JP2022189685A - Water-based ink for soft packaging - Google Patents
Water-based ink for soft packaging Download PDFInfo
- Publication number
- JP2022189685A JP2022189685A JP2021159227A JP2021159227A JP2022189685A JP 2022189685 A JP2022189685 A JP 2022189685A JP 2021159227 A JP2021159227 A JP 2021159227A JP 2021159227 A JP2021159227 A JP 2021159227A JP 2022189685 A JP2022189685 A JP 2022189685A
- Authority
- JP
- Japan
- Prior art keywords
- water
- urethane resin
- resin
- film
- coating film
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000004806 packaging method and process Methods 0.000 title abstract description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 124
- 230000009477 glass transition Effects 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229920000178 Acrylic resin Polymers 0.000 claims description 52
- 239000004925 Acrylic resin Substances 0.000 claims description 52
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000009459 flexible packaging Methods 0.000 claims description 20
- 238000000576 coating method Methods 0.000 abstract description 105
- 239000011248 coating agent Substances 0.000 abstract description 103
- 230000000903 blocking effect Effects 0.000 abstract description 30
- 239000000758 substrate Substances 0.000 abstract description 25
- 238000005406 washing Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 68
- -1 isocyanate compounds Chemical class 0.000 description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 31
- 238000000034 method Methods 0.000 description 24
- 239000000049 pigment Substances 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 238000007774 anilox coating Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000005021 flexible packaging material Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 239000008399 tap water Substances 0.000 description 2
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- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
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- 239000013225 prussian blue Substances 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Printing Methods (AREA)
Abstract
Description
本発明は、軟包装用水性インキに関する。 The present invention relates to a water-based ink for flexible packaging.
食品や日用品等の包装に用いられるプラスチックフィルム等の軟包装材料には、グラビア印刷やフレキソ印刷を用いて意匠性や機能性が表示されている。従来、軟包装用インキは有機溶剤を使用した油性タイプであったが、近年では環境問題などの観点から、有機溶剤を極力減らした水性タイプの要望が強くなっている。
例えば特許文献１には、顔料と、アルカリ可溶型水溶性樹脂と、ロジン系樹脂エマルジョンと、スチレン－アクリル系樹脂エマルジョンと、水を含有する溶剤とを含む水性フレキソ印刷インキ組成物が開示されている。
Design and functionality are displayed on flexible packaging materials such as plastic films used for packaging foods, daily necessities, etc., using gravure printing or flexographic printing. In the past, flexible packaging inks were oil-based inks that used organic solvents, but in recent years, from the viewpoint of environmental issues, there is a strong demand for water-based inks that use as little organic solvents as possible.
For example, Patent Document 1 discloses an aqueous flexographic printing ink composition containing a pigment, an alkali-soluble water-soluble resin, a rosin resin emulsion, a styrene-acrylic resin emulsion, and a water-containing solvent. ing.
しかしながら、水性インキは油性インキに比べて乾燥しにくいため、塗膜形成時に乾燥が不十分であるとプラスチックフィルム等の基材フィルムに印刷した後に巻き取った際にブロッキングが生じることがある。そのため、水性インキには、乾燥が不十分な状態であっても表面がタックフリーとなり、耐ブロッキング性を有する塗膜を形成できることが求められる。
表面がタックフリーとなるような塗膜を形成するためには、例えばガラス転移温度の高いバインダー樹脂を水性インキに配合すればよい。しかし、バインダー樹脂のガラス転移温度が高くなると、基材フィルムに塗工された水性インキが乾燥して基材フィルムに塗膜が定着する際に応力緩和が進まず、基材フィルムに対する塗膜の密着性が低下しやすくなる。
However, since water-based inks are more difficult to dry than oil-based inks, blocking may occur when the substrate film such as a plastic film is printed on and then wound up if the drying is insufficient at the time of coating film formation. Therefore, water-based inks are required to be tack-free on the surface and to be able to form a coating film having anti-blocking properties even in an insufficiently dried state.
In order to form a coating film having a tack-free surface, for example, a binder resin having a high glass transition temperature may be added to the water-based ink. However, when the glass transition temperature of the binder resin becomes high, the stress relaxation does not progress when the water-based ink applied to the base film dries and the coating film is fixed to the base film. Adhesion tends to decrease.
