JP2011161758A - Inkjet recording medium and ink receiving layer forming coating liquid - Google Patents
Inkjet recording medium and ink receiving layer forming coating liquid Download PDFInfo
- Publication number
- JP2011161758A JP2011161758A JP2010026403A JP2010026403A JP2011161758A JP 2011161758 A JP2011161758 A JP 2011161758A JP 2010026403 A JP2010026403 A JP 2010026403A JP 2010026403 A JP2010026403 A JP 2010026403A JP 2011161758 A JP2011161758 A JP 2011161758A
- Authority
- JP
- Japan
- Prior art keywords
- coating liquid
- receiving layer
- recording medium
- ink
- carboxyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000000576 coating method Methods 0.000 title claims abstract description 105
- 239000011248 coating agent Substances 0.000 title claims abstract description 101
- 239000007788 liquid Substances 0.000 title claims description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 54
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- 125000002091 cationic group Chemical group 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 12
- 239000000976 ink Substances 0.000 description 76
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 238000000034 method Methods 0.000 description 31
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- 239000000243 solution Substances 0.000 description 27
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- 239000011575 calcium Substances 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
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- 229940005550 sodium alginate Drugs 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
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- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
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- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
【課題】透明性、特に、インク受容相中のシリカ濃度が高い場合の透明性に優れたインクジェット用記録媒体を提供する。
【解決手段】下記一般式（１）で表される構造単位を有するカルボキシル基含有ポリビニルアルコール系樹脂（Ａ）とカチオン性コロイダルシリカ（Ｂ）及び水を含有する塗工液を支持体上に塗工、乾燥して形成されたインク受容層を有する
（式中、Ｒ1、Ｒ2、Ｒ3は、それぞれ独立して水素原子又はアルキル基を示し、Ｘは炭素数が４〜５０のアルキレンを示し、Ｙは水素原子又はアルカリ金属を示す。）
【選択図】なしAn inkjet recording medium having excellent transparency, particularly transparency when the silica concentration in an ink receiving phase is high is provided.
A coating solution containing a carboxyl group-containing polyvinyl alcohol resin (A) having a structural unit represented by the following general formula (1), cationic colloidal silica (B), and water is coated on a support. Having an ink-receiving layer formed by drying
(In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, X represents an alkylene having 4 to 50 carbon atoms, and Y represents a hydrogen atom or an alkali metal.)
[Selection figure] None
Description
本発明は、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂と略記する。）と無機微粒子を含有するインク受容層を有するインクジェット用記録媒体に関し、さらに詳しくは、透明性、特にインク受容層中のシリカ濃度を高くした時の透明性に優れるインク受容層を有するインクジェット用記録媒体に関する。 The present invention relates to an ink jet recording medium having an ink receiving layer containing a polyvinyl alcohol resin (hereinafter abbreviated as PVA resin) and inorganic fine particles, and more particularly, transparency, particularly silica in the ink receiving layer. The present invention relates to an inkjet recording medium having an ink-receiving layer that is excellent in transparency when the concentration is increased.
インクジェット記録方式は、インクの小滴をノズルより飛翔させ、記録媒体の表面に着弾、定着させて、文字、画像等の記録を行なう方法で、フルカラー印刷が容易、ランニングコストが安い、印刷時の騒音が少ないなどの多くの利点から、家庭やオフィスなどのプリンターに広く用いられている。 The ink jet recording method is a method of recording characters, images, etc. by ejecting ink droplets from nozzles and landing and fixing on the surface of the recording medium. Full color printing is easy, running cost is low, It is widely used in home and office printers because of its many advantages such as low noise.
かかる記録方式で用いられるインクジェット用記録媒体には、ＰＶＡ系樹脂等のバインダーとシリカ等の無機微粒子を含有して、シリカの空隙にインクを吸収させる空隙型のインク受容層を持つものと、インクを吸収して膨潤する樹脂を主成分とする膨潤型のインク受容層を持つものがある。中でも、無機微粒子として非晶質シリカを用いた空隙型インク受容層をもつインクジェット用記録媒体は、インク吸収性（吸収量、吸収速度）が良好であるという利点から、好適に用いられている。しかし、この記録媒体は、シリカの粒子径が比較的大きいため光沢性に欠け、また、空隙内部に吸収されたインクも隠蔽されるため、画像鮮明度が不足しがちであり、写真等の印刷には不適当である。 The ink jet recording medium used in such a recording system includes a binder such as a PVA resin and inorganic fine particles such as silica, and has a void-type ink receiving layer that absorbs ink in the voids of silica, and an ink. Some have a swelling type ink receiving layer mainly composed of a resin that swells by absorbing water. Among them, an ink jet recording medium having a void-type ink receiving layer using amorphous silica as inorganic fine particles is preferably used because of its good ink absorbability (absorption amount, absorption speed). However, this recording medium lacks gloss due to the relatively large particle size of silica, and the ink absorbed inside the voids is also concealed. Inappropriate for
かかる課題に対し、無機微粒子としてコロイダルシリカを含有する塗工液で形成したインク受容層を持つインクジェット用記録媒体が提案されている。（例えば、特許文献１参照。）コロイダルシリカは超微粒子であるため、得られる記録媒体は光沢性に優れ、インク受容層中の光の透過度が高く、鮮明性に優れた画像が得られる。また、コロイダルシリカは、予め均一に分散しているため、形成したインク受容層の均一性が高いという効果も得られる。 In response to such a problem, an ink jet recording medium having an ink receiving layer formed of a coating liquid containing colloidal silica as inorganic fine particles has been proposed. (For example, refer to Patent Document 1.) Since colloidal silica is ultrafine particles, the resulting recording medium has excellent gloss, high light transmittance in the ink-receiving layer, and an image with excellent sharpness. Further, since colloidal silica is uniformly dispersed in advance, an effect that the uniformity of the formed ink receiving layer is high is also obtained.
しかし、近年、デジタルカメラやパソコンの解像度の技術が向上しており、また、医療分野においてもエコー写真やＮＭＲ写真などによる診断の精度を向上させたいという要望があることから、更に解像度の高い画像を鮮明に印刷するための技術及びインクジェット用記録媒体が要求されている。 However, in recent years, the resolution technology of digital cameras and personal computers has been improved, and in the medical field, there is a demand for improving the accuracy of diagnosis using echo photographs and NMR photographs. There is a demand for a technology for clearly printing the image and an ink jet recording medium.
例えば、解像度の高い鮮明な画像の印刷方法として、インク濃度を下げ、多段階印刷することにより鮮明に濃淡を付けるインクジェット記録方式が実施されている。この方法では、濃い色を印刷する部分には、インクの着弾回数を増やす必要がある。この場合、インクの量が多いため、フェザリングが起こりやすく、それによって画像鮮明度が低下する場合がある。そのため、インクジェット用記録媒体は、さらに優れたインク吸収性と定着性が求められる。 For example, as a method for printing a clear image with high resolution, an ink jet recording method in which ink density is lowered and multi-step printing is used to clearly and lightly shade the image has been implemented. In this method, it is necessary to increase the number of times the ink has landed in a portion where a dark color is printed. In this case, since the amount of ink is large, feathering is likely to occur, which may reduce the image definition. Therefore, the ink jet recording medium is required to have further excellent ink absorbability and fixability.
通常、インクジェット印刷に用いられる染料系インクはアニオン性であることから、その定着剤としてカチオン性化合物がインク受容層中に配合されているが、無機微粒子にも同様の機能を持たせるため、カチオン表面処理された無機微粒子の使用が提案されている。例えば、特許文献２には、無機微粒子としてカチオン性コロイダルシリカが用いられている。 In general, dye-based inks used for ink jet printing are anionic, so a cationic compound is incorporated in the ink-receiving layer as a fixing agent. The use of surface-treated inorganic fine particles has been proposed. For example, Patent Document 2 uses cationic colloidal silica as inorganic fine particles.
一方、印字特性（印字濃度やフェザリング）や表面紙力強度の向上を目的として、バインダーとしてカルボキシル基含有ＰＶＡ系樹脂及びポリアクリル酸塩を用いたインクジェット用記録媒体が提案されている。（例えば、特許文献３参照。） On the other hand, for the purpose of improving printing characteristics (printing density and feathering) and surface paper strength, an inkjet recording medium using a carboxyl group-containing PVA resin and polyacrylate as a binder has been proposed. (For example, refer to Patent Document 3.)
そこで、本発明者らは、カルボキシル基含有ＰＶＡ系樹脂とカチオン性コロイダルシリカの組み合わせについて検討を行ったが、塗工液中でアニオン性であるカルボキシル基含有ＰＶＡ系樹脂とカチオン性コロイダルシリカが電気的引力により引き付けられて凝集してしまうため、白濁してしまい、この塗工液を用いて得られたインクジェット用記録媒体は、透明性の点で難があることが判明した。
Therefore, the present inventors have studied the combination of a carboxyl group-containing PVA resin and cationic colloidal silica. However, the carboxyl group-containing PVA resin and cationic colloidal silica, which are anionic in the coating liquid, are electrically Since it is attracted by the attractive force and agglomerates, it becomes cloudy, and it has been found that the ink jet recording medium obtained using this coating solution has difficulty in transparency.
本発明の目的は、ＰＶＡ系樹脂と無機微粒子を含有し、透明性に優れるインク受容層を有するインクジェット用記録媒体の提供である。 An object of the present invention is to provide an ink jet recording medium having an ink receiving layer containing a PVA resin and inorganic fine particles and having excellent transparency.
