙の透気度が８０〜３０，５００秒、より好適には１，３５０〜３０，０００秒、さらに好適には、１，５００〜２９，０００秒に調整可能な範囲で、酸化チタン、クレー、タルク、炭酸カルシウム等の填料を含有するものであってもよい。透気度が、８０秒未満では、転写効率や昇華型捺染インクの裏抜け防止性が低下する問題が生じ、３０，５００秒を超えると、熱伝達が低下し昇華型捺染インクの転写効率が低下すると共に、画像再現性が悪くなる。 The base material preferably has a gas permeability of sublimation type ink jet printing transfer paper according to JIS P 8117 of 80 to 30,500 seconds, more preferably 1,350 to 30,000 seconds, and more preferably, It may contain a filler such as titanium oxide, clay, talc, calcium carbonate and the like within a range adjustable to 1,500 to 29,000 seconds. If the air permeability is less than 80 seconds, there arises a problem that transfer efficiency and prevention of back-through of the sublimation printing ink are deteriorated. If the air permeability exceeds 30,500 seconds, heat transfer is reduced and the transfer efficiency of the sublimation printing ink is decreased. The image reproducibility deteriorates with a decrease.
本発明では基材上に目止め塗工層を設ける。当該目止め塗工層は、非水溶性樹脂及び無機微粒子を含有する塗工液を基材表面に塗工して形成される層であり、印刷時に昇華型捺染インクが基材に浸透するのを抑制することができる。これによって、加熱転写時に昇華型捺染インクが基材の裏面側から昇華する、いわゆる裏抜けの問題を防止することができる。 In the present invention, a sealing coating layer is provided on the substrate. The sealing coating layer is a layer formed by applying a coating liquid containing a water-insoluble resin and inorganic fine particles to the substrate surface, and the sublimation printing ink penetrates the substrate during printing. Can be suppressed. Thereby, it is possible to prevent a so-called back-through problem in which the sublimation printing ink sublimates from the back side of the substrate during heat transfer.
更に、目止め塗工層を設ける事で、得られる昇華型インクジェット捺染転写紙の透気度を１５００秒以上、より好適には３０００秒以上に高めることが可能になると共に、透気度の調整手段としても機能させることが可能になり、先の裏抜け防止効果と相俟って、本発明の課題である昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク吸収乾燥性と画像再現性と裏抜け防止性を有するとともに、転写による被転写物の画像再現性や転写効率を向上させることができる。 Furthermore, by providing a sealing coating layer, it is possible to increase the air permeability of the obtained sublimation type ink jet textile transfer paper to 1500 seconds or more, more preferably 3000 seconds or more, and to adjust the air permeability. It can also function as a means, and combined with the effect of preventing the previous breakthrough, excellent sublimation during printing on sublimation ink jet printing transfer paper using the sublimation printing ink, which is the subject of the present invention It has mold printing ink absorption drying property, image reproducibility, and anti-through-through property, and can improve the image reproducibility and transfer efficiency of the transferred material by transfer.
本発明の目止め塗工層で使用する非水溶性樹脂としては、例えば、合成ゴムラテックスとして、ＳＢＲ、ＮＢＲ、ＭＢＲ等、ビニルポリマー系ラテックスが挙げられる。なかでも、印刷時に昇華型捺染インクの基材への浸透及び裏抜け防止を効果的に抑制できることから、合成ゴムラテックスが好ましい。微細な合成ゴムのエマルジョンからなる合成ゴムラテックスは、被膜形成性に優れるものの、本発明における昇華型捺染インクの溶媒を均等に基材中に浸透せしめ、後述する基材中に含有させる消サイズ剤との相乗効果にて、昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク吸収乾燥性と画像再現性と裏抜け防止性を有するとともに、転写による被転写物の画像再現性や転写効率を向上させることができる。 Examples of the water-insoluble resin used in the sealing coating layer of the present invention include vinyl polymer latexes such as SBR, NBR and MBR as synthetic rubber latex. Among these, synthetic rubber latex is preferable because it can effectively suppress the penetration of the sublimation type printing ink into the base material and the prevention of back-through during printing. Synthetic rubber latex composed of fine synthetic rubber emulsion is excellent in film forming property, but the solvent for sublimation type printing ink in the present invention is uniformly permeated into the base material and is contained in the base material described later. As a result, it has excellent sublimation printing ink absorption drying, image reproducibility, and prevention of back-through when printing on sublimation inkjet printing transfer paper using sublimation printing ink. The image reproducibility and transfer efficiency of the transferred product can be improved.
本発明の目止め塗工層は、無機微粒子を含有する。無機微粒子としては、例えば、軽質炭酸カルシウム、重質炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、カオリン、タルク、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、珪酸マグネシウム、コロイダルシリカ、合成非晶質シリカ、アルミナ、コロイダルアルミナ、アルミナ水和物（擬ベーマイト等）、水酸化アルミニウム、リトポン、ゼオライト、加水ハロイサイト、水酸化マグネシウム等が挙げられる。なかでも、カオリンが好ましい。 The sealing coating layer of the present invention contains inorganic fine particles. Examples of inorganic fine particles include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, magnesium hydroxide, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. Diatomaceous earth, calcium silicate, magnesium silicate, colloidal silica, synthetic amorphous silica, alumina, colloidal alumina, alumina hydrate (such as pseudoboehmite), aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide, etc. Can be mentioned. Of these, kaolin is preferred.
本発明で好適に用いることができるカオリンは、板状結晶構造をもち目止め塗工層表面の平坦性向上に寄与するとともに、昇華型捺染インクの溶媒を速やかに基材に浸透させる効能を有し、ステキヒトサイズに代表されるピンホール的な昇華型捺染インクの基材への浸透や裏抜け防止効果に優れる。 Kaolin, which can be suitably used in the present invention, has a plate-like crystal structure and contributes to improving the flatness of the surface of the sealing coating layer, and has the effect of allowing the solvent of the sublimation printing ink to quickly penetrate into the substrate. In addition, the pinhole-type sublimation printing ink typified by the steecht size is excellent in the penetration into the base material and the effect of preventing the back-through.
目止め塗工層に配合する無機微粒子としては、体積平均粒径が１．０〜２５．０μｍのものが、より好ましくは５．０〜２０．０μｍのものが好ましい。これによって、印刷時に昇華型捺染インクが基材に浸透するのを効果的に抑制できる。体積平均粒径が１．０μｍ未満であると、目止め効果が高くなりすぎて昇華型捺染インクの溶媒の基材中への浸透を阻害する問題を引き起こし、逆に２５．０μｍを超えると、昇華型捺染インクの目止め性が十分でなく、昇華型捺染インクの溶質（染料成分）の基材への浸透や、加熱による昇華捺染工程において、昇華捺染インクの裏抜けが生じやすくなる問題が生じやすくなり好ましくない。 The inorganic fine particles to be blended in the filler coating layer preferably have a volume average particle size of 1.0 to 25.0 μm, more preferably 5.0 to 20.0 μm. Thereby, it is possible to effectively prevent the sublimation printing ink from penetrating into the substrate during printing. When the volume average particle size is less than 1.0 μm, the sealing effect becomes too high, causing a problem of inhibiting the penetration of the solvent of the sublimation printing ink into the base material, and conversely when exceeding 25.0 μm, There is a problem that the sublimation printing ink is not sufficiently sealed, and the solute (dye component) of the sublimation printing ink penetrates into the base material, and the sublimation printing ink tends to break through in the sublimation printing process by heating. It tends to occur and is not preferable.
目止め塗工層では、目止め塗工層固形分のうち、無機微粒子を６０〜９０質量％含有することが好ましい。無機微粒子の含有量が６０質量％未満であると、昇華型捺染インクの目止め性が十分でなく、昇華型捺染インクの溶質（染料成分）の基材への浸透や、加熱による昇華捺染工程において、昇華捺染インクの裏抜けの問題が生じやすくなり、逆に９０質量％を超えると、目止め効果が高くなりすぎて昇華型捺染インクの溶媒の基材中への浸透を阻害する問題を引き起こす場合が生じるため好ましくない。 In the sealing coating layer, it is preferable to contain 60 to 90% by mass of inorganic fine particles in the solid content of the sealing coating layer. When the content of the inorganic fine particles is less than 60% by mass, the sealing property of the sublimation printing ink is not sufficient, and the solute (dye component) of the sublimation printing ink penetrates into the base material, or the sublimation printing process by heating. However, if the amount exceeds 90% by mass, the sealing effect becomes too high, and the problem of inhibiting the penetration of the solvent of the sublimation printing ink into the substrate is likely to occur. Since it may cause, it is not preferable.
目止め塗工層の塗工量は特に限定されないが、乾燥質量で１．０〜８．０ｇ／ｍ２の範囲、より好ましくは２．０〜７．０ｇ／ｍ２が好ましい。塗工量が１．０ｇ／ｍ２未満であると、目止め塗工層の効果の発現が困難であり、逆に８．０ｇ／ｍ２を超えると目止め塗工層の効果が高すぎるとともに、加熱による昇華捺染工程において昇華型捺染インク受容層への熱の伝達が阻害され、昇華型捺染インクの転写効率が低下するため好ましくない。 Although the coating amount of the sealing coating layer is not particularly limited, the dry mass is preferably in the range of 1.0 to 8.0 g / m 2 , more preferably 2.0 to 7.0 g / m 2 . If the coating amount is less than 1.0 g / m 2, it is difficult to express the effect of the sealing coating layer. Conversely, if the coating amount exceeds 8.0 g / m 2 , the effect of the sealing coating layer is too high. At the same time, heat transfer to the sublimation printing ink receiving layer is hindered in the sublimation printing process by heating, which is not preferable because the transfer efficiency of the sublimation printing ink is lowered.
目止め塗工層の塗布方法としては特に限定されないが、例えば、エアーナイフコーター、ロールコーター、バーコーター、コンマコーター、ブレードコーター等の公知の塗工機を用いて塗工することができる。 Although it does not specifically limit as a coating method of a sealing coating layer, For example, it can coat using well-known coating machines, such as an air knife coater, a roll coater, a bar coater, a comma coater, a blade coater.
特に、目止め塗工層において、無機微粒子として体積平均粒径が１．０〜２５．０μｍのものを、目止め塗工層固形分のうち６０〜９０質量％になるよう使用し、かつ非水溶性樹脂として合成ゴムラテックスを使用することで、印刷時に昇華型捺染インクが基材に浸透するのを抑制し、加熱転写時に昇華型捺染インクが基材の裏面側に裏抜けする問題を効果的に防止することができる。 In particular, in the seal coating layer, inorganic fine particles having a volume average particle diameter of 1.0 to 25.0 μm are used so that the solid content of the seal coating layer is 60 to 90% by mass, and By using synthetic rubber latex as a water-soluble resin, it prevents the sublimation printing ink from penetrating into the substrate at the time of printing, and the problem that the sublimation printing ink penetrates to the back side of the substrate at the time of heat transfer is effective. Can be prevented.
このように基材上に目止め塗工層を設けた後、さらに目止め塗工層上に昇華型捺染インク受容層を設ける。昇華型捺染インク受容層は、微細粒子と、バインダーとして水溶性樹脂とを含有するものである。また、後述するが、本発明の好適な態様では昇華型捺染インク受容層の表面は微細粒子の凝集塊による凹凸にて被覆された性状を呈しており、この性状が、印刷時には昇華型捺染インクの吸収乾燥性と紙における画像再現性や作業性を良好にするとともに、昇華捺染のための加温転写時に昇華型捺染インクが昇華型インクジェット捺染転写紙の裏側に裏抜けするのを防止する特性においても優れ、さらには、転写による被転写物の画像再現性や、転写効率の点においても優れた特性を醸し出すものである。 After the sealing coating layer is provided on the substrate in this manner, a sublimation printing ink receiving layer is further provided on the sealing coating layer. The sublimation type printing ink receiving layer contains fine particles and a water-soluble resin as a binder. As will be described later, in the preferred embodiment of the present invention, the surface of the sublimation type printing ink receiving layer has a property of being covered with irregularities by agglomerates of fine particles, and this property is sublimation type printing ink at the time of printing. Properties that improve the absorption and drying properties of paper, image reproducibility and workability on paper, and prevent sublimation-type printing ink from penetrating to the back side of sublimation-type inkjet printing transfer paper during warm transfer for sublimation printing In addition, it also exhibits excellent characteristics in terms of image reproducibility and transfer efficiency of a transfer object by transfer.