ところで、グラビア版のセル中やフレキソ版に残った水性インキが乾燥した場合、転写不良などの原因となる。そのため、塗膜には耐ブロッキング性及び基材フィルムに対する密着性に加えて、版洗浄性や再溶解性に優れることも求められる。ここで、再溶解性とは、水性インキが乾燥して転移不良の原因となる状態の前に、水性インキを構成する溶剤に再溶解する性能のことである。再溶解性は重要な印刷適性の１つと言える。 By the way, when the water-based ink remaining in the cells of the gravure plate or on the flexographic plate dries, it causes poor transfer. Therefore, in addition to blocking resistance and adhesion to the substrate film, the coating film is also required to have excellent plate washability and re-solubility. Here, the re-solubility is the ability to re-dissolve in the solvent constituting the water-based ink before the water-based ink dries and becomes a cause of poor transfer. Re-solubility can be said to be one of the important printability.
本発明の目的は、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性に優れる塗膜を形成できる軟包装用水性インキを提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a water-based ink for flexible packaging capable of forming a coating film excellent in blocking resistance, adhesion to a substrate film, plate washability and resolubility.
本発明は、以下の態様を有する。
［１］ 水性ウレタン樹脂（Ａ１）を含む水性樹脂（Ａ）と、アルカリ性付与剤（Ｂ）とを含有し、
前記水性ウレタン樹脂（Ａ１）は、造膜したときの１００％モジュラスが８ＭＰａ未満である水性ウレタン樹脂（Ａ１１）と、造膜したときの１００％モジュラスが８ＭＰａ以上である水性ウレタン樹脂（Ａ１２）とを含み、
前記水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスが２０ＭＰａ未満であり、かつ前記水性ウレタン樹脂（Ａ１）のガラス転移温度が－３０～１３０℃である、軟包装用水性インキ。
［２］ 前記水性樹脂（Ａ）は、水性アクリル樹脂（Ａ２）及び水性ウレタンアクリル樹脂（Ａ３）の少なくとも一方をさらに含む、前記［１］の軟包装用水性インキ。
［３］ 前記水性ウレタン樹脂（Ａ１１）のガラス転移温度が－５０～５０℃である、前記［１］又は［２］の軟包装用水性インキ。
［４］ 前記水性ウレタン樹脂（Ａ１２）のガラス転移温度が５０～１３０℃である、前記［１］～［３］のいずれかの軟包装用水性インキ。
［５］ 前記水性ウレタン樹脂（Ａ１２）／前記水性ウレタン樹脂（Ａ１１）で表される質量比が、０．２～１０である、前記［１］～［４］のいずれかの軟包装用水性インキ。
The present invention has the following aspects.
[1] Containing an aqueous resin (A) containing an aqueous urethane resin (A1) and an alkalinity-imparting agent (B),
The aqueous urethane resin (A1) includes an aqueous urethane resin (A11) having a 100% modulus of less than 8 MPa when forming a film, and an aqueous urethane resin (A12) having a 100% modulus of 8 MPa or more when forming a film. including
A water-based ink for flexible packaging, wherein the water-based urethane resin (A1) has a 100% modulus of less than 20 MPa when formed into a film, and a glass transition temperature of -30 to 130°C.
[2] The water-based ink for flexible packaging according to [1], wherein the water-based resin (A) further contains at least one of a water-based acrylic resin (A2) and a water-based urethane acrylic resin (A3).
[3] The water-based ink for flexible packaging according to [1] or [2], wherein the water-based urethane resin (A11) has a glass transition temperature of -50 to 50°C.
[4] The water-based ink for flexible packaging according to any one of [1] to [3], wherein the water-based urethane resin (A12) has a glass transition temperature of 50 to 130°C.
[5] The aqueous solution for flexible packaging according to any one of [1] to [4], wherein the mass ratio represented by the water-based urethane resin (A12)/the water-based urethane resin (A11) is 0.2 to 10. ink.
本発明によれば、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性に優れる塗膜を形成できる軟包装用水性インキを提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the water-based ink for flexible packaging which can form the coating film excellent in blocking resistance, adhesion with respect to a base film, plate washability, and resolubility can be provided.