本発明者は、上記の事情に鑑み鋭意検討した結果、一般式（１）に示される構造単位を有するカルボキシル基含有ＰＶＡ系樹脂（Ａ）とカチオン性コロイダルシリカ（Ｂ）及び水を含有する塗工液をインク支持体上に塗工、乾燥して形成したインク受容層を有するインクジェット用記録媒体によって、本発明の目的が達成されることを見出し、本発明を完成した。
（式中、Ｒ1、Ｒ2、Ｒ3は、それぞれ独立して水素原子又はアルキル基を示し、Ｘは炭素数が４〜５０のアルキレンを示し、Ｙは水素原子又はアルカリ金属を示す。）
As a result of intensive studies in view of the above circumstances, the present inventor has found that a coating containing a carboxyl group-containing PVA resin (A) having a structural unit represented by the general formula (1), a cationic colloidal silica (B), and water. The inventors have found that the object of the present invention can be achieved by an ink jet recording medium having an ink receiving layer formed by coating and drying a working liquid on an ink support, and completed the present invention.
(In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, X represents an alkylene having 4 to 50 carbon atoms, and Y represents a hydrogen atom or an alkali metal.)
すなわち本発明は、カルボキシル基含有ＰＶＡ系樹脂とカチオン性コロイダルシリカを含有するインク受容層を有するインクジェット用記録媒体において、かかるカルボキシル基含有ＰＶＡ系樹脂として、主鎖から炭素数４〜５０の長鎖アルキレンを介してカルボキシル基が結合したＰＶＡ系樹脂を用いたことを最大の特徴とするものである。 That is, the present invention relates to an inkjet recording medium having an ink receiving layer containing a carboxyl group-containing PVA resin and cationic colloidal silica, and the carboxyl group-containing PVA resin is a long chain having 4 to 50 carbon atoms from the main chain. The most characteristic feature is that a PVA resin having a carboxyl group bonded thereto through an alkylene is used.
本発明のインクジェット用記録媒体は、透明性、特にインク受容層中のシリカ濃度が高い時の透明性に優れるものであり、優れたインク吸収性を持ち、優れた画像鮮明度を有することが期待できるため、各種印刷用紙に適用でき、特に診察用写真など高解像度の画像を印刷するための用紙として好適である。 The ink jet recording medium of the present invention is excellent in transparency, particularly when the silica concentration in the ink receiving layer is high, and is expected to have excellent ink absorbability and excellent image definition. Therefore, it can be applied to various printing papers, and is particularly suitable as a paper for printing high-resolution images such as medical photographs.
以下、本発明につき詳細に説明するが、これらは望ましい実施様態の一例を示すものであり、この内容に特定されるものではない。 Hereinafter, the present invention will be described in detail, but these show examples of desirable embodiments and are not limited to these contents.
まず、本発明のインク受容層用塗工液について詳細に説明し、その後、その塗工液を用いたインクジェット用記録媒体の製造工程を説明する。
［カルボキシル基含有ＰＶＡ系樹脂（Ａ）］
本発明の塗工液に用いられるカルボキシル基含有ＰＶＡ系樹脂（Ａ）は、下記一般式（１）で表される構造単位を有する。
[Carboxyl group-containing PVA resin (A)]
The carboxyl group-containing PVA resin (A) used in the coating liquid of the present invention has a structural unit represented by the following general formula (1).
上記一般式（１）において、Ｒ1、Ｒ2、Ｒ3は、それぞれ独立して水素原子又はアルキル基であるが、塗工液を調製する際の水への溶解性の点から、中でも、Ｒ1、Ｒ2、Ｒ3が全て水素原子であるものが好ましい。Ｒ1、Ｒ2、Ｒ３がアルキル基である場合は、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、オクチル基等の炭素数１〜８のアルキル基が挙げられ、かかるアルキル基は、ハロゲン基、水酸基、エステル基、カルボン酸基、スルホン酸基等の置換基を有していてもよい。 In the general formula (1), R 1 , R 2 and R 3 are each independently a hydrogen atom or an alkyl group, but from the viewpoint of solubility in water when preparing a coating liquid, R 1 , R 2 and R 3 are preferably all hydrogen atoms. R 1, when R 2, R 3 is an alkyl group such as methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, tert- butyl group, the number of carbon atoms such as octyl The alkyl group of 1-8 is mentioned, This alkyl group may have substituents, such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group.
一般式（１）において、Ｘは通常、炭素数が４〜５０の直鎖状のアルキレンであり、炭素数が６〜４０の直鎖状のアルキレンが好ましく、炭素数が８〜２０の直鎖状のアルキレンがさらに好ましい。炭素数が多すぎると、水への溶解性が低下する傾向があるため、塗工液の調製が困難になる場合があり好ましくなく、逆に炭素数が少なすぎると、カルボキシル基に引き付けられるカチオン性コロイダルシリカ（Ｂ）が主鎖の水酸基に引き付けられるカチオン性コロイダルシリカ（Ｂ）付近に存在しやすくなり、カチオン性コロイダルシリカ（Ｂ）同士が密集しやすいため、インクジェット用記録媒体とした時、目的の透明度が得られない場合があり好ましくない。 In the general formula (1), X is usually a linear alkylene having 4 to 50 carbon atoms, preferably a linear alkylene having 6 to 40 carbon atoms, and a linear chain having 8 to 20 carbon atoms. More preferred are alkylenes. If the number of carbon atoms is too large, the solubility in water tends to decrease, which may make it difficult to prepare a coating solution. On the other hand, if the number of carbon atoms is too small, a cation that is attracted to a carboxyl group. When the cationic colloidal silica (B) is likely to be present in the vicinity of the cationic colloidal silica (B) attracted to the hydroxyl group of the main chain and the cationic colloidal silica (B) is likely to be densely packed, The desired transparency may not be obtained, which is not preferable.
また、Ｙは、通常、水素原子であるが、その一部又は全部がカルボキシル基含有ＰＶＡ系樹脂（Ａ）製造のケン化工程に用いる触媒に由来するナトリウム、カリウム等のアルカリ金属であっても良い。 Y is usually a hydrogen atom, but part or all of it may be an alkali metal such as sodium or potassium derived from the catalyst used in the saponification step for producing the carboxyl group-containing PVA resin (A). good.
かかるカルボキシル基含有ＰＶＡ系樹脂（Ａ）を製造する方法としては、特に限定されないが、下記一般式（２）で示される化合物とビニルエステル系単量体との共重合体をケン化する方法が好ましく用いられる。なお、２種以上の一般式（２）の化合物と２種以上のビニルエステル系単量体とを共重合させても良い。
上記一般式（２）において、Ｒ1、Ｒ2、Ｒ3、Ｘは、上記一般式（１）と同様のものが挙げられる。また、Ｙは、上記一般式（１）と同様のものが挙げられるが、さらに重合後のケン化工程により脱離されるため、エステル基であっても良い。 In the general formula (2), examples of R 1 , R 2 , R 3 , and X are the same as those in the general formula (1). Y may be the same as in the general formula (1), but may be an ester group because it is eliminated by a saponification step after polymerization.
一般式（２）で示される化合物としては、具体的には、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、リノール酸、リノレン酸等の１−アルケン酸およびそのエステルや塩等の誘導体が挙げられ、中でもカチオン性コロイダルシリカ（Ｂ）を密集させにくく、かつ塗工液にする際に水への溶解性が良い点で、Ｒ1、Ｒ2、Ｒ3が水素である１−アルケン酸が好ましく、特にＹが水素で、Ｘが炭素数８のアルキレンであるウンデシレン酸およびその誘導体が好ましい。 Specific examples of the compound represented by the general formula (2) include 1-alkenoic acid such as undecylenic acid, oleic acid, elaidic acid, cetreic acid, erucic acid, linoleic acid, and linolenic acid, and esters and salts thereof. In particular, R 1 , R 2 , and R 3 are hydrogen in that the cationic colloidal silica (B) is less likely to be dense and has good solubility in water when used as a coating solution. Alkenic acid is preferred, and undecylenic acid and its derivatives are particularly preferred wherein Y is hydrogen and X is alkylene having 8 carbon atoms.
ビニルエステル系単量体としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサチック酸ビニル等が挙げられる。なかでも、経済的な点から酢酸ビニルが好ましく用いられる。 Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, Examples include vinyl versatate. Of these, vinyl acetate is preferably used from the economical viewpoint.