本発明者等の知見では、本発明に基づき得られた昇華型インクジェット捺染転写紙のＪＩＳ Ｐ ８１２２に準拠したステキヒトサイズが６０秒〜１２０秒である。ステキヒトサイズが６０秒未満では、昇華型インクジェット捺染転写紙への昇華型捺染インクによるインクジェット印刷時だけでなく、印字加熱による昇華捺染工程において、昇華型捺染インクの裏抜けが生じやすく、１２０秒を超えると、高速印字時の昇華型捺染インクのインク乾燥性が低下し、コスレ汚れや裏移りという問題が生じる。 According to the knowledge of the present inventors, the steecht size based on JIS P 8122 of the sublimation type ink jet printing transfer paper obtained based on the present invention is 60 seconds to 120 seconds. If the steecht size is less than 60 seconds, the sublimation-type printing ink tends to break through not only during ink-jet printing with the sublimation-type printing ink on the sublimation-type ink-jet printing transfer paper, but also in the sublimation printing process by printing heating. If it exceeds 1, the ink drying property of the sublimation type printing ink at the time of high-speed printing is lowered, and there arises a problem of smearing and set-off.
本発明の昇華型インクジェット捺染転写紙のステキヒトサイズ度は、目止め塗工層や昇華型捺染インク受容層の構成による調整も可能と考えられるものの、昇華型インクジェット捺染転写紙の品質維持を考慮すると、基材のサイズ性を調整することが好ましく、最も好適な手法としては基材中に消サイズ剤を含有させることが好適である。 The degree of stickiness of the sublimation ink jet printing transfer paper of the present invention can be adjusted by the composition of the sealing coating layer and the sublimation printing ink receiving layer, but it is necessary to maintain the quality of the sublimation ink jet printing transfer paper. Then, it is preferable to adjust the sizing property of the base material, and as the most suitable method, it is preferable to contain a sizing agent in the base material.
本発明において好適に使用できる消サイズ剤は、嵩高剤とも呼ばれる薬剤であり、紙料に内添して抄紙することで、紙の密度を低下させることができる界面活性剤である。本発明で使用可能な消サイズ剤としては、例えば、アニオン性界面活性剤として、アルキル硫酸塩、ポリオキシアルキレンアルキルエーテル硫酸塩、ポリオキシアルキレン脂肪酸エステル、脂肪酸およびその塩等が挙げられ、カチオン性界面活性剤としては、塩化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム、塩化ベンザルコニウム、アルキルアミン酸塩等が挙げられ、非イオン性界面活性剤としては多価アルコールの脂肪酸エステル、および、当該多価アルコールの脂肪酸エステルのアルキレンオキシド付加物、脂肪酸アミドおよび当該脂肪酸アミドのアルキレンオキシド付加物等が挙げられる。中でも、昇華型捺染インクの定着促進を来たさない、アニオン性界面活性剤、更にはポリオキシアルキレン脂肪酸エステルが易水溶性であり、基材中での分散性に優れ紙力低下が少ない事から最も好適に用いられる。 The sizing agent that can be suitably used in the present invention is a chemical also called a bulking agent, and is a surfactant that can reduce the density of paper by making a paper by adding it internally to a paper material. Examples of the sizing agent that can be used in the present invention include, as anionic surfactants, alkyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene fatty acid esters, fatty acids and salts thereof, and the like. Surfactants include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkylamine salts, etc. Nonionic surfactants include fatty acid esters of polyhydric alcohols, and the polyvalent Examples include alkylene oxide adducts of fatty acid esters of alcohol, fatty acid amides, and alkylene oxide adducts of the fatty acid amides. Among them, anionic surfactants that do not promote fixing of sublimation printing inks, and polyoxyalkylene fatty acid esters are readily water-soluble, and have excellent dispersibility in the base material and little reduction in paper strength. Are most preferably used.
基材中に消サイズ剤を含有することで、基材が嵩高となり、その嵩高な基材が昇華型捺染インクの溶媒部分を迅速に吸収しながら、昇華型捺染インクの溶質部分を昇華型捺染インク受容層の表面にとどめることができる。 By including a sizing agent in the substrate, the substrate becomes bulky, and the bulky substrate quickly absorbs the solvent portion of the sublimation printing ink while sublimating the solute portion of the sublimation printing ink. It can remain on the surface of the ink receiving layer.
上記消サイズ剤の含有量は、基材総量のうち０．０１〜３．０質量％であることが好ましく，さらに０．０５〜０．１質量％であることがより好ましい。消サイズ剤の含有量が０．０１質量％未満であると、消サイズ剤の効果が発現できない問題があり、逆に３．０質量％を超えると、紙力低下を招き目止め塗工層塗工時や昇華型捺染インク受容層塗工時、昇華型捺染工程での加熱時に熱劣化を招き、断紙を生じる問題がある。 The content of the sizing agent is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 0.1% by mass, based on the total amount of the base material. If the content of the sizing agent is less than 0.01% by mass, there is a problem that the effect of the sizing agent cannot be expressed. Conversely, if the content exceeds 3.0% by mass, the paper strength is reduced and the coating layer is stopped. There is a problem of causing paper breakage due to thermal degradation during coating, sublimation printing ink-receiving layer coating, or heating in the sublimation printing process.
また基材中には、酸化澱粉、アセチル化澱粉、エステル化澱粉、エーテル化澱粉等の各種澱粉や、紙力増強剤、内添サイズ剤、外添サイズ剤、歩留向上剤等の添加薬品を含有することもできる。 In the base material, various starches such as oxidized starch, acetylated starch, esterified starch and etherified starch, and additive chemicals such as paper strength enhancer, internal sizing agent, external sizing agent, yield improving agent, etc. Can also be contained.
本発明では、昇華型捺染インク受容層に配合する微細粒子として、合成非晶質シリカを用いることが好ましい。このような合成非晶質シリカとは、ケイ酸のゲル化によりＳｉＯ２の三次元構造を形成させた、細孔容積の多い多孔性で不定形の微粒子であり、１０〜２０００オングストローム程度の細孔径を有する。該合成非晶質シリカを用いることによって、本発明の昇華型インクジェット捺染転写紙の昇華型捺染インクの吸収乾燥性を向上させると共に、昇華型捺染インクの被転写物への転写効率も向上し、被転写物上の画像を一層鮮明にすることができる。 In the present invention, it is preferable to use synthetic amorphous silica as fine particles to be blended in the sublimation type printing ink receiving layer. Such a synthetic amorphous silica is a porous and amorphous fine particle having a large pore volume, in which a three-dimensional structure of SiO 2 is formed by the gelation of silicic acid, and has a fineness of about 10 to 2000 angstroms. Has a pore size. By using the synthetic amorphous silica, the sublimation type printing ink of the present invention is improved in the absorption drying property of the sublimation type printing ink, and the transfer efficiency of the sublimation type printing ink to the transfer object is improved. The image on the transfer object can be made clearer.
このような合成非晶質シリカとしては、市販のものを好適に用いることができ、例えば、ミズカシルＰ−５２６、ミズカシルＰ−８０１、ミズカシルＮＰ−８、ミズカシルＰ−８０２、ミズカシルＰ−８０２Ｙ、ミズカシルＣ−２１２、ミズカシルＰ−７３、ミズカシルＰ−７８Ａ、ミズカシルＰ−７８Ｆ、ミズカシルＰ−８７、ミズカシルＰ−７０５、ミズカシルＰ−７０７、ミズカシルＰ−７０７Ｄ、ミズカシルＰ−７０９、ミズカシルＣ−４０２、ミズカシルＣ−４８４（以上、水澤化学工業（株）製）、トクシールＵ、トクシールＵＲ、トクシールＧＵ、トクシールＡＬ−１、トクシールＧＵ−Ｎ、トクシールＮ、トクシールＮＲ、トクシールＰＲ、ソーレックス、ファインシールＥ−５０、ファインシールＴ−３２、ファインシールＸ−３０、ファインシールＸ−３７、ファインシールＸ−３７Ｂ、ファインシールＸ−４５、ファインシールＸ−６０、ファインシールＸ−７０、ファインシールＲＸ−７０、ファインシールＡ、ファインシールＢ（以上、（株）トクヤマ製）、シペルナート、カープレックスＦＰＳ−１０１、カープレックスＣＳ−７、カープレックス２２Ｓ、カープレックス８０、カープレックス８０Ｄ、カープレックスＸＲ、カープレックス６７（以上、ＤＳＬ．ジャパン（株）製）、サイロイド６３、サイロイド６５、サイロイド６６、サイロイド７７、サイロイド７４、サイロイド７９、サイロイド４０４、サイロイド６２０、サイロイド８００、サイロイド１５０、サイロイド２４４、サイロイド２６６（以上、富士シリシア化学（株）製）、ニップジェルＡＹ−２００、ニップジェルＡＹ−６Ａ２、ニップジェルＡＺ−２００、ニップジェルＡＺ−６Ａ０、ニップジェルＢＹ−２００、ニップジェルＢＹ−２００、ニップジェルＣＸ−２００、ニップジェルＣＹ−２００、ニップシールＥ−１５０Ｊ、ニップシールＥ−２２０Ａ、ニップシールＥ−２００Ａ（以上、東ソー・シリカ（株）製）などが挙げられる。 As such synthetic amorphous silica, commercially available ones can be suitably used. For example, Mizukacil P-526, Mizukacil P-801, Mizukacil NP-8, Mizukacil P-802, Mizukacil P-802Y, Mizukacil. C-212, Mizukacil P-73, Mizukacil P-78A, Mizukacil P-78F, Mizukacil P-87, Mizukacil P-705, Mizukacil P-707, Mizukacil P-707D, Mizukacil P-709, Mizukacil C-402, Mizukacil C-484 (manufactured by Mizusawa Chemical Co., Ltd.), Toxeal U, Toxeal UR, Toxeal GU, Toxeal AL-1, Toxeal GU-N, Toxeal N, Toxeal NR, Toxeal PR, Sorex, Fineseal E- 50, fine seal T-32, fine sea X-30, fine seal X-37, fine seal X-37B, fine seal X-45, fine seal X-60, fine seal X-70, fine seal RX-70, fine seal A, fine seal B (above, (Manufactured by Tokuyama Corporation), Sipernato, Carplex FPS-101, Carplex CS-7, Carplex 22S, Carplex 80, Carplex 80D, Carplex XR, Carplex 67 (above, manufactured by DSL Japan Co., Ltd.) ), Syloid 63, Syroid 65, Syloid 66, Syloid 77, Syloid 74, Syloid 79, Syloid 404, Syloid 620, Syloid 800, Syloid 150, Syloid 244, Syroid 266 (manufactured by Fuji Silysia Chemical Co., Ltd.), Nip gel AY-200, nip gel AY-6A2, nip gel AZ-200, nip gel AZ-6A0, nip gel BY-200, nip gel BY-200, nip gel CX-200, nip gel CY-200, nip seal E-150J, nip seal E-220A, Nip seal E-200A (above, manufactured by Tosoh Silica Co., Ltd.).