以下、本発明を詳細に説明する。以下の実施の形態は、本発明を説明するための単なる例示であって、本発明をこの実施の形態にのみ限定することは意図されない。本発明は、その趣旨を逸脱しない限り、様々な態様で実施することが可能である。
なお、本発明において、水性インキにおける「水性」とは、溶剤として水を含むことを意味する。また、「水性樹脂」とは、「水溶性樹脂」及び「水分散性樹脂（樹脂エマルジョン、樹脂ディスパージョン）」の総称である。
また、本明細書において、「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」の総称である。「（メタ）アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の総称である。
また、本明細書において、「塗膜」とは、本発明の軟包装用水性インキより形成される塗膜のことである。
The present invention will be described in detail below. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention only to these embodiments. The present invention can be implemented in various forms without departing from its spirit.
In addition, in this invention, "water-based" in water-based ink means containing water as a solvent. Further, "aqueous resin" is a general term for "water-soluble resin" and "water-dispersible resin (resin emulsion, resin dispersion)".
Moreover, in this specification, "(meth)acrylate" is a generic term for "acrylate" and "methacrylate". "(Meth)acrylic acid" is a generic term for "acrylic acid" and "methacrylic acid".
Further, in this specification, the term "coating film" means a coating film formed from the water-based ink for flexible packaging of the present invention.
［軟包装用水性インキ］
本発明の一実施形態に係る軟包装用水性インキ（以下、単に「水性インキ」ともいう。）は、以下に示す水性樹脂（Ａ）と、アルカリ性付与剤（Ｂ）と、顔料（Ｃ）と、溶剤（Ｄ）とを含有する。
水性インキは、必要に応じて水性樹脂（Ａ）、アルカリ性付与剤（Ｂ）、顔料（Ｃ）及び溶剤（Ｄ）以外の成分（任意成分）をさらに含有してもよい。
[Water-based ink for flexible packaging]
The water-based ink for flexible packaging according to one embodiment of the present invention (hereinafter also simply referred to as "water-based ink") comprises a water-based resin (A) shown below, an alkalinity-imparting agent (B), and a pigment (C). , a solvent (D).
The water-based ink may further contain components (optional components) other than the water-based resin (A), the alkalinity-imparting agent (B), the pigment (C) and the solvent (D), if necessary.
＜水性樹脂（Ａ）＞
水性樹脂（Ａ）は、バインダー樹脂成分である。
水性樹脂（Ａ）は、水性ウレタン樹脂（Ａ１）を含む。
水性樹脂（Ａ）は、塗膜の耐ブロッキング性及び再溶解性がさらに向上する観点から、水性アクリル樹脂（Ａ２）及び水性ウレタンアクリル樹脂（Ａ３）の少なくとも一方をさらに含むことが好ましい。
<Aqueous resin (A)>
The aqueous resin (A) is a binder resin component.
The aqueous resin (A) contains an aqueous urethane resin (A1).
The water-based resin (A) preferably further contains at least one of the water-based acrylic resin (A2) and the water-based urethane acrylic resin (A3) from the viewpoint of further improving the blocking resistance and re-solubility of the coating film.
（水性ウレタン樹脂（Ａ１））
水性ウレタン樹脂（Ａ１）は、造膜したときの１００％モジュラスが８ＭＰａ未満である水性ウレタン樹脂（Ａ１１）と、造膜したときの１００％モジュラスが８ＭＰａ以上である水性ウレタン樹脂（Ａ１２）とを含む。また、水性ウレタン樹脂（Ａ１）は、造膜したときの１００％モジュラスが２０ＭＰａ未満であり、かつガラス転移温度が－３０～１３０℃である樹脂である。
水性インキがこのような水性ウレタン樹脂（Ａ１）を含むことで、耐ブロッキング性が良好でありながら、基材フィルムに対する密着性に優れる塗膜を形成できる。加えて、塗膜の版洗浄性及び再溶解性も向上する。
(Aqueous urethane resin (A1))
The aqueous urethane resin (A1) includes an aqueous urethane resin (A11) having a 100% modulus of less than 8 MPa when formed into a film and an aqueous urethane resin (A12) having a 100% modulus of 8 MPa or more when formed into a film. include. The water-based urethane resin (A1) is a resin having a 100% modulus of less than 20 MPa and a glass transition temperature of -30 to 130°C when formed into a film.