また、本発明においては、上記の共重合成分以外にも本発明の目的を阻害せず、又、水溶性を維持する範囲において、他の単量体を０．１〜２０モル％程度共重合させることも可能で、例えばエチレンやプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、３−ブテン−１−オール、４−ペンテン−１−オール、５−ヘキセン−１−オール、３，４−ジヒドロキシ−１−ブテン等のヒドロキシ基含有α−オレフィン類およびそのアシル化物などの誘導体、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、ウンデシレン酸等の不飽和酸類、その塩、モノエステル、あるいはジアルキルエステル、アクリロニトリル、メタアクリロニトリル等のニトリル類、ジアセトンアクリルアミド、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸類あるいはその塩、アルキルビニルエーテル類、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、ビニルエチレンカーボネート、２，２−ジアルキル−４−ビニル−１，３−ジオキソラン、グリセリンモノアリルエーテル、等のビニル化合物、酢酸イソプロペニル、１−メトキシビニルアセテート等の置換酢酸ビニル類、塩化ビニリデン、１，４−ジアセトキシ−２−ブテン、１，４−ジヒドロキシ−２−ブテン、ビニレンカーボネート等が挙げられる。 Further, in the present invention, in addition to the above-mentioned copolymerization component, the purpose of the present invention is not hindered, and other monomers are copolymerized in an amount of about 0.1 to 20 mol% within the range of maintaining water solubility. For example, olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, 3-buten-1-ol, 4-penten-1-ol, 5-hexene-1 -Derivatives such as hydroxy group-containing α-olefins such as ol, 3,4-dihydroxy-1-butene and acylated products thereof, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid Unsaturated acids such as salts, monoesters, dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, diacetates Amides such as acrylamide, acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl Vinyl compounds such as ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerol monoallyl ether, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate, vinylidene chloride, 1, 4-diacetoxy-2-butene, 1,4-dihydroxy-2-butene, vinylene carbonate and the like can be mentioned.
また、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル等のポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等が挙げられる。 In addition, polyoxyalkylene (meth) allyl ether such as polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, polyoxyalkylene such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, etc. (Meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, Polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene Vinyl amine, and the like.
さらに、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドプロピルトリメチルアンモニウムクロライド、２−アクリロキシエチルトリメチルアンモニウムクロライド、２−メタクリロキシエチルトリメチルアンモニウムクロライド、２−ヒドロキシ−３−メタクリロイルオキシプロピルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、メタアリルトリメチルアンモニウムクロライド、３−ブテントリメチルアンモニウムクロライド、ジメチルジアリルアンモニウムクロライド、ジエチルジアリルアンモニウムクロライド等のカチオン基含有単量体、アセトアセチル基含有単量体、グリセリンモノアリルエーテル、酢酸イソプロペニル、１−メトキシビニルアセテート等も挙げられる。 Furthermore, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3- Cationic group-containing monomers such as methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, acetoacetyl group-containing monomers Glycerin monoallylate , Isopropenyl acetate, also 1-methoxy-vinyl acetate, and the like.
上記のビニルエステル系単量体と一般式（２）で示される化合物（さらには他の単量体）を共重合する方法及び得られた共重合体をケン化する方法としては、特に制限はなく、特開２００６−１５２２０６号公報等に記載されているような、公知の方法が用いられる。 The method for copolymerizing the above vinyl ester monomer and the compound represented by the general formula (2) (and other monomers) and the method for saponifying the obtained copolymer are not particularly limited. Instead, a known method as described in JP 2006-152206 A or the like is used.
かくして得られるカルボキシル基含有ＰＶＡ系樹脂（Ａ）の側鎖に存在するカルボキシル基含有長鎖アルキル基の含有量（すなわち変性度）は、通常０．１〜２０モル％であり、好ましくは０．５〜１０モル％、特に好ましくは１〜３モル％である。かかる変性度が大きすぎると、水溶液とした時の粘度が増加し、インク受容層を形成しにくくなったり、またはインク受容層にひび割れ等の欠点が生じる場合があり好ましくない。逆に変性度が小さすぎると、カルボキシル基含有長鎖アルキル基の数が少ないため、主鎖の水酸基によるカチオン性コロイダルシリカ（Ｂ）の密集を防ぎにくく、インクジェット用記録媒体とした時、目的の透明度が得られない可能性があるため好ましくない。 The content (that is, the degree of modification) of the carboxyl group-containing long chain alkyl group present in the side chain of the carboxyl group-containing PVA resin (A) thus obtained is usually from 0.1 to 20 mol%, and preferably from 0.8. 5 to 10 mol%, particularly preferably 1 to 3 mol%. If the degree of modification is too large, the viscosity of the aqueous solution increases, which makes it difficult to form the ink receiving layer, or may cause defects such as cracks in the ink receiving layer, which is not preferable. On the other hand, if the degree of modification is too small, the number of carboxyl group-containing long chain alkyl groups is small, so that it is difficult to prevent the cationic colloidal silica (B) from being crowded by the hydroxyl groups of the main chain. Since transparency may not be obtained, it is not preferable.
本発明におけるカルボキシル基含有ＰＶＡ系樹脂（Ａ）の平均重合度（ＪＩＳ Ｋ６７２６に準拠して測定。）は、通常１００〜４０００であり、好ましくは２００〜２０００、より好ましくは３００〜１２００である。平均重合度が大きすぎると、塗工液の粘度が高くなり、インク受容層を形成しにくく、また、塗工液がゲル化する場合があるため好ましくない。逆に平均重合度が小さすぎると、カルボキシル基含有ＰＶＡ系樹脂（Ａ）のバインダー力が低下し、インク受容層を乾燥させる際、インク受容層に亀裂が生じ易くなる場合があり好ましくない。 The average degree of polymerization (measured in accordance with JIS K6726) of the carboxyl group-containing PVA resin (A) in the present invention is usually 100 to 4000, preferably 200 to 2000, more preferably 300 to 1200. If the average degree of polymerization is too large, the viscosity of the coating liquid increases, it is difficult to form an ink receiving layer, and the coating liquid may be gelled, which is not preferable. On the other hand, if the average degree of polymerization is too small, the binder strength of the carboxyl group-containing PVA resin (A) decreases, and when the ink receiving layer is dried, the ink receiving layer may be easily cracked, which is not preferable.
また、かかるカルボキシル基含有ＰＶＡ系樹脂（Ａ）のケン化度は、通常、８０〜９９．９モル％、好ましくは９０〜９９．５モル％、特に好ましくは９６〜９９モル％である。ケン化度が低すぎると水溶性が低下し塗工液の調製が困難になる場合があるため好ましくない。 Moreover, the saponification degree of this carboxyl group-containing PVA-type resin (A) is 80-99.9 mol% normally, Preferably it is 90-99.5 mol%, Most preferably, it is 96-99 mol%. If the degree of saponification is too low, the water solubility is lowered and it may be difficult to prepare a coating solution.
［カチオン性コロイダルシリカ（Ｂ）］
カチオン性コロイダルシリカ（Ｂ）は、粒子表面にカチオン性種を有するコロイダルシリカで、その製造法としては、特開２００４−１１４４５９号公報に記載されているような、気相法シリカを、４級アンモニウム塩を含むカチオン性ポリマーやポリ塩化アルミニウムを含む溶媒中で高圧ホモジナイザーなどにより分散させる方法や、特開２００５−１６２５３３号公報や特開２００６−３２１９７８号公報に記載されているような、アルコキシシランやその誘導体などの加水分解可能なケイ素化合物を加水分解し、アルカリ触媒と反応させて得られたコロイダルシリカを酸性水溶液中で金属化合物やカチオン性シランカップリング剤などのカチオン種と反応させる方法が挙げられる。
[Cationic colloidal silica (B)]
Cationic colloidal silica (B) is colloidal silica having a cationic species on the particle surface. As a method for producing the colloidal silica (B), vapor phase silica as described in JP-A No. 2004-11459 is quaternary. A method of dispersing with a high-pressure homogenizer or the like in a solvent containing a cationic polymer containing ammonium salt or polyaluminum chloride, or an alkoxysilane as described in JP-A Nos. 2005-162533 and 2006-321978 And hydrolyzing a hydrolyzable silicon compound such as a derivative thereof and reacting with an alkali catalyst, colloidal silica obtained by reacting with a cationic species such as a metal compound or a cationic silane coupling agent in an acidic aqueous solution. Can be mentioned.
コロイダルシリカのカチオン種としては、ポリエチレンイミン、ポリジアリルアミン、ポリアリルアミン、アルキルアミン重合体等のカチオン性ポリマー、１〜３級アミノ基、４級アンモニウム塩基を有するポリマー、Ｎａ、Ｋ、Ｃａ、Ｍｇ、Ａｌ、Ｚｎ、Ｂａ、Ｓｒ又はＳｎからなる群から選択される金属の金属石鹸、水酸化物、塩または酸化物が挙げられるが、中でも、容易にカチオン性の高いコロイダルシリカを得ることができ、また、得られる記録媒体に印刷した時の画質が向上し、画像の耐水性を付与することができることからＡｌ又はその化合物が好ましい。これらのカチオン種は少なくとも1種以上含まれていれば良く、複数のものが併用されたものでも良い。 Examples of the cationic species of colloidal silica include cationic polymers such as polyethyleneimine, polydiallylamine, polyallylamine, and alkylamine polymers, polymers having primary to tertiary amino groups, and quaternary ammonium bases, Na, K, Ca, Mg, Examples include metal soaps, hydroxides, salts or oxides of metals selected from the group consisting of Al, Zn, Ba, Sr or Sn. Among them, it is possible to easily obtain highly cationic colloidal silica, In addition, Al or a compound thereof is preferable because image quality when printed on the obtained recording medium is improved and water resistance of the image can be imparted. It is sufficient that at least one of these cation species is contained, and a combination of a plurality of them may be used.
