JP4127531B2 - Transparent inkjet recording sheet - Google Patents
Transparent inkjet recording sheet Download PDFInfo
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- JP4127531B2 JP4127531B2 JP2003309909A JP2003309909A JP4127531B2 JP 4127531 B2 JP4127531 B2 JP 4127531B2 JP 2003309909 A JP2003309909 A JP 2003309909A JP 2003309909 A JP2003309909 A JP 2003309909A JP 4127531 B2 JP4127531 B2 JP 4127531B2
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- recording sheet
- styrene copolymer
- ink
- water
- transparent
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 14
- 229920003169 water-soluble polymer Polymers 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920006026 co-polymeric resin Polymers 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Description
本発明はインクジェット用記録シートに関するものであり、特に、透明インクジェット記録用シートに関する。 The present invention relates to an ink jet recording sheet, in particular, it relates to a transparent ink jet recording sheet.
従来の技術では、特に透明インクジェット記録用シートの受像層は、ポリビニルアルコール、ポリビニルピロリドン、澱粉、水溶性セルロース誘導体が提案されている。しかし、この方法では特に水性顔料インクの吸収性、乾燥性が悪く、乾燥途中で受像層がひび割れる問題がある。更に耐水性も不十分なため、水滴や汗が受像層に付着した場合、記録画像が滲んだり、受像層が基材から剥がれ易いという問題があり、いまだ満足できる結果を得るに至っていない。そこで、耐水性を向上させる方法として、数々の架橋剤を用いることが検討されており、このような架橋剤として、例えば、イソシアネート類、アジリジン類、ホウ酸類等が挙げられる。しかし、このような架橋剤では充分な耐水性を得ることができず、透明度が低下する問題がある。特開２０００−５２６４７、特開２００１−２１９６４５には、オキサゾリン基を有する水溶性ポリマーを含有する、インクジェット用記録シート用コーティング剤が開示されている。しかしながら、オキサゾリン基１種類のみの添加では、塗工液固形分中のオキサゾリン基含有水溶性ポリマーの固形分が４５％〜５０％でありながら、耐水性がいまだ不十分であり、また、充分な耐水性を得られたとしても、記録画像が滲んだり、インクの定着性の低下を引き起こすという欠点がある。また、オキサゾリン基含有水溶性ポリマー多く添加することでコスト的に不利である。従来の透明インクジェット用記録シートは、耐水性の向上と共に、インク吸収性、乾燥性が低下し、印刷画質の低下が問題であった。このため、インク吸収性と印刷物の耐水性とを備え持つ透明インクジェット用記録シートは得られていない。
本発明の目的は、透明インクジェット用記録シートにおいて、特に水性顔料インクの吸収性、乾燥性、発色性に優れ、且つ、耐水性が良好な透明インクジェット用記録シートを提供することにある。 An object of the present invention, a transparent ink jet recording sheet, in particular the absorption of the aqueous pigment ink, drying property, excellent color forming property, and, in the water resistance to provide good transparency ink jet recording sheet.
目的を達成するため、本発明は、カチオン性ポリエーテル系ウレタン樹脂、カチオン性アクリル・スチレン共重合樹脂の２種からなり、架橋剤としてオキサゾリン基を有する水溶性ポリマー及びメタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物を含有することを特徴とするものである。 In order to achieve the object, the present invention comprises a cationic polyether urethane resin, a cationic acrylic / styrene copolymer resin, a water-soluble polymer having an oxazoline group as a crosslinking agent, and methacrylic acid / butyl acrylate / It contains a hydrogen chloride neutralized product of a grafted product of methyl methacrylate / styrene copolymer and polyethyleneimine .
本発明は透明インクジェット用記録シートにおいて、特に水性顔料インクの吸収性、乾燥性、発色性に優れ、且つ、耐水性が良好な透明インクジェット用記録シートを提供することができる。 The present invention is a recording sheet for a transparent ink-jet, in particular the absorption of the aqueous pigment ink, drying property, excellent color forming property, and can be water resistance provides good transparency ink jet recording sheet.