By including such a water-based urethane resin (A1) in the water-based ink, it is possible to form a coating film having excellent adhesion to the base film while having good blocking resistance. In addition, plate washability and resolubility of the coating film are also improved.
水性ウレタン樹脂（Ａ１１）は主に塗膜の基材フィルムに対する密着性に寄与する成分である。
水性ウレタン樹脂（Ａ１１）を造膜したときの１００％モジュラスは、８ＭＰａ未満であり、７ＭＰａ以下が好ましく、６ＭＰａ以下がより好ましい。
塗膜のラミネート適性がより向上する観点から、水性ウレタン樹脂（Ａ１１）を造膜したときの１００％モジュラスは、１ＭＰａ以上が好ましく、２ＭＰａ以上がより好ましい。
なお、本発明における１００％モジュラスは、２５℃で測定したときの値である。
The aqueous urethane resin (A11) is a component that mainly contributes to the adhesion of the coating film to the substrate film.
The 100% modulus when the water-based urethane resin (A11) is formed into a film is less than 8 MPa, preferably 7 MPa or less, more preferably 6 MPa or less.
From the viewpoint of further improving lamination suitability of the coating film, the 100% modulus when the aqueous urethane resin (A11) is formed into a film is preferably 1 MPa or more, more preferably 2 MPa or more.
The 100% modulus in the present invention is a value measured at 25°C.
水性ウレタン樹脂（Ａ１１）を造膜したときの１００％モジュラスは、以下のようにして測定される。
まず、水性ウレタン樹脂（Ａ１１）の試料溶液を離型紙上に塗工し、乾燥させて膜厚が５０μｍの塗工フィルムを作製し、離型紙から剥離する。次いで、引張試験機を用い、温度２５℃、引張速度１００ｍｍ／秒の条件で、塗工フィルムの１００％モジュラスを測定する。
塗工方法としては特に限定されず、例えばハケ塗り、グラビアコーター法、ダイコーター法、バーコーター法、スプレーコート法、フローコート法、ディップコート法、スピンコート法及びカーテンコート法等の公知の方法を用いることができる。
乾燥方法としては離型紙上に塗工された試料溶液の溶媒を除去できれば特に制限されないが、例えば減圧乾燥、加圧乾燥、加熱乾燥、風乾などが挙げられる。加熱する際の温度は３０～１５０℃が好ましく、４０～１００℃がより好ましい。
The 100% modulus when the aqueous urethane resin (A11) is formed into a film is measured as follows.
First, a sample solution of water-based urethane resin (A11) is applied onto release paper and dried to prepare a coating film having a thickness of 50 μm, which is peeled off from the release paper. Then, using a tensile tester, the 100% modulus of the coated film is measured under conditions of a temperature of 25° C. and a tensile speed of 100 mm/sec.
The coating method is not particularly limited, and known methods such as brush coating, gravure coater method, die coater method, bar coater method, spray coating method, flow coating method, dip coating method, spin coating method and curtain coating method. can be used.
The drying method is not particularly limited as long as the solvent of the sample solution coated on the release paper can be removed. The temperature during heating is preferably 30 to 150°C, more preferably 40 to 100°C.
水性ウレタン樹脂（Ａ１１）のガラス転移温度は－５０～５０℃が好ましく、－４５～４０℃がより好ましく、－４３～３０℃がさらに好ましい。水性ウレタン樹脂（Ａ１１）のガラス転移温度が上記下限値以上であれば、塗膜の耐ブロッキング性をより良好に維持できる。水性ウレタン樹脂（Ａ１１）のガラス転移温度が上記上限値以下であれば、塗膜の基材フィルムに対する密着性をより良好に維持できる。 The glass transition temperature of the aqueous urethane resin (A11) is preferably -50 to 50°C, more preferably -45 to 40°C, and still more preferably -43 to 30°C. If the glass transition temperature of the water-based urethane resin (A11) is at least the above lower limit, the blocking resistance of the coating film can be maintained more favorably. If the glass transition temperature of the water-based urethane resin (A11) is at most the above upper limit, the adhesion of the coating film to the substrate film can be maintained more satisfactorily.