コロイダルシリカの一次粒子の平均粒子径は通常３〜２００ｎｍ以下であり、好ましくは１０〜１００ｎｍである。かかる平均粒子径が大きすぎるとかかるシリカを含有する塗工液で形成したインク受容層の平滑性と透明度が低下する場合があり好ましくなく、逆に小さすぎるとインク受容層中の空隙が小さくなり、インク吸収性が低下する場合があり好ましくない。 The average particle diameter of primary particles of colloidal silica is usually 3 to 200 nm or less, preferably 10 to 100 nm. If the average particle size is too large, the smoothness and transparency of the ink-receiving layer formed with such a silica-containing coating solution may be unfavorable. Conversely, if the average particle size is too small, the voids in the ink-receiving layer are reduced. Ink absorbability may decrease, which is not preferable.
分散溶媒としては、主に水が使用される。また、かかる溶媒は、カチオン性コロイダルシリカ（Ｂ）の分散性を向上させる点から、酸性溶媒であることが好ましく、塩酸、硫酸、硝酸等の無機酸が添加されていることが好ましい。 As a dispersion solvent, water is mainly used. In addition, the solvent is preferably an acidic solvent from the viewpoint of improving the dispersibility of the cationic colloidal silica (B), and is preferably added with an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid.
本願で用いるカチオン性コロイダルシリカ（Ｂ）の形状は、通常、平板状、繊維状、針状、球状、棒状等のいずれでも良く、インク吸収性の観点から、インク受容層中の空隙の表面積を大きくすることができる球状が好ましい。 The shape of the cationic colloidal silica (B) used in the present application may be any of a flat plate shape, a fiber shape, a needle shape, a spherical shape, a rod shape, etc., and from the viewpoint of ink absorbability, the surface area of the voids in the ink receiving layer is determined. A spherical shape that can be enlarged is preferred.
上記のカチオン性コロイダルシリカ（Ｂ）の市販品の例としては、ＷＲグレース社製ＬｕｄｏｘＣＬＰや日産化学社製スノーテックＡＫなどが挙げられる。 Examples of commercial products of the above-mentioned cationic colloidal silica (B) include Ludox CLP manufactured by WR Grace and Snowtech AK manufactured by Nissan Chemical.
本発明のインク受容層形成用塗工液は、カチオン性コロイダルシリカ（Ｂ）の他に、本発明の目的を阻害しない範囲であれば、インク吸収性の向上のため、必要に応じて他の微粒子を含んでいても良く、かかる微粒子としては、炭酸カルシウム、炭酸マグネシウム、カオリン、クレー、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、水酸化亜鉛、硫化亜鉛、炭酸亜鉛、ハイドロタルサイト、珪酸アルミニウム、珪酸マグネシウム、珪酸カルシウム、アルミナ、アルミナゾル、水酸化アルミニウム、ゼオライト、水酸化マグネシウム、酸化ジルコニウム、水酸化ジルコニウム、酸化セリウム等が挙げられ、これらを単独、または２種類以上組み合せて用いても良い。 In addition to the cationic colloidal silica (B), the coating liquid for forming the ink receiving layer of the present invention is not limited to the purpose of the present invention. Fine particles may be included, such as calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, hydrotalcite , Aluminum silicate, magnesium silicate, calcium silicate, alumina, alumina sol, aluminum hydroxide, zeolite, magnesium hydroxide, zirconium oxide, zirconium hydroxide, cerium oxide, etc., and these can be used alone or in combination of two or more. Also good.
［インク受容層形成用塗工液］
本発明の塗工液は、上述のカルボキシル基含有ＰＶＡ系樹脂（Ａ）、カチオン性コロイダルシリカ（Ｂ）を含有するものである。
[Ink-receiving layer-forming coating solution]
The coating liquid of the present invention contains the above-mentioned carboxyl group-containing PVA resin (A) and cationic colloidal silica (B).
塗工液中のカルボキシル基含有ＰＶＡ系樹脂（Ａ）とカチオン性コロイダルシリカ（Ｂ）の含有量比（Ａ／Ｂ）は、インク受容層に求められる特性に応じて適宜選定され、通常５／９５〜９５／５である。特に、本発明のインク受容層形成用塗工液はコロイダルシリカの分散性が高く、透明性に優れる受容層が得られることから、シリカの含有量が多い範囲、例えば（Ａ／Ｂ）が５／９５〜５０／５０の範囲が好適に用いられ、より好ましい範囲は８／９２〜３０／７０であり、さらに好ましい範囲は１０／９０〜２０／８０である。カルボキシル基含有ＰＶＡ系樹脂（Ａ）の含有量が少なすぎるとインク受容層表面にひび割れなどの欠点が生じる場合があり好ましくない。逆にカチオン性コロイダルシリカ（Ｂ）の含有量が少なすぎると、インク受容層中の空隙の量が減少し、インク吸収性が低下する場合があるため好ましくない。 The content ratio (A / B) of the carboxyl group-containing PVA resin (A) and the cationic colloidal silica (B) in the coating liquid is appropriately selected according to the characteristics required for the ink receiving layer, and is usually 5 / 95-95 / 5. In particular, the coating liquid for forming an ink receiving layer of the present invention provides a receiving layer having high dispersibility of colloidal silica and excellent transparency, so that the range with a high silica content, for example, (A / B) is 5 A range of / 95 to 50/50 is preferably used, a more preferred range is 8/92 to 30/70, and a further preferred range is 10/90 to 20/80. If the content of the carboxyl group-containing PVA-based resin (A) is too small, there may be defects such as cracks on the surface of the ink receiving layer, which is not preferable. Conversely, if the content of the cationic colloidal silica (B) is too small, the amount of voids in the ink receiving layer is decreased, and the ink absorbability may be lowered, which is not preferable.
また、塗工液中の固形分全体の濃度は、通常５〜３０重量％であり、好ましくは８〜２０重量％、特に好ましくは１０〜１５重量％である。かかる濃度が高すぎると、塗工液の粘度が上昇し、塗工する際、作業性が悪くなる場合があり好ましくなく、逆に低すぎると、水溶性樹脂及び無機微粒子の成分が少ないため、インク受容層のインク吸収性が低下する場合があるため好ましくない。 Moreover, the density | concentration of the whole solid content in a coating liquid is 5-30 weight% normally, Preferably it is 8-20 weight%, Most preferably, it is 10-15 weight%. If the concentration is too high, the viscosity of the coating liquid increases, and when coating, workability may be unfavorable. On the contrary, if it is too low, the components of the water-soluble resin and inorganic fine particles are small. This is not preferable because the ink absorbability of the ink receiving layer may be lowered.
本発明の塗工液の粘度（ＪＩＳ Ｋ７１１７−１に基づき、塗工液の温度２３℃の条件で、Ｂ８Ｌ型粘度計（東京計器社製）を用いて、測定粘度により適宜ローターナンバー及び回転数を変更して測定。）は、通常５〜１８００００ｍＰａ・Ｓであり、特には５０〜５００００ｍＰａ・Ｓであることが好ましく、更には１００〜１００００ｍＰａ・Ｓであることが好ましい。かかる粘度が高すぎると、形成したインク受容層の表面平滑性が悪くなる場合があり好ましくなく、逆に粘度が低すぎると、乾燥の際、インク受容層に風紋などの欠点が生じる場合があり好ましくない。 Viscosity of the coating liquid of the present invention (based on JIS K7117-1, using a B8L viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the condition of a coating liquid temperature of 23 ° C. Is usually 5 to 180000 mPa · S, particularly preferably 50 to 50000 mPa · S, and more preferably 100 to 10000 mPa · S. If the viscosity is too high, the surface smoothness of the formed ink-receiving layer may be deteriorated, which is not preferable. Conversely, if the viscosity is too low, defects such as wind ripples may occur in the ink-receiving layer during drying. It is not preferable.
本発明の塗工液は、特にゲルコート法による塗工に好適に用いることができるものである。ゲルコート法とは、塗工膜をゲル化させた後、乾燥してインク受容層を形成する方法である。ゲルコート法を用いると乾燥時に、熱風による波紋等の欠点ができにくくなり、光沢性が良好となる。この塗工膜をゲル化させる方法としては、例えば、塗工液中にホウ酸等の架橋剤を添加する方法や、塗工膜を形成後、加熱又は冷却する方法等が用いられている。しかしながら、架橋剤を用いると塗工液の安定性が低下し、ゲル化の制御も難しくなるという問題点がある。 Especially the coating liquid of this invention can be used suitably for the coating by a gel coat method. The gel coating method is a method of forming an ink receiving layer by gelling a coating film and then drying it. When the gel coat method is used, defects such as ripples caused by hot air are less likely to occur during drying, and glossiness is improved. As a method for gelling the coating film, for example, a method of adding a crosslinking agent such as boric acid in the coating liquid, a method of heating or cooling after forming the coating film, and the like are used. However, when a cross-linking agent is used, there is a problem that the stability of the coating solution is lowered and it is difficult to control gelation.