本発明者は鋭意検討の結果、水性顔料インクを用いて画像を形成する透明インクジェット用記録シートにおいて、該記録シートの受像層が、カチオン性ポリエーテル系ウレタン樹脂、カチオン性アクリル・スチレン共重合樹脂の２種からなり、架橋剤としてオキサゾリン基を有する水溶性ポリマー及びメタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物を含有することを特徴とする透明インクジェット用記録シートを提供するに至った。 As a result of intensive studies, the present inventor has found that in an inkjet recording sheet for forming an image using an aqueous pigment ink, the image receiving layer of the recording sheet is a cationic polyether urethane resin, a cationic acrylic / styrene copolymer resin The water-soluble polymer having an oxazoline group as a cross-linking agent and a hydrogen chloride neutralized product of a grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine as a crosslinking agent It came to provide the recording sheet for transparent inkjet .
受像層固形分中のカチオン性ポリエーテル系ウレタン樹脂とカチオン性アクリル・スチレン共重合体樹脂の重量比は、カチオン性ポリエーテル系ウレタン樹脂が６５〜８５％で、カチオン性アクリル・スチレン共重合体樹脂が１５〜３５％のものが好ましい。さらには、カチオン性ポリエーテル系ウレタン樹脂が７０〜８０％で、カチオン性アクリル・スチレン共重合体樹脂が２０〜３０％のものが好ましい。カチオン性ポリエーテル系ウレタン樹脂が６５％を下回るとインク吸収性が不十分であり、８５％を上回ると耐水性が悪くなる。カチオン性アクリル・スチレン共重合体樹脂が１５％を下回ると基材との密着が悪くなり耐水性が不十分であり、３５％より大きくなるとインク吸収性、乾燥性が不十分で且つ、印刷画像に滲みを生じる。 The weight ratio of the cationic polyether urethane resin to the cationic acrylic / styrene copolymer resin in the solid content of the image receiving layer is 65 to 85% of the cationic polyether urethane resin , and the cationic acrylic / styrene copolymer is The resin is preferably 15 to 35%. Furthermore, it is preferable that the cationic polyether urethane resin is 70 to 80% and the cationic acrylic / styrene copolymer resin is 20 to 30%. When the cationic polyether urethane resin is less than 65%, the ink absorbability is insufficient, and when it exceeds 85%, the water resistance is deteriorated. If the cationic acrylic / styrene copolymer resin is less than 15%, the adhesion to the substrate is poor and the water resistance is insufficient. If the cationic acrylic / styrene copolymer resin is more than 35%, the ink absorptivity and drying properties are insufficient, and the printed image. Bleeding occurs.
受像層固形分中に含まれるオキサゾリン基を有する水溶性ポリマーは０.３〜２.０％が好ましい。さらには、０.５〜１.５％が好ましい。受像層固形分中に含まれるオキサゾリン基を有する水溶性ポリマーが０.５％を下回ると充分な耐水性を得ることができず、１.５％を上回るとインク吸収性、乾燥性が低下する。メタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物は２.０〜３.７％が好ましい。さらには、２.５〜３.５％が好ましい。メタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物が２.５％を下回ると充分な耐水性を得られず、また、インクの定着力も低下する。また、３.５％を上回ると、インク吸収性が低下する。 The water-soluble polymer having an oxazoline group contained in the solid content of the image-receiving layer is preferably 0.3 to 2.0%. Furthermore, 0.5 to 1.5% is preferable. If the water-soluble polymer having an oxazoline group contained in the solid content of the image-receiving layer is less than 0.5%, sufficient water resistance cannot be obtained, and if it exceeds 1.5%, ink absorbency and drying properties are lowered. . The hydrogen chloride neutralized product of the grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine is preferably 2.0 to 3.7%. Furthermore, 2.5 to 3.5% is preferable. When the hydrogen chloride neutralized product of the grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine is less than 2.5%, sufficient water resistance cannot be obtained, and the fixing ability of the ink is also low. descend. On the other hand, if it exceeds 3.5%, the ink absorbability is lowered.