水性ウレタン樹脂（Ａ１１）のガラス転移温度は、ＪＩＳ Ｋ ７１２１に準拠し、以下のようにして測定される。
示差走査熱量計を用い、水性ウレタン樹脂（Ａ１１）１０ｍｇを－１００℃から１６０℃まで、２０℃／分の条件で昇温させて得られる曲線（ＤＳＣ曲線）におけるベースラインと吸熱カーブの接線との交点からガラス転移温度を求める。
The glass transition temperature of the aqueous urethane resin (A11) conforms to JIS K 7121 and is measured as follows.
Using a differential scanning calorimeter, 10 mg of the water-based urethane resin (A11) is heated from −100° C. to 160° C. at 20° C./min. Obtain the glass transition temperature from the intersection of
水性ウレタン樹脂（Ａ１１）の質量平均分子量は、１００００～１０００００が好ましく、２００００～８００００がより好ましく、２５０００～６００００がさらに好ましい。水性ウレタン樹脂（Ａ１１）の質量平均分子量が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。水性ウレタン樹脂（Ａ１１）の質量平均分子量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性がより向上する。 The weight average molecular weight of the aqueous urethane resin (A11) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 25,000 to 60,000. If the weight average molecular weight of the water-based urethane resin (A11) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the weight average molecular weight of the water-based urethane resin (A11) is equal to or less than the above upper limit, the adhesion of the coating film to the substrate film is further improved.
水性ウレタン樹脂（Ａ１１）の質量平均分子量は、標準ポリスチレン分子量換算による質量平均分子量であり、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）を用いて測定することができる。 The weight average molecular weight of the aqueous urethane resin (A11) is weight average molecular weight in terms of standard polystyrene molecular weight, and can be measured using gel permeation chromatography (GPC).
水性ウレタン樹脂（Ａ１２）は主に水性ウレタン樹脂（Ａ１２）は主に塗膜の耐ブロッキング性に寄与する成分である。
水性ウレタン樹脂（Ａ１２）を造膜したときの１００％モジュラスは、８ＭＰａ以上であり、８．５ＭＰａ以上が好ましく、９ＭＰａ以上がより好ましい。
水性ウレタン樹脂（Ａ１２）を造膜したときの１００％モジュラスの上限値については特に制限されず、水性ウレタン樹脂（Ａ１２）は測定限界を超える高いモジュラスを有するものであってもよい。
水性ウレタン樹脂（Ａ１２）を造膜したときの１００％モジュラスは、水性ウレタン樹脂（Ａ１１）を造膜したときの１００％モジュラスと同様の方法により測定することができる。
The water-based urethane resin (A12) is a component that mainly contributes to the blocking resistance of the coating film.
The 100% modulus when the water-based urethane resin (A12) is formed into a film is 8 MPa or more, preferably 8.5 MPa or more, and more preferably 9 MPa or more.
The upper limit of the 100% modulus when the water-based urethane resin (A12) is formed into a film is not particularly limited, and the water-based urethane resin (A12) may have a high modulus exceeding the measurement limit.
The 100% modulus when the water-based urethane resin (A12) is formed can be measured by the same method as the 100% modulus when the water-based urethane resin (A11) is formed.
水性ウレタン樹脂（Ａ１２）のガラス転移温度５０～１３０℃が好ましく、６０～１２０℃がより好ましく、７０～１１０℃がさらに好ましい。水性ウレタン樹脂（Ａ１２）のガラス転移温度が上記下限値以上であれば、塗膜の耐ブロッキング性及び耐擦過性がより向上する。水性ウレタン樹脂（Ａ１２）のガラス転移温度が上記上限値以下であれば、塗膜の基材フィルムに対する密着性及び耐割れ性をより良好に維持できる。
水性ウレタン樹脂（Ａ１２）のガラス転移温度は、水性ウレタン樹脂（Ａ１１）のガラス転移温度と同様の方法により測定することができる。
The glass transition temperature of the aqueous urethane resin (A12) is preferably 50 to 130°C, more preferably 60 to 120°C, even more preferably 70 to 110°C. When the glass transition temperature of the water-based urethane resin (A12) is at least the above lower limit, the blocking resistance and scratch resistance of the coating film are further improved. If the glass transition temperature of the water-based urethane resin (A12) is at most the above upper limit, the adhesion and crack resistance of the coating film to the substrate film can be maintained more satisfactorily.