一方、塗工液が高粘度であると塗工膜をわずかな温度変化でゲル化することが可能であるが、通常、例えば未変性のＰＶＡ系樹脂などをバインダーとして用いた場合、シリカ濃度を高くすると、塗工液中のＰＶＡ系樹脂の含有量が少ないため、塗工液の固形分濃度を挙げたとしても、その粘度は上がり難く、ゲルコート法に適さないものである。しかし、本発明における塗工液では、カルボキシル基含有ＰＶＡ系樹脂（Ａ）のカルボキシル基含有長鎖アルキル基によりカルボキシル基含有ＰＶＡ系樹脂（Ａ）分子同士が絡み易く、シリカ濃度が高い場合においても塗工液の粘度が高く、さらに塗工液の固形分濃度を上げることにより、粘度を上昇させることができるため、ゲルコート法に適しているものである。 On the other hand, if the coating liquid has a high viscosity, the coating film can be gelled with a slight temperature change. Usually, for example, when an unmodified PVA resin or the like is used as a binder, the silica concentration is reduced. If it is increased, the content of the PVA resin in the coating solution is small, so even if the solid content concentration of the coating solution is given, its viscosity is difficult to increase and is not suitable for the gel coating method. However, in the coating liquid in the present invention, the carboxyl group-containing PVA resin (A) molecules are easily entangled by the carboxyl group-containing long chain alkyl group of the carboxyl group-containing PVA resin (A), and even when the silica concentration is high. Since the viscosity of the coating liquid is high and the viscosity can be increased by increasing the solid content concentration of the coating liquid, it is suitable for the gel coating method.
また、この塗工液は適度に高粘度であるため、塗工液を厚塗りすることができ、乾燥工程の際、さらに欠点ができにくくなる利点がある。また、記録媒体の端面付近のインク受容層が型崩れしにくく、紙面全体の厚みが均一となり、記録媒体は、均一なインク吸収性を持つものになる。また、通常より膜を厚くすることができるためインク吸収性を向上させることも可能であるため、さらに画像鮮明度を向上させることができる。 Moreover, since this coating liquid is moderately high-viscosity, the coating liquid can be applied thickly, and there is an advantage that defects are less likely to occur during the drying process. In addition, the ink receiving layer near the end face of the recording medium is not easily deformed, the thickness of the entire paper surface becomes uniform, and the recording medium has uniform ink absorbability. In addition, since the film can be made thicker than usual, it is possible to improve the ink absorbency, so that the image definition can be further improved.
なお、かかる塗工液の粘度は、塗工液中の固形分濃度により粘度調整することも可能であり、例えば、塗工液の粘度が高すぎる場合、加水することにより、適度な粘度範囲まで減粘することができる。また、カルボキシル基含有ＰＶＡ系樹脂（Ａ）の構造により調製することも可能であり、かかる場合の一例として、カルボキシル基含有ＰＶＡ系樹脂（Ａ）の重合度を変える方法が挙げられる。 The viscosity of the coating liquid can be adjusted by the solid content concentration in the coating liquid. For example, when the viscosity of the coating liquid is too high, by adding water, the viscosity can be adjusted to an appropriate viscosity range. Can reduce viscosity. Moreover, it is also possible to prepare by the structure of carboxyl group-containing PVA resin (A), and an example of such a case is a method of changing the degree of polymerization of the carboxyl group-containing PVA resin (A).
また、本発明の塗工液は、カルボキシル基含有ＰＶＡ系樹脂（Ａ）を含有しているため、塗工液のｐＨを変更することにより、粘度調整することも可能である。カルボキシル基含有ＰＶＡ系樹脂（Ａ）が側鎖に有するカルボキシル基の等電点に塗工液のｐＨを調整すると、カルボキシル基含有長鎖アルキル基の電荷が低下するため、カルボキシル基含有ＰＶＡ系樹脂（Ａ）分子同士の電気的反発が小さくなり、お互いが絡み易くなるため、塗工液の粘度が上昇する。かかるｐＨは、カルボキシル基含有ＰＶＡ系樹脂（Ａ）の構造やカルボキシル基含有アルキル基の変性量に左右されるが、通常、２〜６であり、特に３〜５であることが好ましい。 Moreover, since the coating liquid of this invention contains carboxyl group-containing PVA-type resin (A), it is also possible to adjust a viscosity by changing the pH of a coating liquid. When the pH of the coating liquid is adjusted to the isoelectric point of the carboxyl group in the side chain of the carboxyl group-containing PVA resin (A), the charge of the carboxyl group-containing long chain alkyl group decreases, so the carboxyl group-containing PVA resin (A) Since the electrical repulsion between molecules is reduced and the molecules are easily entangled with each other, the viscosity of the coating liquid is increased. Such pH depends on the structure of the carboxyl group-containing PVA resin (A) and the amount of modification of the carboxyl group-containing alkyl group, but is usually 2 to 6, and particularly preferably 3 to 5.
なお、本発明の塗工液は、特に架橋剤や増粘剤を添加しなくても粘度調製が容易なものであるが、必要であれば、本発明の目的が阻害されない範囲で併用しても良い。かかる架橋剤としては、例えば、ホウ素化合物、ホルムアルデヒド、アセトアルデヒド、グリオキザール、グルタルジアルデヒド等のアルデヒド化合物、尿素樹脂、グアナミン樹脂、メラミン樹脂等のアミノ樹脂、エポキシ樹脂、ポリアミドポリアミンエピクロルヒドリン等のエポキシ系化合物、アジピン酸ジヒドラジド、カルボジヒドラジド、ポリアクリル酸ヒドラジド等のヒドラジド系化合物、酸無水物、ポリエソシアネート、ブロックイソシアネート等のイソシアネート化合物などの有機系架橋剤、テトラアルコキシチタネート等のチタン化合物、硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウム等のアルミニウム化合物、亜リン酸エステル、ビスフェノールA変性ポリリン酸等のリン化合物、アルコキシ変性シリコーン、グリシジル変性シリコーン等の変性シリコーン、クロロヒドロキシオキソジルコニウム、硝酸ジルコニウム、硝酸ジルコニル等のジルコニウム化合物などの無機系架橋剤が挙げられる。 The coating liquid of the present invention can be easily prepared without adding a crosslinking agent or thickener, but if necessary, it can be used in combination as long as the object of the present invention is not impaired. Also good. Examples of such crosslinking agents include boron compounds, aldehyde compounds such as formaldehyde, acetaldehyde, glyoxal and glutardialdehyde, amino resins such as urea resins, guanamine resins and melamine resins, epoxy compounds such as epoxy resins and polyamide polyamine epichlorohydrin, Hydrazide compounds such as adipic acid dihydrazide, carbodihydrazide, polyacrylic acid hydrazide, organic crosslinking agents such as isocyanate compounds such as acid anhydrides, polyesocyanates and block isocyanates, titanium compounds such as tetraalkoxy titanates, aluminum sulfate, chloride Aluminum compounds such as aluminum and aluminum nitrate, phosphorus compounds such as phosphites and bisphenol A-modified polyphosphoric acid, alkoxy-modified silicones, Inorganic crosslinking agents such as modified silicones such as sidyl-modified silicones and zirconium compounds such as chlorohydroxyoxozirconium, zirconium nitrate and zirconyl nitrate.
さらに、本発明のインク受容層用塗工液には、本発明の目的が阻害されない範囲で、顔料分散剤、流動性改良剤、界面活性剤、消泡剤、離型剤、浸透剤、染料、顔料、蛍光増白剤、紫外線吸収剤、酸化防止剤、防腐剤、紙力増強剤などを配合しても良い。 Furthermore, the coating liquid for the ink receiving layer of the present invention includes a pigment dispersant, a fluidity improver, a surfactant, an antifoaming agent, a release agent, a penetrating agent, and a dye as long as the object of the present invention is not impaired. , Pigments, fluorescent brighteners, ultraviolet absorbers, antioxidants, preservatives, paper strength enhancers, and the like may be incorporated.
塗工液の製造方法は、例えば、カルボキシル基含有ＰＶＡ系樹脂（Ａ）及びカチオン性コロイダルシリカ（Ｂ）を配合した後、カチオン性コロイダルシリカ（Ｂ）を分散させるため混合する方法が挙げられる。塗工液の配合方法としては、通常、カルボキシル基含有ＰＶＡ系樹脂（Ａ）の水溶液とカチオン性コロイダルシリカ（Ｂ）の分散液を混合するか、カチオン性コロイダルシリカ（Ｂ）の分散液にカルボキシル基含有ＰＶＡ系樹脂（Ａ）を加え、攪拌溶解する方法がある。また、混合方法としては、通常のプロペラ攪拌、タービン型攪拌、ホモミキサー型攪拌等で予備混練し、次にボールミル、ビーズミル、サンドグラインダー等のメディアミル、高圧ホモジナイザー、超高圧ホモジナイザー等の圧力式分散機、超音波分散機、及び薄膜旋回型分散機等を使用して、固形成分が均一に分散するように混合する方法等がある。 Examples of the method for producing the coating liquid include a method in which the carboxyl group-containing PVA resin (A) and the cationic colloidal silica (B) are mixed and then mixed to disperse the cationic colloidal silica (B). As a blending method of the coating liquid, usually, an aqueous solution of a carboxyl group-containing PVA resin (A) and a dispersion of cationic colloidal silica (B) are mixed, or a dispersion of cationic colloidal silica (B) is carboxylated. There is a method in which the group-containing PVA resin (A) is added and dissolved by stirring. In addition, as a mixing method, pre-kneading with ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc., then pressure type dispersion such as media mill such as ball mill, bead mill, sand grinder, high pressure homogenizer, ultra high pressure homogenizer, etc. And a method of mixing so that the solid components are uniformly dispersed using a pulverizer, an ultrasonic disperser, a thin film swirl disperser, and the like.
［インクジェット用記録媒体］
本発明のインクジェット用記録媒体は、支持体上に、本発明のインク受容層形成用塗工液を塗工、乾燥して、インク受容層を形成することにより製造されるものである。
[Inkjet recording medium]
The ink jet recording medium of the present invention is produced by coating the ink receiving layer forming coating liquid of the present invention on a support and drying to form an ink receiving layer.