本発明で用いられる合成非晶質シリカは微細な粒子の凝集体であることが好ましく、凝集体の平均粒子径が１．７μｍ〜１３μｍ、好適には２．３μｍ〜１２．７μｍの範囲内にあることが好ましい。合成非晶質シリカとして平均粒子径が１．７μｍ〜１３．０μｍの凝集体を使用することにより、高品質な色再現性、画像再現性を得ることができる。微細な粒子の凝集体の平均粒子径が１．７μｍ未満であると昇華型捺染インクの吸収乾燥性が低下する傾向があり、また、微細な粒子の凝集体の平均粒子径が１３．０μｍを超えると転写したプリント物の発色濃度が低くなる場合がある。 The synthetic amorphous silica used in the present invention is preferably an aggregate of fine particles, and the average particle diameter of the aggregate is in the range of 1.7 μm to 13 μm, preferably 2.3 μm to 12.7 μm. Preferably there is. By using an aggregate having an average particle size of 1.7 μm to 13.0 μm as the synthetic amorphous silica, high quality color reproducibility and image reproducibility can be obtained. If the average particle size of the fine particle aggregate is less than 1.7 μm, the absorption drying property of the sublimation type printing ink tends to be lowered, and the average particle size of the fine particle aggregate is 13.0 μm. If it exceeds, the color density of the transferred printed matter may be lowered.
本発明では、合成非晶質シリカを１種類のみの単独での凝集体を用いることができるが、好適には、凝集体の平均粒子径が異なる２種類以上の合成非晶質シリカ凝集体を組み合わせて使用することが好ましい。特に、凝集体の平均粒子径が１．７〜５．０μｍの合成非晶質シリカ凝集体と、凝集体の平均粒子径が５μｍを超える合成非晶質シリカ凝集体とを併用し、組合せた微細粒子の混合体を用いることが好ましい。このように平均粒子径が数μｍの範囲で異なる合成非晶質シリカ凝集体を併用することによって、凝集体と凝集体の間隙を異なる平均粒子径の凝集体が補完する凝集塊が形成され、昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク乾燥性と画像再現性、裏抜け防止性及び耐熱性を有するとともに、転写による被転写物の画像再現性や転写効率の点でも良好な特性を得ることができる。 In the present invention, only one kind of aggregate of synthetic amorphous silica can be used, but preferably two or more kinds of synthetic amorphous silica aggregates having different average particle diameters of aggregates are used. It is preferable to use in combination. Particularly, a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm and a synthetic amorphous silica aggregate having an average particle diameter exceeding 5 μm were used in combination. It is preferable to use a mixture of fine particles. In this way, by using together different synthetic amorphous silica aggregates having an average particle diameter in the range of several μm, aggregates are formed in which aggregates of different average particle diameters complement the gaps between the aggregates and the aggregates, Sublimation-type ink-jet printing using sublimation-type printing ink Excellent sublimation-type printing ink drying, image reproducibility, anti-through-through prevention and heat resistance when printing on paper Good characteristics can also be obtained in terms of performance and transfer efficiency.
更に好適には、理由が明確ではないが、２種類以上の合成非晶質シリカ凝集体を組み合わせて使用することで、後述の凹凸の形成が容易になり、優れた昇華型捺染インク乾燥性など本発明の効果を達成することができる。 More preferably, although the reason is not clear, the use of a combination of two or more kinds of synthetic amorphous silica aggregates facilitates the formation of irregularities described later, and excellent sublimation printing ink drying properties, etc. The effects of the present invention can be achieved.
このような合成非晶質シリカ凝集体としては、市販のものを用いることができ、例えば、凝集体の平均粒子径が１．７〜５．０μｍの合成非晶質シリカ凝集体の市販品としてはニップジェルＡＹ−２００等が挙げられ、凝集体の平均粒子径が５．０μｍを超える合成非晶質シリカ凝集体の市販品としてはニップジェルＡＹ−６Ａ２等が挙げられる。 As such a synthetic amorphous silica aggregate, a commercially available one can be used, for example, as a commercial product of a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm. Nipgel AY-200 and the like, and as a commercial product of a synthetic amorphous silica aggregate in which the average particle diameter of the aggregate exceeds 5.0 μm, nipgel AY-6A2 and the like can be mentioned.
本発明でいう平均粒子径（体積平均粒子径）は、少量のサンプルをメタノール溶液に添加し、超音波分散器で３分間分散した溶液をコールターカウンター法粒度分布測定器（ＣＯＵＬＴＥＲ ＥＬＥＣＴＲＯＮＩＣＳ ＩＮＳ製ＴＡ−ＩＩ型）にて、５０μｍのアパチャーを用いて測定を行った。 In the present invention, the average particle size (volume average particle size) is obtained by adding a small amount of sample to a methanol solution and dispersing the solution for 3 minutes with an ultrasonic disperser, using a Coulter counter particle size distribution analyzer (TA- manufactured by COULTER ELECTRONICS INS). In type II), measurement was performed using an aperture of 50 μm.
好適な平均粒子径が異なる合成非晶質シリカ凝集体の組合せにおいて、凝集体の平均粒子径が１．７〜５．０μｍの合成非晶質シリカ凝集体と、凝集体の平均粒子径が５．０μｍを超える合成非晶質シリカ凝集体の配合比としては、特に限定されないが、好適には、固形分の質量比で１０：９０〜５０：５０程度であることが好ましい。固形分の質量比で１０：９０〜５０：５０程度とすることで、粒子径の大きいシリカ凝集体の間隙を、粒子径の小さいシリカ凝集体が埋めるため、得られる凝集塊の多孔性が増し、昇華型捺染インク受容層表面の凹凸の形成において、均等な凝集塊の凹凸による被覆が得られるため、優れた昇華型捺染インクの吸収乾燥性、昇華型インクジェット捺染転写紙における画像の再現性、被転写物における画像の再現性と、高い昇華型捺染インクの転写効率を得ることができる。 In a combination of synthetic amorphous silica aggregates having different preferred average particle diameters, a synthetic amorphous silica aggregate having an average particle diameter of 1.7 to 5.0 μm and an average particle diameter of 5 Although it does not specifically limit as a compounding ratio of the synthetic amorphous silica aggregate exceeding 0.0 micrometer, It is preferable that it is about 10: 90-50: 50 by mass ratio of solid content suitably. By setting the mass ratio of the solid content to about 10:90 to 50:50, the silica aggregate having a small particle diameter fills the gap between the silica aggregate having a large particle diameter, so that the porosity of the obtained aggregate increases. In the formation of unevenness on the surface of the sublimation printing ink receiving layer, a uniform agglomerate unevenness coating is obtained, so that excellent sublimation printing ink absorption drying, image reproducibility on sublimation inkjet printing transfer paper, Image reproducibility on the transfer object and high transfer efficiency of the sublimation printing ink can be obtained.
本発明の効果を奏する限りにおいて、合成非晶質シリカとともに、合成非晶質シリカ以外の微細粒子を配合することが可能である。他の微細粒子としては、例えば、軽質炭酸カルシウム、重質炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、カオリン、タルク、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、珪酸マグネシウム、コロイダルシリカ、アルミナ、コロイダルアルミナ、アルミナ水和物（擬ベーマイト等）、水酸化アルミニウム、リトポン、ゼオライト、加水ハロイサイト、水酸化マグネシウム等の無機顔料、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、ポリエチレン、マイクロカプセル、尿素樹脂、メラミン樹脂等の有機顔料等が挙げられる。 As long as the effects of the present invention are exhibited, fine particles other than synthetic amorphous silica can be blended together with synthetic amorphous silica. Other fine particles include, for example, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, magnesium hydroxide, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, Aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, colloidal silica, alumina, colloidal alumina, alumina hydrate (pseudo boehmite, etc.), aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium hydroxide and other inorganic pigments, styrene And organic pigments such as polyethylene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.
前記昇華型捺染インク受容層中の微細粒子の含有量は２０〜８０質量％が好ましく、２３〜６５質量％がより好ましい。含有量が２０質量％未満だと昇華型捺染インク受容量が少なくなり転写効率が低下する傾向がある。また８０質量％を超えると、昇華型捺染インク受容量は多くなるが、転写時の昇華効率が低下する傾向があり、汚損の問題が生じる場合がある。なお、昇華型捺染インク受容層中の水溶性樹脂が熱可塑性を示すため、昇華型捺染インク受容層中の微細粒子の含有率を高くすることにより、昇華捺染転写紙の耐熱性が向上する。 The content of fine particles in the sublimation type printing ink receiving layer is preferably 20 to 80% by mass, and more preferably 23 to 65% by mass. When the content is less than 20% by mass, the sublimation printing ink acceptance amount is decreased and the transfer efficiency tends to be lowered. On the other hand, when the amount exceeds 80% by mass, the sublimation printing ink acceptance amount increases, but the sublimation efficiency at the time of transfer tends to decrease, which may cause a problem of fouling. In addition, since the water-soluble resin in the sublimation printing ink receiving layer exhibits thermoplasticity, the heat resistance of the sublimation printing transfer paper is improved by increasing the content of fine particles in the sublimation printing ink receiving layer.
本発明において水溶性樹脂は主としてバインダーとして用いられ、例えば、澱粉、酸化澱粉、カチオン化澱粉、エーテル化澱粉、リン酸エステル化澱粉等の澱粉誘導体、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、セルロースサルフェート等のセルロース誘導体、各種鹸化度のポリビニルアルコール又はそのシラノール変性物、カルボキシル化物、カチオン化物等の各種誘導体、カゼイン、ゼラチン、変性ゼラチン、大豆蛋白等の水溶性天然高分子、ポリビニルピロリドン、ポリアクリル酸ナトリウム、スチレン−無水マレイン酸共重合体ナトリウム塩、ポリスチレンスルフォン酸ナトリウム等の水溶性合成高分子が挙げられ、これらの水溶性高分子を単独で若しくは併用して用いることができる。 In the present invention, the water-soluble resin is mainly used as a binder, for example, starch derivatives such as starch, oxidized starch, cationized starch, etherified starch, and phosphate esterified starch, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate and the like. Cellulose derivatives, various saponified polyvinyl alcohols or their silanol-modified products, carboxylated products, cationized products and other derivatives, water-soluble natural polymers such as casein, gelatin, modified gelatin, soybean protein, polyvinylpyrrolidone, sodium polyacrylate Water-soluble synthetic polymers such as sodium styrene-maleic anhydride copolymer and sodium polystyrene sulfonate. These water-soluble polymers can be used alone or in combination. That.
本発明者らが見出した最も好適な水溶性樹脂としては、ポリビニルアルコールとカルボキシメチルセルロースが挙げられ、最も好適には、両者を併用することが好ましい。 Examples of the most preferable water-soluble resin found by the present inventors include polyvinyl alcohol and carboxymethyl cellulose, and it is most preferable to use both in combination.
ポリビニルアルコールとしては特に限定されず、各種ケン化度のポリビニルアルコールを使用することができるが、ケン化度としては、８７〜８９ｍｏｌ％程度が好ましい。重合度としては特に限定されないが、例えば、重合度が約１０００以下のものが、カルボキシメチルセルロースとの相溶性や昇華型捺染インクをインク受容層に留め置くに特に好ましい。このようなポリビニルアルコールの市販品としては、ポバールＰＶＡ−２１０、ポバールＰＶＡ−２０５（（株）クラレ製）等が挙げられる。 It does not specifically limit as polyvinyl alcohol, Although polyvinyl alcohol of various saponification degrees can be used, As a saponification degree, about 87-89 mol% is preferable. The degree of polymerization is not particularly limited, but, for example, those having a degree of polymerization of about 1000 or less are particularly preferred for compatibility with carboxymethylcellulose and for retaining sublimation printing inks in the ink receiving layer. Examples of such commercially available polyvinyl alcohol include Poval PVA-210, Poval PVA-205 (manufactured by Kuraray Co., Ltd.), and the like.