The glass transition temperature of the aqueous urethane resin (A12) can be measured by the same method as for the glass transition temperature of the aqueous urethane resin (A11).
上述したように、水性インキに含まれるバインダー樹脂のガラス転移温度が高くなると塗膜の耐ブロッキング性は良好となるが、基材フィルムに対する塗膜の密着性が低下しやすくなる。
しかし、本発明では、ガラス転移温度が比較的高い、具体的には５０～１３０℃である水性ウレタン樹脂（Ａ１２）を使用しても、水性ウレタン樹脂（Ａ１１）を併用することで、塗膜の基材フィルムに対する密着性をより良好に維持でき、塗膜の耐ブロッキング性と、基材フィルムに対する密着性のバランスがより良好なものとなる。
As described above, when the glass transition temperature of the binder resin contained in the water-based ink increases, the blocking resistance of the coating film is improved, but the adhesion of the coating film to the substrate film tends to decrease.
However, in the present invention, even if the water-based urethane resin (A12) having a relatively high glass transition temperature, specifically 50 to 130 ° C., is used in combination with the water-based urethane resin (A11), the coating film The adhesion to the base film can be maintained better, and the blocking resistance of the coating film and the adhesion to the base film are well balanced.
水性ウレタン樹脂（Ａ１２）の質量平均分子量は、１００００～１０００００が好ましく、２００００～９００００がより好ましく、３００００～８００００がさらに好ましい。水性ウレタン樹脂（Ａ１２）の質量平均分子量が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。水性ウレタン樹脂（Ａ１２）の質量平均分子量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性がより向上する。
水性ウレタン樹脂（Ａ１２）の質量平均分子量は、水性ウレタン樹脂（Ａ１１）の質量平均分子量と同様の方法により測定することができる。
The weight average molecular weight of the water-based urethane resin (A12) is preferably 10,000 to 100,000, more preferably 20,000 to 90,000, even more preferably 30,000 to 80,000. If the weight average molecular weight of the water-based urethane resin (A12) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the weight average molecular weight of the water-based urethane resin (A12) is equal to or less than the above upper limit, the adhesion of the coating film to the substrate film is further improved.
The weight average molecular weight of the aqueous urethane resin (A12) can be measured by the same method as for the weight average molecular weight of the aqueous urethane resin (A11).
水性ウレタン樹脂（Ａ１１）と水性ウレタン樹脂（Ａ１２）との配合比率は、水性ウレタン樹脂（Ａ１）全体として、１００％モジュラスが２０ＭＰａ未満となり、かつガラス転移温度が－３０～１３０℃となれば特に制限されない。例えば、インキ組成物の総質量に対して、水性ウレタン樹脂（Ａ１１）は１～１５質量％が好ましく、２～１０質量％がより好ましい。また、インキ組成物の総質量に対して、水性ウレタン樹脂（Ａ１２）は２～１５質量％が好ましく、４～１２質量％がより好ましい。 The blending ratio of the water-based urethane resin (A11) and the water-based urethane resin (A12) is particularly when the 100% modulus of the water-based urethane resin (A1) as a whole is less than 20 MPa and the glass transition temperature is -30 to 130 ° C. Not restricted. For example, the water-based urethane resin (A11) is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, relative to the total mass of the ink composition. The water-based urethane resin (A12) is preferably 2 to 15% by mass, more preferably 4 to 12% by mass, relative to the total mass of the ink composition.
また、水性ウレタン樹脂（Ａ１１）の質量に対する水性ウレタン樹脂（Ａ１２）の質量比、すなわち、水性ウレタン樹脂（Ａ１２）／水性ウレタン樹脂（Ａ１１）で表される質量比（以下、「Ａ１２／Ａ１１比」ともいう。）は、０．２～１０が好ましく、０．４～７がより好ましく、０．５～５がさらに好ましい。Ａ１２／Ａ１１比が上記下限値以上であれば、塗膜の耐ブロッキング性をより良好に維持できる。Ａ１２／Ａ１１比が上記上限値以下であれば、塗膜の基材フィルムに対する密着性をより良好に維持できる。 Further, the mass ratio of the water-based urethane resin (A12) to the mass of the water-based urethane resin (A11), that is, the mass ratio represented by the water-based urethane resin (A12) / water-based urethane resin (A11) (hereinafter referred to as "A12/A11 ratio ” is preferably 0.2 to 10, more preferably 0.4 to 7, and even more preferably 0.5 to 5. When the A12/A11 ratio is at least the above lower limit, the blocking resistance of the coating film can be maintained more satisfactorily. If the A12/A11 ratio is equal to or less than the above upper limit value, the adhesion of the coating film to the substrate film can be maintained more satisfactorily.