本発明の記録媒体に使用できる支持体としては、特に制限されるものではないが、例えば、紙（マニラボール、白ボール、ライナー等の板紙、一般上質紙、中質紙、グラビア用紙等の印刷用紙、上・中・下級紙、新聞用紙、剥離紙、カーボン紙、ノンカーボン紙、グラシン紙など）、樹脂コート紙、合成紙、不織布、布、金属箔、ポリオレフィン樹脂（例えばポリエチレン、ＰＥＴ、ポリプロピレン、ポリ塩化ビニル、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体）等の熱可塑性樹脂からなるフィルムやシート、ポリカーボネート系樹脂やポリエステル系樹脂を主成分とするプラスチック板やディスクなどが使用できる。 The support that can be used in the recording medium of the present invention is not particularly limited. For example, printing of paper (manila balls, white balls, liners and other paperboard, general fine paper, medium paper, gravure paper, etc.) Paper, upper / middle / lower grade paper, newsprint, release paper, carbon paper, non-carbon paper, glassine paper, etc.), resin-coated paper, synthetic paper, non-woven fabric, cloth, metal foil, polyolefin resin (eg, polyethylene, PET, polypropylene) , Polyvinyl chloride, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer) and other plastic films and sheets made of thermoplastic resin such as polycarbonate resin or polyester resin. it can.
支持体上に塗布液を塗布してインク受容層を形成する方法としては、バーコーター法、エアナイフコーター法、ブレードコーター法、カーテンコーター法などの公知の塗工方法が用いられる。 As a method for forming an ink receiving layer by applying a coating solution on a support, known coating methods such as a bar coater method, an air knife coater method, a blade coater method, and a curtain coater method are used.
塗工液の塗布量は、所望するインク受容層の厚さや支持体の種類などによって異なるため、一概には言えないが、通常、乾燥後のインク受容層の厚さが３〜１００μｍ、さらには６〜５０μｍ、特には１０〜３０μｍとなるような塗布量で塗布することが好ましい。
また、ゲルコート法により形成する場合、乾燥後のインク受容層の厚みは、通常、２０〜８０μｍであり、特に３０〜７０μｍであることが好ましく、更には２０〜５０μｍであることが好ましい。
Since the coating amount of the coating liquid varies depending on the desired thickness of the ink receiving layer and the type of the support, it cannot be generally stated. Usually, however, the thickness of the ink receiving layer after drying is 3 to 100 μm, It is preferable to apply at an application amount of 6 to 50 μm, particularly 10 to 30 μm.
Moreover, when forming by a gel coat method, the thickness of the ink receiving layer after drying is usually 20 to 80 μm, particularly preferably 30 to 70 μm, and further preferably 20 to 50 μm.
支持体上に塗布液を塗布した後の乾燥条件としては特に制限されないが、通常５０〜１００℃で１〜３０分程度乾燥させればよい。
また、乾燥前の湿潤状態で、あるいは一旦乾燥させた後に再び湿潤させて湿潤状態とし、インク受容層表面をキャストドラムに圧接して乾燥させることで、表面光沢性・平滑性を付与する方法も、好ましく用いられる。
Although it does not restrict | limit especially as drying conditions after apply | coating a coating liquid on a support body, What is necessary is just to dry normally for about 1 to 30 minutes at 50-100 degreeC.
Also, there is a method of imparting surface glossiness and smoothness by wetting before drying or by once again drying and then moistening again to make a wet state and pressing the surface of the ink receiving layer against a cast drum and drying. Are preferably used.
かかるインク受容層には、本発明の目的が阻害されない範囲で、カルボキシル基含有ＰＶＡ系樹脂（Ａ）とは別の水溶性、水分散性樹脂を含有しても良い。例えば、デンプン、酸化デンプン、カチオン変性デンプン等のデンプン誘導体、ゼラチン、カゼイン、等の天然系たんぱく質類、メチルセルロース、ヒドロキシエチルセルロース、カルボキシルメチルセルロース等のセルロース誘導体、アルギン酸ナトリウム、ペクチン酸塩などの水溶性樹脂、ＳＢＲラテックス、ＮＢＲラテックス、酢酸ビニル系樹脂系エマルジョン、エチレン−酢酸ビニル共重合体エマルジョン、ウレタン樹脂系エマルジョンなどが挙げられる。 Such an ink receiving layer may contain a water-soluble and water-dispersible resin different from the carboxyl group-containing PVA resin (A) as long as the object of the present invention is not impaired. For example, starch derivatives such as starch, oxidized starch, and cation-modified starch, natural proteins such as gelatin and casein, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, water-soluble resins such as sodium alginate and pectate, Examples thereof include SBR latex, NBR latex, vinyl acetate resin emulsion, ethylene-vinyl acetate copolymer emulsion, urethane resin emulsion and the like.
また、インク受容層には、本発明の目的が阻害されない範囲で、アニオン性染料インクの定着剤としてカチオン性樹脂を併用しても良い。かかるカチオン性樹脂としては、例えば、ポリエチレンポリアミン、ポリプロピレンポリアミンなどのポリアルキレンポリアミン類またはその誘導体、第２級アミノ基、第３級アミノ基や第４級アンモニウム塩を有するアクリル重合体、ポリビニルアミン共重合体、ポリビニルアミジン共重合体、ジシアンジアミド・ホルマリン共重合体、ジメチルアミン・エピクロルヒドリン共重合体、アクリルアミド・ジアリルアミン共重合体、ジアリルジメチルアンモニウムクロライド共重合体などが挙げられる。 In the ink receiving layer, a cationic resin may be used in combination as a fixing agent for the anionic dye ink as long as the object of the present invention is not impaired. Examples of such cationic resins include polyalkylene polyamines such as polyethylene polyamine and polypropylene polyamine or derivatives thereof, acrylic polymers having secondary amino groups, tertiary amino groups, and quaternary ammonium salts, and polyvinylamine copolymers. Examples thereof include a polymer, a polyvinylamidine copolymer, a dicyandiamide / formalin copolymer, a dimethylamine / epichlorohydrin copolymer, an acrylamide / diallylamine copolymer, and a diallyldimethylammonium chloride copolymer.
また、本発明のインクジェット用記録媒体には、公知の光沢層がインク受容層上に塗工されていても良い。インク受容層にかかる光沢層を塗工する場合、その乾燥後の膜厚は、特に制限されないが、通常２〜１０μｍ、好ましくは３〜５μｍである。 In the ink jet recording medium of the present invention, a known gloss layer may be coated on the ink receiving layer. When the gloss layer applied to the ink receiving layer is applied, the film thickness after drying is not particularly limited, but is usually 2 to 10 μm, preferably 3 to 5 μm.
本発明のインクジェット用記録媒体は、透明性が優れているものである。また、インク受容層中のシリカ濃度を高くすることが可能であり、インク吸収性に優れ、印字の鮮明性、発色性が良いインクジェット用記録媒体が得られる。 The inkjet recording medium of the present invention is excellent in transparency. Further, it is possible to increase the silica concentration in the ink receiving layer, and it is possible to obtain an ink jet recording medium having excellent ink absorbability, good print sharpness, and good color development.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はその要旨を超えない限り、実施例の記載に限定されるものではない。
また、例中「部」、「％」とあるのは、断りのない限り重量基準を意味する。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to description of an Example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.
実施例１
〔カルボキシル基含有ＰＶＡ系樹脂（Ａ）の製造〕
還流冷却器、滴下漏斗、撹拌機を備えた反応缶に、酢酸ビニル１０００部、メタノール３００部、ウンデシレン酸４２．８１部（酢酸ビニルに対して２モル％）を仕込み、アゾビスイソブチロニトリルを０．２モル％（対仕込み酢酸ビニル）投入し、撹拌しながら窒素気流下で温度を上昇させ重合を行った。重合を開始して３時間後に、更にアゾビスイソブチロニトリル０．１モル％（対初期の仕込み酢酸ビニル）を添加し、更に重合を続けた。その後、酢酸ビニルの重合率が７０％となった時点で、重合禁止剤を仕込み、重合を終了した。続いて、メタノール蒸気を吹き込む方法により未反応の酢酸ビニル単量体を系外に除去して、共重合体のメタノール溶液を得た。
Example 1
[Production of carboxyl group-containing PVA resin (A)]
A reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 1000 parts of vinyl acetate, 300 parts of methanol, and 42.81 parts of undecylenic acid (2 mol% based on vinyl acetate), and azobisisobutyronitrile. Was added in an amount of 0.2 mol% (compared with vinyl acetate), and polymerization was carried out by increasing the temperature under a nitrogen stream while stirring. Three hours after the start of the polymerization, 0.1 mol% of azobisisobutyronitrile (vs. initial vinyl acetate) was added, and the polymerization was further continued. Thereafter, when the polymerization rate of vinyl acetate reached 70%, a polymerization inhibitor was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed from the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
次いで、該溶液をメタノールで希釈し、濃度４０％に調整してニーダーに仕込み、溶液温度を４０℃に保ちながら、水酸化ナトリウムの２％メタノール溶液を共重合体中の酢酸ビニル１モルに対して４５ミリモルとなるように加えてケン化を行った。ケン化が進行すると共にケン化物が析出し、遂には粒子状となった。生成したＰＶＡ系樹脂を濾別し、メタノールでよく洗浄して熱風乾燥機中で乾燥し、カルボキシル基含有ＰＶＡ系樹脂（Ａ）を得た。 Next, the solution was diluted with methanol, adjusted to a concentration of 40%, charged into a kneader, and while maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to 1 mol of vinyl acetate in the copolymer. And saponification was carried out. Saponification progressed as saponification progressed, and finally became particulate. The produced PVA resin was filtered off, washed well with methanol, and dried in a hot air dryer to obtain a carboxyl group-containing PVA resin (A).