基材は、ポリエステル、ポリオレフィン、ポリ塩化ビニル等の透明合成樹脂フィルムが挙げられる。また、基材はコロナ放電処理などの表面処理によりインク受像層のコーティング性を改善させることもできる。基材の厚みは２５〜４００μｍの範囲が好ましく、プリンタへの装着性や取り扱いを考慮すると５０〜３００μｍが好ましい。基材の厚みが２５μｍ未満では、ハンドリングやプリンタでの装着性が悪いほか、プリンタに装着した記録材がフィードされる際に皺が発生したり等正常に紙送りされないことがある。また、基材が４００μｍを超えるとプリンタへの装着が困難になったり、正常に紙送りされないことがある。 Examples of the base material include transparent synthetic resin films such as polyester, polyolefin, and polyvinyl chloride. Further, the coating property of the ink image-receiving layer can be improved by surface treatment such as corona discharge treatment. The thickness of the substrate is preferably in the range of 25 to 400 [mu] m, and is preferably 50 to 300 [mu] m in consideration of the mountability to the printer and handling. If the thickness of the substrate is less than 25 μm, handling and printer mounting properties are not good, and paper may not be fed normally, such as wrinkles when the recording material mounted on the printer is fed. If the substrate exceeds 400 μm, it may be difficult to mount the printer on the printer or the paper may not be fed normally.
インク受像層の厚みは、５〜５０μｍが好ましく、さらには１０〜３０μｍが好ましいが、これに限定するものではない。上述により得られた透明インクジェット用記録シートは必要に応じて粘着層を設けることも可能である。 The thickness of the ink image-receiving layer is preferably 5 to 50 μm, more preferably 10 to 30 μm, but is not limited thereto. The transparent ink jet recording sheet obtained as described above can be provided with an adhesive layer as required.
以下に実施例を挙げて本発明を具体的に説明するが、本発明がこれによって限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
基材として帝人デュポンフィルム株式会社製ポリエステルフィルムを使用し、その基材の一方に、乾燥重量比がポリエーテル系ウレタン樹脂（第一工業製薬株式会社 スーパーフレックス６００ 固形分２５％）７２％、アクリル・スチレン共重合樹脂（中央理化工業株式会社 リカボンド FK-８２０ 固形分３９％）２４％、オキサゾリン基を有する水溶性ポリマー（固形分４０％）０.５％、メタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物（固形分４９％）３.５％となるようにイオン交換水に順次投入し攪拌処理を行なった後、乾燥塗膜が１６μｍとなるようにインク受像層を設けて透明インクジェット用記録シートを得た。 A polyester film manufactured by Teijin DuPont Films Ltd. is used as a base material. One of the base materials has a dry weight ratio of 72% polyether urethane resin (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 600, solid content 25%), acrylic. -Styrene copolymer resin (Chuo Rika Kogyo Co., Ltd. Rikabond FK-820 solid content 39%) 24%, water-soluble polymer having oxazoline group (solid content 40%) 0.5%, methacrylic acid / butyl acrylate / methacrylic acid After the hydrogen chloride neutralized product (solid content 49%) of the grafted product of methyl / styrene copolymer and polyethyleneimine is added to ion-exchanged water in order to give 3.5%, a dry coating film is formed. An ink image-receiving layer was provided so as to be 16 μm to obtain a transparent inkjet recording sheet .
実施例１で用いたオキサゾリン基を有する水溶性ポリマーの乾燥重量比を１.５％、メタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物の乾燥重量比を２.５％とした以外は、実施例１と同様にして透明インクジェット用記録シートを得た。
(比較例１)
The water-soluble polymer having an oxazoline group used in Example 1 has a dry weight ratio of 1.5%, and a hydrogen chloride neutralized product of a grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine. A transparent ink jet recording sheet was obtained in the same manner as in Example 1 except that the dry weight ratio was 2.5%.
(Comparative Example 1)
実施例１で用いたオキサゾリン基を有する水溶性ポリマー及びメタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物を添加しない以外は、実施例１と同様にして透明インクジェット用記録シートを得た。
(比較例２)
Example 1 except that the water-soluble polymer having an oxazoline group used in Example 1 and a hydrogen chloride neutralized product of a grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine were not added. In the same manner, a recording sheet for transparent ink jet was obtained.