水溶性樹脂として、ケン化度が８７〜８９ｍｏｌ％程度で、重合度が約１０００以下のポリビニルアルコールをインク受容層に用いることで、インク受容層塗料の調整において用いる合成非晶質シリカの分散性、特に２種類以上の合成非晶質シリカ凝集体を組み合わせて使用する際における凹凸の形成能が向上し、昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク乾燥性と画像再現性、裏抜け防止性及び耐熱性を有するとともに、転写による被転写物の画像再現性や転写効率の点でも良好な特性を得ることができる。 Dispersibility of synthetic amorphous silica used in the preparation of the ink-receiving layer coating by using polyvinyl alcohol having a saponification degree of about 87 to 89 mol% and a polymerization degree of about 1000 or less as the water-soluble resin in the ink-receiving layer coating. In particular, the ability to form irregularities when using a combination of two or more kinds of synthetic amorphous silica aggregates is improved, and an excellent sublimation type at the time of printing on a sublimation ink jet printing transfer paper using a sublimation printing ink. In addition to having printing ink drying properties, image reproducibility, anti-through-through properties, and heat resistance, it is also possible to obtain good characteristics in terms of image reproducibility and transfer efficiency of a transfer object by transfer.
ポリビニルアルコールの配合量としては、固形分で、少なくとも合成非晶質シリカを含む微細粒子１００質量部に対して１〜２００質量部程度が好ましく、２〜１００質量部程度がより好ましい。この範囲によって、優れた昇華型捺染インクの乾燥性と、高度の昇華型捺染インク裏抜け防止性を両立することができる。 As a compounding quantity of polyvinyl alcohol, about 1-200 mass parts is preferable with respect to 100 mass parts of microparticles | fine-particles which contain a synthetic amorphous silica at least by solid content, and about 2-100 mass parts is more preferable. By this range, it is possible to achieve both excellent drying properties of the sublimation printing ink and a high level of sublimation printing ink prevention.
微細粒子１００質量部に対してポリビニルアルコールの配合量が１質量部未満では、ポリビニルアルコールによるバインダー効果が十分に発揮されず、インク受容層の剥離や傷が入りやすくなり、画像再現性を低下させる問題が生じる。 When the blending amount of polyvinyl alcohol is less than 1 part by mass with respect to 100 parts by mass of fine particles, the binder effect due to the polyvinyl alcohol is not sufficiently exerted, and the ink receiving layer is easily peeled off or scratched, thereby reducing image reproducibility. Problems arise.
微細粒子１００質量部に対してポリビニルアルコールの配合量が２００質量部を超えると、ポリビニルアルコールによる被膜形成のため、昇華型捺染インク乾燥性の低下が問題となる。 When the blending amount of polyvinyl alcohol exceeds 200 parts by mass with respect to 100 parts by mass of fine particles, a decrease in the drying property of the sublimation type printing ink becomes a problem due to the formation of a film by polyvinyl alcohol.
好適に用いられる水溶性樹脂としてのカルボキシメチルセルロースとしては、特に限定されず、エーテル化度で０．５〜１．０の範囲のものが好ましい。 The carboxymethyl cellulose as the water-soluble resin suitably used is not particularly limited, and those having a degree of etherification in the range of 0.5 to 1.0 are preferable.
水溶性樹脂として、エーテル化度で０．５〜１．０のカルボキシメチルセルロースは、好適に組合わせて使用されるポリビニルアルコール、特にケン化度が８７〜８９ｍｏｌ％程度で、重合度が約１０００以下のポリビニルアルコールとの相溶性が良好であると共に、合成非晶質シリカの分散性、特に２種類以上の合成非晶質シリカ凝集体を組み合わせて使用する際における凹凸の形成能を阻害させることなく、昇華型捺染インクを用いた昇華型インクジェット捺染転写紙への印刷時の優れた昇華型捺染インク乾燥性と画像再現性、裏抜け防止性及び耐熱性を有するとともに、転写による被転写物の画像再現性や転写効率の点でも良好な特性を得ることができる。 As a water-soluble resin, carboxymethylcellulose having a degree of etherification of 0.5 to 1.0 is preferably used in combination with polyvinyl alcohol, particularly a saponification degree of about 87 to 89 mol%, and a polymerization degree of about 1000 or less. Has good compatibility with polyvinyl alcohol and does not hinder the dispersibility of synthetic amorphous silica, particularly the ability to form irregularities when using a combination of two or more types of synthetic amorphous silica aggregates. , Sublimation-type ink-jet printing using sublimation-type printing inks Sublimation-type printing inks have excellent drying properties, image reproducibility, anti-through-through prevention, and heat resistance when printed on transfer paper, and images of transferred objects by transfer Good characteristics can be obtained in terms of reproducibility and transfer efficiency.
市販品としては、セロゲン７Ａ（以上、第一工業製薬（株）製）等を使用することができる。 As a commercially available product, Serogen 7A (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can be used.
好適には、ポリビニルアルコールとカルボキシメチルセルロースを前記範囲にて併用した水溶性樹脂を用いることによって、優れた昇華型捺染インクの乾燥性と、高度の昇華型捺染インク裏抜け防止性を両立することができる。 Preferably, by using a water-soluble resin in which polyvinyl alcohol and carboxymethyl cellulose are used in the above-mentioned range, it is possible to achieve both excellent drying properties of sublimation printing ink and a high degree of sublimation printing ink prevention. it can.
本発明の昇華型インクジェット捺染転写紙の好適な態様では、従来品とは異なり、昇華型捺染インク受容層が特異な凹凸の表面構造を呈している。従来品では図２に示すように、昇華型捺染インク受容層は顔料とバインダーがほぼ一定の厚みで基材表面を被覆するものであったが、本発明では、昇華型捺染インク受容層の表面には図１に示すように凹凸が形成されている。この凹凸は、微細粒子による凝集塊であることが好ましいが、特に、粒子径の異なる２種類の合成非晶質シリカ凝集体が凝集することによって得られる凝集塊により形成された凹凸であることがより好ましい。最も好ましくは、凝集塊により、好ましくは幅が１０μｍ以上の凸部が多数形成され、このような凹凸を表面に有する昇華型捺染インク受容層が基材の表面を被覆することによって本発明の昇華型インクジェット捺染転写紙が形成されている。 In a preferred embodiment of the sublimation ink jet printing transfer paper of the present invention, unlike the conventional product, the sublimation printing ink receiving layer has a unique uneven surface structure. In the conventional product, as shown in FIG. 2, the sublimation type printing ink receiving layer has a pigment and binder covering the surface of the substrate with a substantially constant thickness. In the present invention, the surface of the sublimation type printing ink receiving layer is used. As shown in FIG. The irregularities are preferably aggregates of fine particles, but in particular, the irregularities formed by aggregates obtained by agglomeration of two types of synthetic amorphous silica aggregates having different particle diameters. More preferred. Most preferably, a large number of convex portions having a width of 10 μm or more are formed by the agglomerates, and the sublimation printing ink receiving layer having such irregularities on the surface covers the surface of the substrate, whereby the sublimation of the present invention. A type inkjet textile transfer paper is formed.
この凹凸が存在するために基材表面の比表面積が増大するので、昇華型捺染インクを昇華型捺染インク受容層で瞬時に吸収、保持（乾燥）することが可能になり昇華型捺染インクの吸収乾燥性が向上する。更に、滲みが少なく、画像再現性に優れ、基材に昇華型捺染インクが含浸し難いため、寸法安定性と耐コックリング性にも優れたものとなる。これとともに、昇華型インクジェット捺染転写紙として比較的透気度が低いため当該熱が用紙の厚み方向に伝達しやすくなり、熱の損失が少なくなる。そのため、凝集塊に保持された昇華型捺染インクへの熱伝達速度が高くなり、かつ伝達熱量も多くなることから、転写効率が飛躍的に向上するものと考えられる。 The uneven surface area increases the specific surface area of the substrate surface, so that the sublimation printing ink can be instantly absorbed and retained (dried) by the sublimation printing ink receiving layer. Dryability is improved. Furthermore, since there is little bleeding, it is excellent in image reproducibility, and it is hard to impregnate a base material with a sublimation type | mold printing ink, Therefore It becomes excellent also in dimensional stability and cockling resistance. At the same time, since the air permeability is relatively low as the sublimation type ink jet textile transfer paper, the heat is easily transmitted in the thickness direction of the paper, and the heat loss is reduced. For this reason, the heat transfer speed to the sublimation printing ink held in the agglomerates is increased and the amount of heat transferred is increased, so that it is considered that the transfer efficiency is drastically improved.
ここで、本発明で云う凹凸とは、微細粒子の凝集塊による昇華型捺染インク受容層表面の起伏のことを云い、その形成は昇華型捺染インク受容層を形成する塗工液の攪拌段階で水溶性樹脂に微細粒子を添加し、混合分散処理する事により得られるものである。混合分散時の物理的剪断力が強すぎると、微細粒子の均質な分散が生じ凹凸を形成し難くなるため、好適には分散処理を適宜調整し、塗工液中に微細粒子の凝集塊を形成させ、昇華型捺染インク受容層形成時に凹凸を形成させる。凹凸を形成するメカニズムは明確ではないが、水溶性樹脂が基材に含浸することで、水溶性樹脂中に分散された微細粒子の凝集塊が表出し、基材表面上に昇華型捺染インク受容層を形成すると共に、凝集塊による凹凸を形成する。 Here, the unevenness referred to in the present invention means the undulation of the surface of the sublimation printing ink receiving layer due to agglomerates of fine particles, and the formation thereof is at the stirring stage of the coating liquid for forming the sublimation printing ink receiving layer. It can be obtained by adding fine particles to a water-soluble resin and mixing and dispersing it. If the physical shearing force at the time of mixing and dispersion is too strong, uniform dispersion of fine particles will occur and it will be difficult to form irregularities, so it is preferable to adjust the dispersion treatment appropriately so that fine particle aggregates are formed in the coating liquid. When the sublimation type printing ink receiving layer is formed, irregularities are formed. The mechanism for forming the irregularities is not clear, but when the substrate is impregnated with the water-soluble resin, agglomerates of fine particles dispersed in the water-soluble resin appear and the sublimation printing ink is received on the substrate surface. In addition to forming a layer, irregularities due to agglomerates are formed.
凝集塊を形成する好適な条件としては、水溶性樹脂中に、予め水溶液に分散させた微細粒子を固形分濃度２〜２５質量％になるように含有させ、分散時間を３０分以内、好適には２０分以内とする事で、３０μｍ以下、好適には２０μｍ以下の凝集塊を形成できる。更に好適には固形分濃度を３〜１２質量％とすることが、凝集塊に均一な物理的剪断力を加え易く、均質な凝集塊が得られ、均質な昇華型捺染インク受容層の凹凸を形成させることができるので好ましい。前記条件をはずれると、微細又は過大な凝集塊の生成が生じ、均質な昇華型捺染インク受容層の凹凸を形成し難くなる。 As a suitable condition for forming the agglomerates, fine particles previously dispersed in an aqueous solution are contained in a water-soluble resin so that the solid content concentration is 2 to 25% by mass, and the dispersion time is preferably within 30 minutes. Is within 20 minutes, it is possible to form an aggregate of 30 μm or less, preferably 20 μm or less. More preferably, the solid content concentration is 3 to 12% by mass, and it is easy to apply a uniform physical shearing force to the agglomerate, and a homogeneous agglomerate is obtained, and the unevenness of the uniform sublimation printing ink receiving layer is improved. It is preferable because it can be formed. If the conditions are not met, fine or excessive agglomerates are generated, and it becomes difficult to form unevenness of the homogeneous sublimation printing ink receiving layer.