得られたカルボキシル基含有ＰＶＡ系樹脂（Ａ）のケン化度は、残存酢酸ビニル単位の加水分解に要するアルカリ消費量で分析を行ったところ、９８．９モル％であり、平均重合度は、ＪＩＳ Ｋ６７２６に準じて測定したところ９００であり、温度２３℃における４％水溶液粘度はＪＩＳ Ｋ７１１７−１に基づき、Ｂ８Ｌ型粘度計（東京計器社製）により測定した結果、８．１ｍＰａ・ｓであった。また、カルボキシル基含有ＰＶＡ系樹脂（Ａ）の変性量は１Ｈ−ＮＭＲ測定（「Ｕｎｉｔｙ３００」Ｖａｒｉａｎ社製、共鳴周波数：３００ＭＨｚ、内部標準物質：テトラメチルシラン、溶媒：ＤＭＳＯ−ｄ６、温度：５０℃）より算出したところ２モル％であった。 The saponification degree of the obtained carboxyl group-containing PVA resin (A) was 98.9 mol% when analyzed by the alkali consumption required for hydrolysis of the remaining vinyl acetate units, and the average polymerization degree was It was 900 when measured according to JIS K6726, and the viscosity of a 4% aqueous solution at a temperature of 23 ° C. was 8.1 mPa · s as a result of measurement with a B8L viscometer (manufactured by Tokyo Keiki Co., Ltd.) based on JIS K7117-1. It was. The modification amount of the carboxyl group-containing PVA resin (A) was 1 H-NMR measurement (“Unity 300”, manufactured by Varian, resonance frequency: 300 MHz, internal standard substance: tetramethylsilane, solvent: DMSO-d6, temperature: 50 It was 2 mol% when computed from (degreeC).
得られたカルボキシル基含有ＰＶＡ系樹脂（Ａ）の１Ｈ−ＮＭＲのスペクトルの帰属は以下の通りであった。
［１Ｈ−ＮＭＲ］
１．２１〜１．２３ｐｐｍ：メチレンプロトン（変性種に起因）
１．３５〜１．５８ｐｐｍ：メチレンプロトン
１．８６〜１．９２ｐｐｍ：メチレンプロトン（変性種に起因）
３．８１〜３．８５ｐｐｍ：メチンプロトン
４．１３〜４．７８ｐｐｍ：水酸基
The attribution of the spectrum of 1 H-NMR of the obtained carboxyl group-containing PVA resin (A) was as follows.
[1H-NMR]
1.21-1.23 ppm: Methylene proton (due to modified species)
1.35 to 1.58 ppm: methylene proton 1.86 to 1.92 ppm: methylene proton (due to modified species)
3.81 to 3.85 ppm: Methine proton 4.13 to 4.78 ppm: Hydroxyl group
［インク受容層形成用塗工液調製］
カルボキシル基含有ＰＶＡ系樹脂（Ａ）１５％水溶液及びカチオン性コロイダルシリカ（Ｂ）（商品名「ＬｕｄｏｘＣＬ−Ｐ」、ＷＲグレース社製）１５％水分散液を、塗工液中の含有量比（カルボキシル基含有ＰＶＡ系樹脂（Ａ）／カチオン性コロイダルシリカ（Ｂ））が１０／９０になるように加え、ホモジナイザー（特殊機化工業社製Ｔ.Ｋ.ＲＯＢＯＭＩＣＳ、回転数５０００ｒｐｍ）にて５分間混合してインク受容層用塗工液とした。得られた塗工液のｐＨは３．９であった。
[Preparation of coating solution for forming ink receiving layer]
Carboxyl group-containing PVA-based resin (A) 15% aqueous solution and cationic colloidal silica (B) (trade name “LudoxCL-P”, manufactured by WR Grace Co., Ltd.) 15% aqueous dispersion, the content ratio ( Add the carboxyl group-containing PVA resin (A) / cationic colloidal silica (B) to 10/90, and use a homogenizer (T.K. ROBOMICS, revolution speed 5000 rpm manufactured by Tokushu Kika Kogyo Co., Ltd.) for 5 minutes. It mixed and it was set as the coating liquid for ink receiving layers. The resulting coating solution had a pH of 3.9.
［粘度測定方法］
上記で得られた塗工液を室温で１日放置したものサンプルとし、ＪＩＳ Ｋ７１１７−１に基づき、塗工液の温度２３℃で、Ｂ８Ｌ型粘度計（東京計器社製）を用いて、Ｂ８Ｌ型粘度計（東京計器社製）にて測定した。測定結果を表２に記載した。
[Viscosity measurement method]
The coating liquid obtained above was left as a sample at room temperature for 1 day, and based on JIS K7117-1, using a B8L viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a coating liquid temperature of 23 ° C., B8L It measured with the type | mold viscosity meter (made by Tokyo Keiki Co., Ltd.). The measurement results are shown in Table 2.
［インクジェット用記録媒体の製造］
上記で得られた塗工液をＰＥＴ上に５０μｍのアプリケーターにて塗工し、その後、温度６０℃で５分間乾燥し、記録媒体とした。
[Manufacture of inkjet recording media]
The coating solution obtained above was coated on PET with a 50 μm applicator and then dried at a temperature of 60 ° C. for 5 minutes to obtain a recording medium.
［ヘイズ測定方法］
上記で得られた記録媒体をヘイズメーターＮＤＨ２０００（日本電飾社製）にて、測定回数ｎ＝９で測定し、その平均値を測定結果とした。測定結果を表２に記載した。
[Haze measurement method]
The recording medium obtained above was measured with a haze meter NDH2000 (manufactured by Nippon Denka Co., Ltd.) with the number of measurements n = 9, and the average value was taken as the measurement result. The measurement results are shown in Table 2.
実施例２
塗工液調製の際、塗工液中の含有量比（カルボキシル基含有ＰＶＡ系樹脂（Ａ）／カチオン性コロイダルシリカ（Ｂ））を２０／８０とした以外は実施例１と同様にして、塗工液及び記録媒体を得た。得られた塗工液のｐＨは４．０であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果を表２に記載した。
Example 2
When preparing the coating liquid, the same as in Example 1, except that the content ratio in the coating liquid (carboxyl group-containing PVA resin (A) / cationic colloidal silica (B)) was 20/80, A coating liquid and a recording medium were obtained. The resulting coating solution had a pH of 4.0. Table 2 shows the measurement results of the viscosity of the coating liquid and the haze of the recording medium.
実施例３
塗工液調製の際、塗工液中の含有量比（カルボキシル基含有ＰＶＡ系樹脂（Ａ）／カチオン性コロイダルシリカ（Ｂ））を２５／７５とした以外は実施例１と同様にして、塗工液及び記録媒体を得た。得られた塗工液のｐＨは４．１であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果を表２に記載した。
Example 3
When preparing the coating liquid, the same as in Example 1, except that the content ratio in the coating liquid (carboxyl group-containing PVA resin (A) / cationic colloidal silica (B)) was 25/75, A coating liquid and a recording medium were obtained. The resulting coating solution had a pH of 4.1. Table 2 shows the measurement results of the viscosity of the coating liquid and the haze of the recording medium.
実施例４
塗工液調製の際、塗工液中の含有量比（カルボキシル基含有ＰＶＡ系樹脂（Ａ）／カチオン性コロイダルシリカ（Ｂ））を３０／７０とした以外は実施例１と同様にして、塗工液及び記録媒体を得た。かかる塗工液のｐＨは４．０であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果は表２に記載した。
Example 4
When preparing the coating liquid, the same as in Example 1, except that the content ratio in the coating liquid (carboxyl group-containing PVA resin (A) / cationic colloidal silica (B)) was 30/70. A coating liquid and a recording medium were obtained. The pH of this coating solution was 4.0. The measurement results of the viscosity of the coating liquid and the haze of the recording medium are shown in Table 2.
比較例１
［未変性ＰＶＡ系樹脂の製造］
実施例１において、ウンデシレン酸を仕込まず、酢酸ビニルのみを重合（Ｓ／Ｍ＝０．５、Ｓ：メタノール、Ｍ：酢酸ビニル）し、ケン化を行った以外は同様に行い、未変性ＰＶＡ系樹脂を得た。
得られた未変性ＰＶＡ系樹脂のケン化度は、酢酸ビニル単位の加水分解に要するアルカリ消費量で分析を行ったところ、９８．１モル％であり、平均重合度はＪＩＳ Ｋ６７２６に準じて測定したところ８１０であり、温度２３℃における４％水溶液粘度は、ＪＩＳ Ｋ７１１７−１に基づき、Ｂ８Ｌ型粘度計（東京計器社製）で測定した結果、７．６ｍＰａ・ｓであった。
Comparative Example 1
[Production of unmodified PVA resin]
In Example 1, undecylenic acid was not charged, but only vinyl acetate was polymerized (S / M = 0.5, S: methanol, M: vinyl acetate), and saponification was performed in the same manner, unmodified PVA A system resin was obtained.