(Comparative Example 2)
実施例１で用いたオキサゾリン基を有する水溶性ポリマーを添加せず、メタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物を４.０％とした以外は、実施例１と同様にして透明インクジェット用記録シートを得た。
(比較例３)
Without adding the water-soluble polymer having an oxazoline group used in Example 1, 4.0% of a hydrogen chloride neutralized product of a grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine was used. A transparent ink jet recording sheet was obtained in the same manner as in Example 1 except that .
(Comparative Example 3)
実施例１で用いたメタクリル酸・アクリル酸ブチル・メタクリル酸メチル・スチレン共重合物とポリエチレンイミンのグラフト化物の塩化水素中和物を添加せず、オキサゾリン基を有する水溶性ポリマーを４.０％とした以外は、実施例１と同様にして透明インクジェット用記録シートを得た。
(比較例４)
4.0% of the water-soluble polymer having an oxazoline group was added without adding the hydrogen chloride neutralized product of the grafted product of methacrylic acid / butyl acrylate / methyl methacrylate / styrene copolymer and polyethyleneimine used in Example 1. A transparent ink jet recording sheet was obtained in the same manner as in Example 1 except that.
(Comparative Example 4)
実施例１で用いたカチオン性ポリエーテル系ウレタン樹脂を添加しない以外は、実施例１と同様にして透明インクジェット用記録シートを得た。
(比較例５)
A transparent inkjet recording sheet was obtained in the same manner as in Example 1 except that the cationic polyether urethane resin used in Example 1 was not added.
(Comparative Example 5)
実施例１で用いたカチオン性アクリル・スチレン共重合体樹脂を添加しない以外は、実施例１と同様にして透明インクジェット用記録シートを得た。 A transparent inkjet recording sheet was obtained in the same manner as in Example 1 except that the cationic acrylic / styrene copolymer resin used in Example 1 was not added.
このようにして得られた透明インクジェット用記録シートを、セイコーエプソン株式会社製、MC-２０００を用いイエロー・マゼンタ・シアン・ブラックの文字およびベタを印字し評価を行った。インク吸収性、乾燥性の評価は、印字後、綿棒で印字部表面を擦り、綿棒に付着したインクの状態を目視で確認した。○：綿棒にインクが付着しない、×：綿棒にインクが付着している。耐水性の評価は、印字物を水に浸漬し３時間放置後、指で擦り受像層の耐水性、インクの定着性を確認した。○：指で擦っても、受像層、インクがとれない、×：指で擦ると受像層及びインクが取れてしまう。発色性の評価は印字部を目視にて確認した。○：印刷画像が鮮明である、×：滲みが生じている The transparent inkjet recording sheet thus obtained was evaluated by printing yellow, magenta, cyan, and black letters and solids using MC-2000 manufactured by Seiko Epson Corporation. The ink absorbability and the drying property were evaluated by rubbing the surface of the printed part with a cotton swab after printing, and visually confirming the state of the ink attached to the cotton swab. ○: Ink does not adhere to the cotton swab, ×: Ink adheres to the cotton swab. The water resistance was evaluated by immersing the printed matter in water and allowing it to stand for 3 hours, and then rubbing with a finger to confirm the water resistance of the image receiving layer and the ink fixing property. ○: Image receiving layer and ink cannot be removed by rubbing with a finger, x: Image receiving layer and ink are removed by rubbing with a finger. The evaluation of color development was made by visually checking the printed part. ○: The printed image is clear, ×: Bleeding occurs
これらの結果を表１に示す。 These results are shown in Table 1.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003309909A JP4127531B2 (en) | 2003-09-02 | 2003-09-02 | Transparent inkjet recording sheet |
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| JP2003309909A JP4127531B2 (en) | 2003-09-02 | 2003-09-02 | Transparent inkjet recording sheet |
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| JP2005074880A JP2005074880A (en) | 2005-03-24 |
| JP4127531B2 true JP4127531B2 (en) | 2008-07-30 |
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| JP5252483B2 (en) * | 2008-04-02 | 2013-07-31 | ユニオンケミカー株式会社 | Inkjet receiving layer |
| JP5318674B2 (en) | 2009-06-23 | 2013-10-16 | セイコーエプソン株式会社 | Inkjet recording sheet |
| JP5644208B2 (en) * | 2010-06-24 | 2014-12-24 | セイコーエプソン株式会社 | Inkjet recording medium |
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