吸水度に関しては、ＪＩＳ Ｐ ８１４０に準拠した前記昇華型捺染インク受容層の吸水度が１５ｇ／ｍ２以上であり、更に好適には２０〜９０ｇ／ｍ２が好ましい。吸水度が１５ｇ／ｍ２未満であるとインク受容量が少なく、良好な吸収乾燥性や転写効率を達成することができない。また、吸水度に関係して、従来品はインク受容能力が１０ｇ／ｍ２程度であったが、微細粒子が合成非晶質シリカで且つ昇華型捺染インク受容層が微細粒子を２０〜８０質量％含有する系では、５０ｇ／ｍ２程度までインクを受容することが可能になる。転写効率を考えると２０〜３０ｇ／ｍ２のインク受容能を有することが好ましい。 With respect to water absorbency, water absorption of the sublimation printing ink-receiving layer conforming to JIS P 8140 is not less 15 g / m 2 or more, more preferably preferably 20~90g / m 2. When the water absorption is less than 15 g / m 2 , the ink receiving amount is small, and good absorption drying property and transfer efficiency cannot be achieved. In relation to the water absorption, the conventional product has an ink receiving capacity of about 10 g / m 2 , but the fine particles are synthetic amorphous silica and the sublimation printing ink receiving layer contains 20 to 80 mass of fine particles. In a system containing 1%, it is possible to receive ink up to about 50 g / m 2 . Considering the transfer efficiency, it is preferable to have an ink receiving capacity of 20 to 30 g / m 2 .
凹凸の存在は後述のように分析走査型電子顕微鏡（日本電子データム（株）製ＪＳＭ−６３９０Ａ型）を用いて確認することができる。本発明者らの知見によると、凹凸を形成する凝集塊の凸部の幅が大きくなりすぎると、昇華型捺染インクの裏抜け防止性が低下する傾向があるので、３０μｍ程度以下が好ましく、２０μｍ程度以下がより好ましい。なお、この幅は無作為に選択した凝集塊６０個の、個々の長短の幅からの平均値を実測し、最小値５個、最大値５個を除く５０個の実測平均値を測定した。 Existence of irregularities can be confirmed using an analytical scanning electron microscope (JSM-6390A type manufactured by JEOL Datum Co., Ltd.) as described later. According to the knowledge of the present inventors, if the width of the convex portion of the agglomerate forming the unevenness tends to be too small, there is a tendency that the prevention of the back-through of the sublimation type printing ink tends to be lowered, so about 30 μm or less is preferable, and 20 μm A degree or less is more preferable. The average value of 60 randomly selected agglomerates from individual long and short widths was actually measured, and 50 actually measured average values excluding 5 minimum values and 5 maximum values were measured.
また、当該昇華型捺染インク受容層の表面粗さをレーザー顕微鏡（キーエンス（株）製カラーレーザー顕微鏡 高解像度タイプＶＫ−９７００型）で測定すると、二乗平均粗さで３μｍ以上を満足することが好ましい。好ましくは４μｍ以上である。上限は２１μｍ以下、あるいは２０μｍ以下程度が好ましい。表面粗さが３μｍ未満と低すぎると昇華型捺染インクの乾燥性が十分でなく、２１μｍを超える過大な粗さの場合は、昇華型インクジェット捺染転写紙における画像再現性が低下すると共に、被転写物における画像再現性、転写効率が低下するほか本発明の効果を達成するのに不都合である。なお、従来品における二乗平均粗さは３μｍ未満である。 Further, when the surface roughness of the sublimation printing ink receiving layer is measured with a laser microscope (Color Laser Microscope High Resolution Type VK-9700, manufactured by Keyence Corporation), it is preferable that the root mean square roughness satisfies 3 μm or more. . Preferably it is 4 micrometers or more. The upper limit is preferably about 21 μm or less, or about 20 μm or less. If the surface roughness is too low, less than 3 μm, the drying property of the sublimation printing ink is not sufficient. If the surface roughness is more than 21 μm, the image reproducibility on the sublimation ink jet printing transfer paper is lowered and the image is transferred. In addition to the image reproducibility and transfer efficiency of the object being lowered, it is inconvenient for achieving the effects of the present invention. In addition, the root mean square roughness in a conventional product is less than 3 μm.
本発明の昇華型インクジェット捺染転写紙では昇華型捺染インク受容層の表面に凹凸が形成されているものであるが、昇華型捺染インク受容層同士の静摩擦係数としてＪＩＳ Ｐ ８１４７に準拠して０．２０〜１．０５、好適には０．３０〜０．９９、更に好適には、０．３５〜０．９５とすることが好ましい。静摩擦係数が０．２０未満と低すぎると昇華型捺染インクの乾燥性が十分でなく、逆に、１．０５を超えるほど高すぎると昇華型捺染インクの転写効率や裏抜け防止性が低下する傾向がある。なお、従来品における静摩擦係数は０．２０未満である。 In the sublimation type ink jet printing transfer paper of the present invention, irregularities are formed on the surface of the sublimation type printing ink receiving layer, but the static friction coefficient between the sublimation type printing ink receiving layers is set to 0. 0 according to JIS P 8147. 20 to 1.05, preferably 0.30 to 0.99, and more preferably 0.35 to 0.95. If the coefficient of static friction is too low (less than 0.20), the drying property of the sublimation printing ink is not sufficient. Conversely, if the coefficient of static friction is too high, the transfer efficiency and the prevention of back-through are reduced. Tend. The static friction coefficient in the conventional product is less than 0.20.
昇華型捺染インク受容層を、主成分として水溶性樹脂と微細粒子にて構成し、昇華型捺染インク受容層同士の静摩擦係数としてＪＩＳ Ｐ ８１４７に準拠して０．２０〜１．０５になるように、昇華型捺染インク受容層の表面に凹凸を形成することで、更に、本発明の昇華型インクジェット捺染転写紙は、印刷時には昇華型捺染インクの吸収乾燥性と紙における画像再現性や作業性に優れているとともに、昇華捺染のための加温転写時に昇華型捺染インクが昇華型インクジェット捺染転写紙の裏側に裏抜けするのを防止する特性においても優れている。さらには、転写による被転写物の画像再現性や、転写効率の点においても優れた特性を得ることができる。 The sublimation printing ink receiving layer is composed of a water-soluble resin and fine particles as main components, and the coefficient of static friction between the sublimation printing ink receiving layers is 0.20 to 1.05 in accordance with JIS P 8147. In addition, by forming irregularities on the surface of the sublimation type printing ink receiving layer, the sublimation type ink jet printing transfer paper of the present invention is also capable of absorbing and drying the sublimation type printing ink and image reproducibility and workability on the paper during printing. In addition, it is excellent in the property of preventing the sublimation type printing ink from penetrating to the back side of the sublimation type ink jet printing transfer paper at the time of warm transfer for sublimation printing. Furthermore, it is possible to obtain excellent characteristics in terms of image reproducibility of the transfer object by transfer and transfer efficiency.
本発明の昇華型インクジェット捺染転写紙は、主として凹凸を形成する微細粒子による凝集塊に保持された昇華型捺染インクに転写時の熱が迅速に伝達することによって、昇華型捺染インクの転写効率を向上させるものであるが、基材中の空気は熱の伝達を阻害するものと考えられ、当該昇華型インクジェット捺染転写紙の透気度は低く調整したほうが好ましい。 The sublimation type ink jet printing transfer paper of the present invention has the transfer efficiency of the sublimation type printing ink by rapidly transferring heat during transfer to the sublimation type printing ink held in the agglomerates mainly composed of fine particles forming irregularities. Although it is improved, it is thought that the air in a base material inhibits heat transfer, and it is preferable to adjust the air permeability of the sublimation type inkjet printing transfer paper to be low.
具体的には、ＪＩＳ Ｐ ８１１７に準拠した透気度として、３０，５００秒以下が好ましく、３０，０００秒以下、更には２５，０００秒以下がより好ましい。しかし逆に低すぎると転写効率や昇華型捺染インクの裏抜け防止性が低下するので、８０秒以上が好ましく、１，３５０秒以上、より好適には１，５００秒以上がより好ましく、７，０００秒以上がさらに好ましい。 Specifically, the air permeability in accordance with JIS P 8117 is preferably 30,500 seconds or less, more preferably 30,000 seconds or less, and even more preferably 25,000 seconds or less. On the other hand, if it is too low, the transfer efficiency and the back-through prevention property of the sublimation type printing ink are lowered. Therefore, it is preferably 80 seconds or longer, more preferably 1,350 seconds or longer, more preferably 1,500 seconds or longer, More preferable is 000 seconds or more.
基材として透気度の高い基材を用いることが好ましいが、昇華型インクジェット捺染転写紙としての透気度が昇華型捺染インクへの加熱時の熱を伝える上で調整が必要であり、透気度をＪＩＳ Ｐ ８１１７に準拠した透気度として、３０，５００秒以下とし、熱による寸法安定性や昇華型捺染インクへの熱伝達を考慮して基材として紙を選択し、好適には片艶紙を選択し、昇華型捺染インク受容層における昇華型捺染インクの保持と昇華が適切に成される微細粒子を用い、好適には緻密な多孔性を形成する少なくとも粒子径の異なる２種類の凝集体を併用して形成される凝集塊を用い、更には、昇華型捺染インク受容層を前記凝集塊から成る凹凸で被覆することで、印刷時には昇華型捺染インクの吸収乾燥性と紙における画像再現性や作業性に優れているとともに、昇華捺染のための加温転写時に昇華型捺染インクが昇華型インクジェット捺染転写紙の裏側に裏抜けするのを防止する特性においても優れ、更には、転写による被転写物の画像再現性や、転写効率の点においても優れた昇華型インクジェット捺染転写紙を得ることができる。 It is preferable to use a substrate having a high air permeability as the substrate, but the air permeability as the sublimation type ink jet printing transfer paper needs to be adjusted in order to transmit heat during heating to the sublimation type printing ink. The air permeability according to JIS P 8117 is set to 30,500 seconds or less, and paper is selected as the base material in consideration of dimensional stability by heat and heat transfer to the sublimation printing ink. Select one-sided glossy paper, use fine particles that can properly hold and sublimate sublimation-type printing ink in the sublimation-type printing ink-receiving layer, and at least two types with different particle diameters that form dense porosity In addition, the sublimation printing ink receiving layer is covered with the unevenness formed of the agglomerates, and at the time of printing, the absorption drying property of the sublimation printing ink and the paper Image reproducibility and workability In addition, it has excellent properties for preventing sublimation-type printing ink from penetrating to the back side of sublimation-type inkjet printing transfer paper during warm transfer for sublimation printing. It is possible to obtain a sublimation type ink jet textile transfer paper excellent in image reproducibility and transfer efficiency.
インク受容層の塗工量としては、３〜２５ｇ／ｍ２が好ましく、さらに６〜１５ｇ／ｍ２がより好ましい。３ｇ／ｍ２未満では十分な昇華型インクの吸収容量が確保できず、転写画像の解像性が悪化し、ベタ画像部にムラが発生する傾向がある。インク受容層の塗工量が２５ｇ／ｍ２を超えると、相対的に表面強度が低下し、粉落ち等が発生して作業性を低下させる原因になる。 The coating amount of the ink receiving layer is preferably 3 to 25 g / m 2, further 6 to 15 g / m 2 is more preferable. If it is less than 3 g / m 2 , a sufficient absorption capacity of the sublimation ink cannot be secured, the resolution of the transferred image is deteriorated, and unevenness tends to occur in the solid image portion. When the coating amount of the ink receiving layer exceeds 25 g / m 2 , the surface strength is relatively lowered, causing powder falling or the like, which causes workability to be lowered.