The degree of saponification of the resulting unmodified PVA resin was 98.1 mol% when analyzed by the alkali consumption required for hydrolysis of vinyl acetate units, and the average degree of polymerization was measured according to JIS K6726. As a result, the viscosity of the 4% aqueous solution at 23 ° C. was 7.6 mPa · s as a result of measurement with a B8L viscometer (manufactured by Tokyo Keiki Co., Ltd.) based on JIS K7117-1.
得られた未変性ＰＶＡ系樹脂を用いた以外は実施例２と同様にして塗工液及び記録媒体を得た。かかる塗工液のｐＨは４．１であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果は表２に記載した。 A coating liquid and a recording medium were obtained in the same manner as in Example 2 except that the obtained unmodified PVA resin was used. The pH of this coating solution was 4.1. The measurement results of the viscosity of the coating liquid and the haze of the recording medium are shown in Table 2.
比較例２
塗工液調製の際、未変性ＰＶＡ系樹脂を用いた以外は実施例３と同様にして塗工液及び記録媒体を得た。かかる塗工液のｐＨは４．１であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果は表２に記載した。
Comparative Example 2
When preparing the coating liquid, a coating liquid and a recording medium were obtained in the same manner as in Example 3 except that the unmodified PVA resin was used. The pH of this coating solution was 4.1. The measurement results of the viscosity of the coating liquid and the haze of the recording medium are shown in Table 2.
比較例３
［マレイン酸変性ＰＶＡ系樹脂の製造］
重合缶に酢酸ビニル９５部、マレイン酸１．９部（酢酸ビニルに対して２モル％）、メタノール４０部を仕込んで、系内を撹拌下、窒素気流中で昇温して６８℃で３０分間還流後、アゾビスイソブチロニトリルを酢酸ビニルに対して０．２モル％加え、マレイン酸のメタノール溶液を仕込み変性度が２．０モル％になるように滴下して６時間重合を行って反応終了後メタノール蒸気を吹き込んで未反応のモノマーを除去し、共重合体のメタノール溶液を得た。次いで、得られたメタノール溶液を４０％になるようにメタノールで希釈した。更に共重合体中の酢酸ビニルに対して水酸化ナトリウムを４０ミリモル％加えてケン化して、得られたケン化物を濾過し、７０℃で乾燥してマレイン酸変性ＰＶＡ系樹脂を得た。
得られたマレイン酸変性ＰＶＡ系樹脂のケン化度は、酢酸ビニル単位の加水分解に要するアルカリ消費量で分析を行ったところ、９９．３モル％であり、平均重合度はＪＩＳ Ｋ６７２６に準じて測定したところ１２００であり、温度２３℃における４％水溶液粘度は、ＪＩＳ Ｋ７１１７−１に基づき、Ｂ８Ｌ型粘度計（東京計器社製）を用いて測定した結果、１４．７ｍＰａ・ｓであった。
Comparative Example 3
[Production of maleic acid-modified PVA resin]
A polymerization can was charged with 95 parts of vinyl acetate, 1.9 parts of maleic acid (2 mol% with respect to vinyl acetate), and 40 parts of methanol. After refluxing for 5 minutes, 0.2 mol% of azobisisobutyronitrile was added to vinyl acetate, and a methanol solution of maleic acid was added dropwise so that the degree of modification was 2.0 mol%, followed by polymerization for 6 hours. After completion of the reaction, methanol vapor was blown to remove unreacted monomers to obtain a methanol solution of the copolymer. Subsequently, the obtained methanol solution was diluted with methanol so that it might become 40%. Furthermore, 40 mmol% of sodium hydroxide was added to vinyl acetate in the copolymer to saponify, and the resulting saponified product was filtered and dried at 70 ° C. to obtain a maleic acid-modified PVA resin.
The degree of saponification of the obtained maleic acid-modified PVA resin was 99.3 mol% when analyzed by the alkali consumption required for hydrolysis of vinyl acetate units, and the average degree of polymerization was in accordance with JIS K6726. It was 1200 when measured, and the viscosity of a 4% aqueous solution at a temperature of 23 ° C. was 14.7 mPa · s as a result of measurement using a B8L viscometer (manufactured by Tokyo Keiki Co., Ltd.) based on JIS K7117-1.
塗工液調製の際、マレイン酸変性ＰＶＡ系樹脂を用いた以外は実施例２と同様にして、塗工液及び記録媒体を得た。得られた塗工液のｐＨは４．３であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果を表２に記載した。 A coating liquid and a recording medium were obtained in the same manner as in Example 2 except that a maleic acid-modified PVA resin was used when preparing the coating liquid. The resulting coating solution had a pH of 4.3. Table 2 shows the measurement results of the viscosity of the coating liquid and the haze of the recording medium.
比較例４
塗工液調製の際、カチオン性コロイダルシリカ（Ｂ）のかわりにアニオン性コロイダルシリカ（商品名「ＬｕｄｏｘＡＳ−４０」、ＷＲグレース社製）を用いた以外は実施例２と同様にして、塗工液及び記録媒体を得た。得られた塗工液のｐＨは９．３であった。また、塗工液の粘度及び記録媒体のヘイズの測定結果を表２に記載した。
Comparative Example 4
Coating was carried out in the same manner as in Example 2 except that anionic colloidal silica (trade name “LudoxAS-40”, manufactured by WR Grace) was used instead of cationic colloidal silica (B) during the preparation of the coating liquid. A liquid and a recording medium were obtained. The resulting coating solution had a pH of 9.3. Table 2 shows the measurement results of the viscosity of the coating liquid and the haze of the recording medium.
カルボキシル基含有長鎖アルキル基を有するカルボキシル基含有ＰＶＡ系樹脂（Ａ）とカチオン性コロイダルシリカ（Ｂ）を含有する実施例１〜４の条件で得られた記録媒体のヘイズ値は、未変性ＰＶＡ系樹脂とカチオン性コロイダルシリカ（Ｂ）を用いた比較例１，２の条件で得られた記録媒体のヘイズ値、主鎖にカルボキシル基を有するマレイン酸変性ＰＶＡ系樹脂とカチオン性コロイダルシリカ（Ｂ）を用いた比較例３の条件で得られた記録媒体のヘイズ値及びカルボキシル基含有ＰＶＡ系樹脂（Ａ）とアニオン性コロイダルシリカを用いた比較例４の条件で得られた記録媒体のヘイズ値より小さく、かかる組み合わせの記録媒体は優れた透明性を有するものである。 The haze value of the recording medium obtained under the conditions of Examples 1 to 4 containing the carboxyl group-containing PVA resin (A) having a carboxyl group-containing long chain alkyl group and the cationic colloidal silica (B) is unmodified PVA. Haze value of the recording medium obtained under the conditions of Comparative Examples 1 and 2 using a base resin and a cationic colloidal silica (B), a maleic acid-modified PVA resin having a carboxyl group in the main chain and a cationic colloidal silica (B ) And the haze value of the recording medium obtained under the conditions of Comparative Example 4 using the carboxyl group-containing PVA resin (A) and anionic colloidal silica. Smaller, such a combination of recording media has excellent transparency.
上述した通り、本発明のインクジェット用記録媒体は、優れた透明性を有するものであり、特に、カチオン性コロイダルシリカ（Ｂ）の含有量比が高いほど、優れた透明性を示すものである。また優れたインク吸収性を有することが期待できるため、優れた画像鮮明性が得られることが予想され、各種印刷用紙に適用でき、特に診察用写真などの高解像度の画像を印刷するための用紙として好適である。 As described above, the inkjet recording medium of the present invention has excellent transparency. In particular, the higher the content ratio of the cationic colloidal silica (B), the better the transparency. In addition, since it can be expected to have excellent ink absorptivity, it is expected that excellent image sharpness can be obtained, and it can be applied to various printing papers, especially for printing high-resolution images such as diagnostic photographs. It is suitable as.
Claims (4)
（式中、Ｒ1、Ｒ2、Ｒ3は、それぞれ独立して水素原子又はアルキル基を示し、Ｘは炭素数が４〜５０のアルキレンを示し、Ｙは水素原子又はアルカリ金属を示す。） A coating solution containing a carboxyl group-containing polyvinyl alcohol resin (A) having a structural unit represented by the following general formula (1), cationic colloidal silica (B), and water is coated on a support and dried. An ink jet recording medium comprising an ink receiving layer formed in the above manner.
(In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, X represents an alkylene having 4 to 50 carbon atoms, and Y represents a hydrogen atom or an alkali metal.)
（式中、Ｒ1、Ｒ2、Ｒ3は、それぞれ独立して水素原子又はアルキル基を示し、Ｘは炭素数が４〜５０のアルキレンを示し、Ｙは水素原子又はアルカリ金属を示す。） A coating liquid for forming an ink-receiving layer, comprising a carboxyl group-containing polyvinyl alcohol resin (A) having a structural unit represented by the following general formula (1), cationic colloidal silica (B), and water. .
(In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, X represents an alkylene having 4 to 50 carbon atoms, and Y represents a hydrogen atom or an alkali metal.)
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| EP2551665A1 (en) | 2011-07-25 | 2013-01-30 | Sony Corporation | Information processing apparatus, information processing method, program, and method of correcting intensity of fluorescence spectrum |
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