昇華型捺染インク受容層の塗工にあたってその手法は特に限定されないが、本発明の効果を効率よく達成するには、水溶性樹脂の好適な例としてポリビニルアルコールとカルボキシメチルセルロースの組合せを選択し説明すると、まず、濃度が３０質量％の合成非晶質シリカ粒子（特に粒子径の異なる２種類の合成非晶質シリカ）分散液とポリビニルアルコールとを予め混合しておき、次にカルボキシメチルセルロースを加えた後、５％濃度に調整した塗工液を、塗工量が乾燥質量で３〜２５ｇ／ｃｍ２となるように基材上に塗工する方法が好ましい。塗布方法としては特に限定されないが、例えば、エアーナイフコーター、ロールコーター、バーコーター、コンマコーター、ブレードコーター等の公知の塗工機を用いて塗工することができる。その後、凹凸の調整又は静摩擦係数の調整のために、マシンカレンダーやソフトカレンダー等を用いて平坦化処理することも出来る。またカール等の補正を目的にバックコート層を設けることも可能である。 The method for coating the sublimation printing ink receiving layer is not particularly limited, but in order to efficiently achieve the effects of the present invention, a combination of polyvinyl alcohol and carboxymethyl cellulose will be described as a suitable example of a water-soluble resin. First, a dispersion of synthetic amorphous silica particles (particularly two types of synthetic amorphous silica having different particle diameters) having a concentration of 30% by mass and polyvinyl alcohol were previously mixed, and then carboxymethylcellulose was added. Thereafter, a method of applying the coating liquid adjusted to a concentration of 5% onto the substrate so that the coating amount is 3 to 25 g / cm 2 in terms of dry mass is preferable. Although it does not specifically limit as a coating method, For example, it can coat using well-known coating machines, such as an air knife coater, a roll coater, a bar coater, a comma coater, a blade coater. Thereafter, in order to adjust the unevenness or the static friction coefficient, a flattening process can be performed using a machine calendar, a soft calendar, or the like. It is also possible to provide a backcoat layer for the purpose of correcting curl or the like.
以下に、インクジェット記録方法を用いて昇華型捺染インクにて昇華捺染型記録用紙に記録を行った場合の実施例を掲げて本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例で示す「部」及び「％」は、特に明示しない限り質量部、及び質量％を示す。なお、配合において示す部数は、固形分の部数である。 Hereinafter, the present invention will be described in detail with reference to examples in the case where recording is performed on sublimation printing type recording paper with sublimation type printing ink using an ink jet recording method, but the present invention is not limited to these examples. It is not something. In the examples, “parts” and “%” indicate parts by mass and mass% unless otherwise specified. In addition, the part shown in a mixing | blending is a part of solid content.
実施例１
フリーネス５３０ｍｌ（Ｃ．Ｓ．Ｆ．）の広葉樹晒クラフトパルプ（ＬＢＫＰ）とフリーネス５８０ｍｌ（Ｃ．Ｓ．Ｆ．）の針葉樹晒クラフトパルプ（ＮＢＫＰ）を等質量配合し、助剤として、カチオン化デンプンを０．８％、内添サイズ剤を１．１％、アニオン変性ポリアクリルアマイドを０．３％、消サイズ剤としてポリオキシアルキレン脂肪酸エステル（星光ＰＭＣ株式会社製、品番ＤＦ４５）を０．１０％添加して紙料を調製し、ヤンキードライヤーを備えた抄紙機で抄紙し、米坪１００ｇ／ｍ２、平滑度６０秒の片艶紙を製造した。
Example 1
Freeness 530ml (C.S.F.) hardwood bleached kraft pulp (LBKP) and freeness 580ml (C.S.F.) softwood bleached kraft pulp (NBKP) are mixed in equal mass, and cationized starch is used as an auxiliary agent. 0.8%, internal sizing agent 1.1%, anion-modified polyacrylamide 0.3%, polyoxyalkylene fatty acid ester (manufactured by Seiko PMC Co., Ltd., product number DF45) 0.10 as a sizing agent A paper stock was prepared by adding%, and paper was made with a paper machine equipped with a Yankee dryer to produce glossy paper with 100 g / m 2 of rice basis weight and a smoothness of 60 seconds.
無機微粒子として、カオリン（エリエール商工社製、体積平均粒径８．０μｍ）を７０部、非水溶性重合体として、ＳＢＲラテックス（住友Ａ＆Ｌ社製、型番：ＳＮ３０７）を３０部使用し、固形分濃度４５％の目止め塗工層塗料を調製した。この塗料を前記基材の艶面に乾燥塗工量が５ｇ／ｍ２になるよう塗工して、目止め塗工層を形成した。 次いで、微細粒子として、平均粒子径が３．７μｍの合成非晶質シリカであるシリカＡ（トクヤマ社製、型番：ファインシールＸ３７Ｂ）を８５部、平均粒子径が６．２μｍの合成非晶質シリカであるシリカＢ（トクヤマ社製、型番：ファインシールＸ６０）を１５部、前記微細粒子１００部に対して、水溶性樹脂としてカルボキシメチルセルロースナトリウム（以下ＣＭＣと略す。） ＣＭＣ−Ａ（第一工業製薬社製、商品名：セロゲンＰＲ、重合度２２０〜２５０、分子量４７０００〜５４０００）を２００部、ポリビニルアルコール（以下ＰＶＡと略す。） ＰＶＡ−Ａ（クラレ社製、商品名：ＰＶＡ−２０５、ケン化度８７〜８９ｍｏｌ％、重合度５００）を２５部使用し、固形分濃度６．６％の昇華型捺染インク受容層塗料を調製した。微細粒子の凝集塊を形成するため、６５〜８０℃の高温のＣＭＣ中に、２０℃〜３０℃の低温のシリカ分散スラリーを添加しシリカを凝集させ、ゲル化した混合物を得た。その後ＰＶＡを添加し、２０〜４５℃にて混合分散しシリカ凝集塊の大きさが１５μｍになるよう物理的剪断力を調整した。 As inorganic fine particles, 70 parts of kaolin (manufactured by Eliere Shoko Co., Ltd., volume average particle size 8.0 μm) is used, and 30 parts of SBR latex (manufactured by Sumitomo A & L Co., model number: SN307) is used as a water-insoluble polymer. A filler coating layer coating having a concentration of 45% was prepared. This paint was applied to the glossy surface of the base material so that the dry coating amount was 5 g / m 2 , thereby forming a sealing coating layer. Next, 85 parts of silica A (manufactured by Tokuyama, model number: Fine Seal X37B), which is a synthetic amorphous silica having an average particle size of 3.7 μm, is used as fine particles, and the synthetic amorphous material has an average particle size of 6.2 μm. 15 parts of silica B (manufactured by Tokuyama, model number: Fine Seal X60) as silica, and sodium carboxymethylcellulose (hereinafter abbreviated as CMC) as a water-soluble resin with respect to 100 parts of the fine particles CMC-A (Daiichi Kogyo) Made by Pharmaceutical Co., Ltd., trade name: Serogen PR, polymerization degree 220-250, molecular weight 47000-54000) 200 parts, polyvinyl alcohol (hereinafter abbreviated as PVA) PVA-A (Kuraray, trade name: PVA-205, Ken) A sublimation type printing ink receiving layer coating material having a solid content concentration of 6.6% was prepared using 25 parts of a conversion degree of 87-89 mol% and a polymerization degree of 500). In order to form an agglomerate of fine particles, a silica dispersion slurry at a low temperature of 20 ° C. to 30 ° C. was added to a high temperature CMC at 65 ° C. to 80 ° C. to agglomerate the silica to obtain a gelled mixture. Thereafter, PVA was added and mixed and dispersed at 20 to 45 ° C., and the physical shearing force was adjusted so that the size of the silica agglomerates was 15 μm.
微細粒子の凝集塊を調整した塗液は、前記目止め塗工層上に乾燥塗工量が５ｇ／ｍ２になるよう塗工し、昇華型捺染転写紙を得た。製造した昇華型捺染転写紙を、後述する評価基準により評価した。 The coating liquid prepared by adjusting the agglomerates of fine particles was applied onto the sealing coating layer so that the dry coating amount was 5 g / m 2 to obtain a sublimation printing transfer paper. The manufactured sublimation printing transfer paper was evaluated according to the evaluation criteria described later.
以下の実施例、比較例は、実施例１の条件を基本に、表１〜３に示すとおり、基材、目止め塗工層の非水溶性粒子及び無機微粒子、インク受容層の微細粒子、水溶性樹脂及び塗工量を変更して昇華型捺染転写紙を製造し、実施例１と同様に評価した。 The following examples and comparative examples are based on the conditions of Example 1, and as shown in Tables 1 to 3, the base material, the water-insoluble particles and inorganic fine particles of the filler coating layer, the fine particles of the ink receiving layer, Sublimation printing transfer paper was produced by changing the water-soluble resin and the coating amount, and evaluated in the same manner as in Example 1.
消サイズ剤としては、実施例１で使用したもののほか以下を使用した。
アルキル硫酸塩：（日光ケミカルズ社製、型番：ＮＩＫＫＯＬ ＳＬＳ）
ポリオキシアルキレンアルキルエーテル硫酸塩：（第一工業製薬社製、型番：ハイテノール１２）
塩化アルキルトリメチルアンモニウム：（花王株式会社製、型番：エレクトロストリッパーＱＮ）
多価アルコールの脂肪酸エステル：（花王株式会社製、型番：エキセパールＰＥ−ＭＯ）
合成非晶質シリカとしては、実施例１で使用したもののほか以下を使用した。
シリカＣ（東ソー・シリカ社製、型番：ニップジェルＡＺ−２０４、平均粒子径が１．７μｍ）
シリカＤ（ＤＳＬ．ジャパン（株）製、型番：カープレックスＢＳ−３１２ＡＪ、平均粒子径が４．３μｍ）
シリカＦ（ＤＳＬ．ジャパン（株）製、型番：カープレックスＢＳ−３０４Ｎ、平均粒子径が１０．１μｍ）
シリカＧ（ＤＳＬ．ジャパン（株）製、型番：カープレックスＢＳ−３０３、平均粒子径が１２．７μｍ）
実施例８では、平均粒径６．３μｍの焼成クレーを使用した。
As the sizing agent, the following were used in addition to those used in Example 1.
Alkyl sulfate: (manufactured by Nikko Chemicals, model number: NIKKOL SLS)
Polyoxyalkylene alkyl ether sulfate: (Daiichi Kogyo Seiyaku Co., Ltd., model number: Hightenol 12)
Alkyltrimethylammonium chloride: (manufactured by Kao Corporation, model number: electro stripper QN)
Fatty acid ester of polyhydric alcohol: (manufactured by Kao Corporation, model number: EXCEPARL PE-MO)
As the synthetic amorphous silica, the following were used in addition to those used in Example 1.
Silica C (manufactured by Tosoh Silica Co., Ltd., model number: Nipgel AZ-204, average particle size is 1.7 μm)
Silica D (manufactured by DSL. Japan, model number: Carplex BS-312AJ, average particle size is 4.3 μm)
Silica F (manufactured by DSL. Japan, model number: Carplex BS-304N, average particle size is 10.1 μm)
Silica G (manufactured by DSL. Japan, model number: Carplex BS-303, average particle size is 12.7 μm)
In Example 8, a fired clay having an average particle size of 6.3 μm was used.
カルボキシメチルセルロースナトリウムとしては、実施例１で使用したもののほか以下を使用した。
ＣＭＣ−Ｂ（第一工業製薬社製、商品名：セロゲン７Ａ、重合度１２０〜１５０、分子量２７０００〜３３０００）
ＣＭＣ−Ｃ（第一工業製薬社製、商品名：セロゲン５Ａ、重合度１２０以下、分子量２７０００以下）
ＣＭＣ−Ｄ（第一工業製薬社製、商品名：セロゲンＷＳ−Ａ、重合度４６０〜５００、分子量１０００００〜１１００００）
ＣＭＣ−Ｅ（第一工業製薬社製、商品名：セロゲンＢＳ−Ｈ、重合度５００〜８００、分子量１８００００〜１９００００）
ポリビニルアルコールとしては、実施例１で使用したもののほか以下を使用した。
ＰＶＡ−Ｂ（クラレ社製、商品名：ＰＶＡ２１０、ケン化度８７〜８９ｍｏｌ％、重合度１０００）
ＰＶＡ−Ｃ（クラレ社製、商品名：ＰＶＡ２０３、ケン化度８７〜８９ｍｏｌ％、重合度３００）
ＰＶＡ−Ｄ（クラレ社製、商品名：ＰＶＡ１１０、ケン化度９８〜９９ｍｏｌ％、重合度１０００）
ＰＶＡ−Ｅ（クラレ社製、商品名：ＰＶＡ１２０、ケン化度９８〜９９ｍｏｌ％、重合度２０００）
実施例１６では目止め塗工層の非水溶性樹脂としてＮＢＲラテックス（日本ゼオン（株）社製、型番：ＮＩＰＯＬ ＬＸ ５３１Ｂ）を使用した。
As carboxymethylcellulose sodium, the following were used in addition to those used in Example 1.
CMC-B (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen 7A, polymerization degree 120-150, molecular weight 27000-33000)
CMC-C (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen 5A, polymerization degree 120 or less, molecular weight 27000 or less)
CMC-D (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen WS-A, degree of polymerization 460 to 500, molecular weight 100000 to 110000)
CMC-E (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen BS-H, polymerization degree 500-800, molecular weight 180,000-190000)
As polyvinyl alcohol, in addition to those used in Example 1, the following were used.
PVA-B (made by Kuraray Co., Ltd., trade name: PVA210, saponification degree 87-89 mol%, polymerization degree 1000)
PVA-C (manufactured by Kuraray Co., Ltd., trade name: PVA203, saponification degree 87-89 mol%, polymerization degree 300)
PVA-D (manufactured by Kuraray Co., Ltd., trade name: PVA110, saponification degree 98 to 99 mol%, polymerization degree 1000)
PVA-E (manufactured by Kuraray Co., Ltd., trade name: PVA120, saponification degree 98-99 mol%, polymerization degree 2000)
In Example 16, NBR latex (manufactured by Nippon Zeon Co., Ltd., model number: NIPOL LX 531B) was used as the water-insoluble resin for the sealing coating layer.
比較例１〜４では、目止め塗工層では非水溶性樹脂ではなく水溶性樹脂である酸化澱粉又はポリビニルアルコールを使用した。 In Comparative Examples 1-4, the starch coating layer used not the water-insoluble resin but the water-soluble resin, oxidized starch or polyvinyl alcohol.
＜測定・評価方法＞
昇華型捺染インクを用いたインクジェット記録評価には、ミマキ株式会社製、ＪＶ４型インクジェットプリンタを用いて、ＩＳＯ３００にて規定されているインクジェット記録評価用の画像を、ミマキ製の昇華型インク（ＳＰＣ−３７０シリーズ）を用いて行った。
<Measurement and evaluation method>
For ink jet recording evaluation using sublimation type textile printing ink, an image for ink jet recording evaluation defined in ISO300 was used by using a JV4 type ink jet printer manufactured by Mimaki Co., Ltd., and sublimation ink (SPC- 370 series).
被転写物には、ポリエステル布素材を使用した。 A polyester cloth material was used for the transfer object.
（１）シリカ凝集塊の有無：走査型電子顕微鏡（日本電子データム社製ＪＳＭ−６３９０Ａ型）を用い、シリカ凝集隗の有無を確認した。
○：凝集隗を確認でき、凝集隗と凝集隗との間に５μｍ以上の空隙が確認できる。
△：凝集隗を確認できるが、凝集隗と凝集隗の間に５μｍ以上の空隙が確認できない。
×：凝集隗が確認できない。
(1) Presence / absence of silica agglomerates: Using a scanning electron microscope (JSM-6390A type, manufactured by JEOL Datum), the presence / absence of silica agglomerates was confirmed.
○: Agglomerated wrinkles can be confirmed, and voids of 5 μm or more can be confirmed between the agglomerated wrinkles.
(Triangle | delta): Although the aggregation flaw can be confirmed, the space | gap of 5 micrometers or more cannot be confirmed between the aggregation flaws.
X: Agglomerated wrinkles cannot be confirmed.
（２）塗工液の塗工性：シリカ凝集隗を塗工する際には、凝集隗を起点としたストリーク欠陥の発生と樹脂の中の泡による未塗工欠損による塗工性を考慮する必要がある。
（ｉ）ストリーク欠陥：基材に塗工液をウェブし、定量塗工する目的でブレードにて余除塗工液を掻き落す際に、異物またはシリカ凝集隗を起点に未塗工部が発生する欠陥の発生を、塗工機に設置した反射型欠陥検出器による欠陥検出個数で決定した。
◎：流れ１０，０００ｍに０〜１個
○：流れ１０，０００ｍに２〜４個
△：流れ１０，０００ｍに５〜７個
×：流れ１０，０００ｍに８個以上
（ｉｉ）スクラッチ欠陥：基材に塗工液をウェブし、定量塗工する目的でブレードにて余除塗工液を掻き落す際に、樹脂の破泡等による未塗工欠損の発生の数を塗工機で目視確認した数で決定した。
◎：流れ５，０００ｍに１回
○：流れ５，０００ｍに２回
△：流れ５，０００ｍに３〜４回
×：流れ５，０００ｍに５回以上
(2) Coating properties of coating solution: When applying silica coagulated wrinkles, take into account the occurrence of streak defects starting from the coagulated wrinkles and the uncoated defects caused by bubbles in the resin. There is a need.
(I) Streak defect: When the excess coating liquid is scraped off with a blade for the purpose of coating the coating liquid on the substrate and applying it quantitatively, an uncoated part is generated starting from foreign matter or silica agglomerated flaws. The number of defects detected was determined by the number of defects detected by a reflective defect detector installed in the coating machine.
A: 0 to 1 in a flow 10,000 m ○: 2 to 4 in a flow 10,000 m Δ: 5 to 7 in a flow 10,000 m ×: 8 or more in a flow 10,000 m (ii) Scratch defect: base When the excess coating liquid is scraped off with a blade for the purpose of applying the coating liquid to the material and applying it quantitatively, visually check the number of uncoated defects caused by resin breakage, etc. The number was determined.
◎: Once in flow 5,000m ○: Twice in flow 5,000m △: 3-4 times in flow 5,000m ×: 5 times or more in flow 5,000m
（３）瞬間吸液性：試料ホルダーに両面テープを気泡が入らないように貼り、両面テープの上に試料を張り合わせた。動的液体浸透性測定装置（ドイツＥＭＣＯ社製 ＤＰＭ３３およびＤＰＭ３−２−Ｔ）試料ホルダーをセットし、測定を開始し、超音波透過強度データを得た。超音波透過強度の相対値は、受信信号の最小値を１００％になるように次式より算出した。
超音波透過強度の相対値（％）＝超音波受信信号の最小値／各測定時間における超音波受信信号×１００ （超音波受信信号は負の値で。）
超音波透過強度の相対値の経時変化を図４のようにグラフに表示し、最小値のピークが現れた時間を表４に示す。
(3) Instantaneous liquid absorbency: A double-sided tape was affixed to the sample holder so that no air bubbles entered, and the sample was laminated on the double-sided tape. A dynamic liquid permeability measurement device (DPM33 and DPM3-2-T manufactured by EMCO, Germany) was set, a measurement was started, and ultrasonic transmission intensity data was obtained. The relative value of the ultrasonic transmission intensity was calculated from the following equation so that the minimum value of the received signal was 100%.
Relative value of ultrasonic transmission intensity (%) = Minimum value of ultrasonic reception signal / Ultrasonic reception signal at each measurement time × 100 (The ultrasonic reception signal is a negative value.)
The change with time of the relative value of the ultrasonic transmission intensity is displayed in a graph as shown in FIG. 4, and the time when the peak of the minimum value appears is shown in Table 4.
（４）接触角：ＪＩＳ Ｒ ３２５７に準拠したぬれ性試験方法の静滴法により、昇華型捺染インク受容層の表面の接触角を測定した。 (4) Contact angle: The contact angle of the surface of the sublimation type printing ink receiving layer was measured by the sessile drop method of the wettability test method based on JIS R 3257.
（５）凹凸の有無及び凸部の幅：製造した各転写紙のインク受容層表面に対して、走査型電子顕微鏡（日本電子データム社製ＪＳＭ−６３９０Ａ型）を用い、凹凸の有無を観察し、凹凸がある場合については、任意の凝集塊６０個の幅を実測し、個々の長短の幅からの平均値を実測し、最小値５個、最大値５個を除く５０個の実測平均値を測定した。 (5) Presence / absence of projections and depressions and width of projections: The surface of the ink receiving layer of each transfer paper produced was observed for the presence / absence of projections and depressions using a scanning electron microscope (JSM-6390A type, manufactured by JEOL Datum). When there are irregularities, measure the width of 60 arbitrary agglomerates, measure the average value from individual long and short widths, and measure 50 average values excluding the minimum value of 5 and the maximum value of 5 Was measured.
（６）インク受容層の表面平均粗さ：インク受容層の表面粗さをレーザー顕微鏡（キーエンス社製カラーレーザー顕微鏡 ＶＫ−９７００型）を用い、２乗平均粗さ（μｍ）として測定した。 (6) Surface average roughness of the ink receiving layer: The surface roughness of the ink receiving layer was measured as a mean square roughness (μm) using a laser microscope (Keyence Color Laser Microscope VK-9700 type).
（７）インク乾燥性：製造した各転写紙にインクジェットプリンタで黒ベタ印字した直後に印字面をテッシュペーパーにて擦り、拭取った際に紙面上のインクの伸びを目視で確認し、下記の基準にて５段階評価した。３段階以上の評価が実用レベルである。
５：乾燥が早い。テッシュペーパーによる擦り拭取りした紙面は、インクの伸びがない。
４：乾燥が早い。テッシュペーパーによる擦り拭取りした紙面は、インクの伸びが殆どない。
３：乾燥が若干遅いが、実用上問題ないレベル。テッシュペーパーによる擦り拭取りした紙面は、インクの伸びが少しある。
２：乾燥が遅く、テッシュペーパーによる擦り拭取りした紙面は、インクの伸びがある。
１：乾燥が遅く、装置汚れや印字部の汚れにつながり、使用不可。テッシュペーパーによる擦り拭取りした紙面は、インクの伸びが長い。
(7) Ink drying property: Immediately after black printing on each transfer paper produced by an inkjet printer, the print surface was rubbed with tissue paper and wiped to visually check the elongation of the ink on the following surface. Five levels were evaluated based on the standard. Three or more grades are practical levels.
5: Drying is fast. The surface of the paper wiped off with tissue paper does not stretch the ink.
4: Drying is fast. The surface of the paper wiped off with tissue paper has almost no ink growth.
3: Slightly slow drying, but no problem in practical use. The surface of the paper that has been wiped off with tissue paper has a slight ink elongation.
2: Drying is slow, and the surface of the paper wiped off with tissue paper has ink elongation.
1: Drying is slow, leading to device stains and print stains, and cannot be used. The surface of the paper wiped off with tissue paper has a long ink elongation.
（８）画像再現性：目視にて、ＩＳＯ３００に規定されるデジタル画像の転写紙紙面への画像再現性を下記の基準にて５段階評価した。３段階以上の評価が実用レベルである。
５：原版と差異の無い画像再現性である。
４：画像再現性が良好。
３：画像再現性がやや劣るが使用可能。
２：画像再現性が劣り、使用不可能。
１：画像再現性が悪く、使用不可。
(8) Image reproducibility: Visually, the image reproducibility of the digital image prescribed in ISO300 on the surface of the transfer paper was evaluated in five stages according to the following criteria. Three or more grades are practical levels.
5: Image reproducibility with no difference from the original.
4: Good image reproducibility.
3: Although the image reproducibility is slightly inferior, it can be used.
2: Image reproducibility is inferior and cannot be used.
1: Image reproducibility is poor and cannot be used.
（９）寸法安定性：１０×１５０ｍｍの各転写紙について、自動式紙伸縮計（熊谷理機工業株式会社製）を用いて温度による伸びを測定した。測定は、２０℃におけるサンプルの長さを基準にして６０℃で３０分保持後の伸びを測定し、２０℃におけるサンプルの長さ（基準長さ）に対する伸びを％表示した。下記の基準にて５段階評価した。３段階以上の評価が実用レベルである。
５：換算値が３０未満
４：換算値が３０以上〜３５未満
３：３５以上〜４０未満
２：４０以上〜５０未満
１：５０以上
(9) Dimensional stability: For each transfer paper of 10 × 150 mm, the elongation due to temperature was measured using an automatic paper extensometer (manufactured by Kumagaya Riki Kogyo Co., Ltd.). In the measurement, the elongation after holding at 60 ° C. for 30 minutes was measured based on the sample length at 20 ° C., and the elongation relative to the sample length (reference length) at 20 ° C. was expressed in%. The following criteria were used for the 5-level evaluation. Three or more grades are practical levels.
5: Conversion value is less than 30 4: Conversion value is 30 or more and less than 35 3:35 or more and less than 40 2:40 or more and less than 50 1:50 or more
（１０）インクの裏抜け（昇華性染料裏抜け防止性）：製造した各転写紙に昇華性インクを印字し、熱源より熱を加えた際に、製造した転写紙のインク受容層面の反対面へのインクの裏抜けを目視で判定し、裏抜け防止性を下記の基準にて５段階評価した。３段階以上の評価が実用レベルである。
５：昇華性インクの裏抜けが全くない。
４：僅かに昇華性インクの裏抜けが殆どない。
３：僅かに昇華性インクの裏抜けがあるが実用上全く問題がない。
２：昇華性インクの裏抜けが認められ、熱源が少し汚れる。
１：昇華性染料の裏抜けが多く認められ、熱源装置を激しく汚す。
(10) Back-through of ink (prevention of sublimation dye back-through): The surface of the manufactured transfer paper opposite to the ink receiving layer surface when sublimation ink is printed on each transfer paper and heat is applied from a heat source. The ink breakthrough of the ink was visually judged, and the prevention of breakthrough was evaluated in five levels according to the following criteria. Three or more grades are practical levels.
5: There is no showthrough of sublimation ink.
4: Slightly sublimation ink does not show through.
3: There is slight penetration of sublimation ink, but there is no problem in practical use.
2: Sublimation of sublimation ink is observed and the heat source is slightly stained.
1: Many see-throughs of sublimation dyes are observed, and the heat source device is severely soiled.
（１１）耐熱性：製造した各転写紙に昇華性インクを印字し、温度条件を変えた熱源より熱を加えた際に、製造した転写紙のインク受容層面の劣化が始まる温度を測定した。２１０℃以上が実用レベルである。 (11) Heat resistance: Sublimation ink was printed on each manufactured transfer paper, and the temperature at which deterioration of the ink receiving layer surface of the manufactured transfer paper started when heat was applied from a heat source with different temperature conditions was measured. 210 ° C. or higher is a practical level.
（１２）透気度：ＪＩＳ−Ｐ−８１１７ 「紙及び板紙−透気度試験方法−ガーレー試験方法」に準拠して測定した。 (12) Air permeability: Measured according to JIS-P-8117 “Paper and paperboard—Air permeability test method—Gurley test method”.
（１３）ステキヒトサイズ度：ＪＩＳ−Ｐ−８１２２（２００４） 「紙及び板紙−サイズ度試験方法−ステキヒト法」に準拠して測定した。 (13) Steecht sizing degree: Measured according to JIS-P-8122 (2004) “Paper and paperboard—Sizing degree test method—Steechtton method”.
（１４）転写効率：（ｉ）解像性の評価、（ｉｉ）ベタ画像部の評価（ベタ画像部の画像濃度と均一性）に分けて目視で判定して昇華捺染型インクジェット記録の転写効率を下記の基準にて５段階評価した。３段階以上の評価が実用レベルである。
（ｉ）解像性
５：解像性良好。印字面にゆがみなどの現象が認められず、印字原稿に匹敵する印字調子の再現性がある。
４：解像性良好。印字面にゆがみなどの現象が認められないが、印字原稿に匹敵する印字調子の再現性が若干劣る。
３：解像性がやや劣るが、実用上全く問題が無い。印字面にゆがみなどの現象が認められず、印字原稿に匹敵する印字調子の再現性がやや劣るが被転写物の使用上問題が起こらない。
２：解像性がやや悪いが、条件によって使用可能。印字面にゆがみなどの現象が僅かに認められ、印字原稿に匹敵する印字調子の再現性がやや劣る。
１：解像性が悪く、使用不可。印字面にゆがみなどの現象が認められ、印字原稿に匹敵する印字調子の再現性がない。
（ｉｉ）ベタ画像部
５：画像濃度が高く、ベタ画像部にムラがない。
４：画像濃度が高く、ベタ画像部に若干ムラが認められる。
３：画像濃度やや高く、ベタ画像部にムラが認められるが実用上全く問題がない。
２：画像濃度がやや低く、ベタ画像部にムラが認められる。
１：画像濃度が低く、ベタ画像部に多くのムラが認められる。
(14) Transfer efficiency: (i) Evaluation of resolution, (ii) Evaluation of solid image portion (image density and uniformity of solid image portion) and transfer determination efficiency of sublimation printing type ink jet recording by visual judgment Was evaluated according to the following criteria. Three or more grades are practical levels.
(I) Resolution 5: Good resolution. There is no phenomenon such as distortion on the print surface, and the print tone is comparable to the printed document.
4: Good resolution. Although a phenomenon such as distortion is not recognized on the printing surface, the reproducibility of the printing tone comparable to the printed document is slightly inferior.
3: Although the resolution is slightly inferior, there is no problem in practical use. There is no phenomenon such as distortion on the printing surface, and the reproducibility of the printing tone comparable to that of the printed document is slightly inferior, but there is no problem in using the transferred material.
2: The resolution is slightly poor, but can be used depending on conditions. Phenomena such as distortion are slightly observed on the printing surface, and the reproducibility of the printing tone comparable to the printed document is slightly inferior.
1: Poor resolution and cannot be used. Phenomena such as distortion are recognized on the printing surface, and there is no reproducibility of the printing tone comparable to the printed document.
(Ii) Solid image portion 5: The image density is high and there is no unevenness in the solid image portion.
4: The image density is high, and some unevenness is observed in the solid image portion.
3: The image density is slightly high and unevenness is observed in the solid image portion, but there is no problem in practical use.
2: The image density is slightly low, and unevenness is observed in the solid image portion.
1: The image density is low, and a lot of unevenness is observed in the solid image portion.
以上により得られた結果を表３〜４に示す。 The result obtained by the above is shown to Tables 3-4.
Claims (3)
前記基材上に目止め塗工層が設けられ、前記目止め塗工層上に前記昇華型捺染インク受容層が設けられており、
前記昇華型捺染インク受容層は、水溶性樹脂と微細粒子を含有し、
前記目止め塗工層は、非水溶性樹脂と無機微粒子を含有し、
ＪＩＳ Ｐ ８１２２に準拠したステキヒトサイズが６０秒〜１２０秒であることを特徴とする昇華型インクジェット捺染転写紙。 A sublimation ink jet printing transfer paper having a substrate and a sublimation printing ink receiving layer,
A sealing coating layer is provided on the substrate, and the sublimation printing ink receiving layer is provided on the sealing coating layer,
The sublimation printing ink receiving layer contains a water-soluble resin and fine particles,
The sealing coating layer contains a water-insoluble resin and inorganic fine particles,
A sublimation type ink-jet printing transfer paper characterized in that the Stethich size according to JIS P 8122 is 60 seconds to 120 seconds.
前記昇華型捺染インク受容層は、前記微細粒子を２０〜８０質量％含有することを特徴とする請求項１記載の昇華型インクジェット捺染転写紙。 The base material is craft paper having a glossy surface on one side, and the sealing coating layer is provided on the glossy surface,
2. The sublimation type inkjet printing transfer paper according to claim 1, wherein the sublimation type printing ink receiving layer contains 20 to 80% by mass of the fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008284781A JP5215132B2 (en) | 2008-11-05 | 2008-11-05 | Sublimation type inkjet printing transfer paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008284781A JP5215132B2 (en) | 2008-11-05 | 2008-11-05 | Sublimation type inkjet printing transfer paper |
Publications (2)
| Publication Number | Publication Date |
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| JP2010110973A JP2010110973A (en) | 2010-05-20 |
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| CN103538386A (en) * | 2012-07-16 | 2014-01-29 | 苏州市全佳涂布制品有限公司 | Quick-drying ink-jet thermal dye sublimation transfer printing medium and preparation method thereof |
| JP6239541B2 (en) * | 2015-02-05 | 2017-11-29 | 三菱製紙株式会社 | Printing paper used for paper printing |
| JP6239539B2 (en) | 2015-02-05 | 2017-11-29 | 三菱製紙株式会社 | Printing paper used for paper printing |
| WO2016136122A1 (en) * | 2015-02-27 | 2016-09-01 | 大王製紙株式会社 | Sublimation-type inkjet textile printing transfer paper and method for producing same |
| JP6689050B2 (en) * | 2015-09-11 | 2020-04-28 | 大王製紙株式会社 | Sublimation type inkjet printing transfer paper and method for producing the same |
| JP6689043B2 (en) * | 2015-08-10 | 2020-04-28 | 大王製紙株式会社 | Sublimation type inkjet printing transfer paper and method for producing the same |
| JP2018001668A (en) * | 2016-07-06 | 2018-01-11 | 三菱製紙株式会社 | Transfer paper |
| JP6514670B2 (en) * | 2016-08-08 | 2019-05-15 | 三菱製紙株式会社 | Transfer paper |
| JP6514674B2 (en) * | 2016-08-17 | 2019-05-15 | 三菱製紙株式会社 | Transfer paper |
| JP6717708B2 (en) * | 2016-08-26 | 2020-07-01 | 大王製紙株式会社 | Sublimation type inkjet printing transfer paper and method for producing the same |
| JP6930351B2 (en) * | 2017-10-02 | 2021-09-01 | 王子ホールディングス株式会社 | Sublimation type printing transfer paper |
| WO2022054435A1 (en) * | 2020-09-10 | 2022-03-17 | 三菱製紙株式会社 | Transfer paper and transfer printing method |
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| JP2001277707A (en) * | 2000-03-30 | 2001-10-10 | Mitsubishi Paper Mills Ltd | Medium to be recorded by ink jetting and transfer recording method to print medium |
| JP2006001219A (en) * | 2004-06-21 | 2006-01-05 | Oji Paper Co Ltd | Support for inkjet recording medium, and inkjet recording medium |
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