水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスは、２０ＭＰａ未満であり、１５ＭＰａ以下が好ましく、１０ＭＰａ以下がより好ましい。水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスが上記上限値未満であれば、塗膜の基材フィルムに対する密着性が向上する。
塗膜の耐ブロッキング性がより向上する観点から、水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスは、２ＭＰａ以上が好ましく、３ＭＰａ以上がより好ましく、４ＭＰａ以上がさらに好ましい。
The 100% modulus when the water-based urethane resin (A1) is formed into a film is less than 20 MPa, preferably 15 MPa or less, more preferably 10 MPa or less. When the 100% modulus of the water-based urethane resin (A1) is less than the above upper limit, the adhesion of the coating film to the substrate film is improved.
From the viewpoint of further improving the blocking resistance of the coating film, the 100% modulus when the aqueous urethane resin (A1) is formed into a film is preferably 2 MPa or more, more preferably 3 MPa or more, and even more preferably 4 MPa or more.
水性ウレタン樹脂（Ａ１）のガラス転移温度は、－３０～１３０℃であり、－１０～１１０℃が好ましく、１０～９０℃がより好ましい。水性ウレタン樹脂（Ａ１）のガラス転移温度が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で維持できる。水性ウレタン樹脂（Ａ１）のガラス転移温度が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を良好に維持できる。 The glass transition temperature of the aqueous urethane resin (A1) is -30 to 130°C, preferably -10 to 110°C, more preferably 10 to 90°C. When the glass transition temperature of the water-based urethane resin (A1) is at least the above lower limit, the blocking resistance of the coating film can be maintained within an allowable range. If the glass transition temperature of the water-based urethane resin (A1) is at most the above upper limit, the adhesion of the coating film to the substrate film can be maintained satisfactorily.
水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラス及びガラス転移温度は、水性ウレタン樹脂（Ａ１１）と水性ウレタン樹脂（Ａ１２）を含む混合物の状態で測定する。
水性ウレタン樹脂（Ａ１１）と水性ウレタン樹脂（Ａ１２）を含む混合物を造膜したときの１００％モジュラスは、水性ウレタン樹脂（Ａ１１）を造膜したときの１００％モジュラスと同様の方法により測定することができる。
水性ウレタン樹脂（Ａ１１）と水性ウレタン樹脂（Ａ１２）を含む混合物のガラス転移温度は、水性ウレタン樹脂（Ａ１１）のガラス転移温度と同様の方法により測定することができる。
The 100% modulus and glass transition temperature when the water-based urethane resin (A1) is formed into a film are measured in the state of a mixture containing the water-based urethane resin (A11) and the water-based urethane resin (A12).
The 100% modulus when the mixture containing the water-based urethane resin (A11) and the water-based urethane resin (A12) is formed is measured by the same method as the 100% modulus when the water-based urethane resin (A11) is formed. can be done.
The glass transition temperature of the mixture containing the aqueous urethane resin (A11) and the aqueous urethane resin (A12) can be measured by the same method as the glass transition temperature of the aqueous urethane resin (A11).
なお、水性ウレタン樹脂（Ａ１１）と水性ウレタン樹脂（Ａ１２）を含む混合物の状態ではなく、それぞれ単独で１００％モジュラス及びガラス転移温度を測定する場合は、各々の１００％モジュラス及びガラス転移温度の値から加重平均により、水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラス及びガラス転移温度をそれぞれ求めてもよい。具体的には、下記式（１）より求められる値を水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスとし、下記式（２）より求められる値を水性ウレタン樹脂（Ａ１）のガラス転移温度とする。混合物の状態で測定した１００％モジュラスの値と、下記式（１）より求めた１００％モジュラスの値は概ね一致する。同様に、混合物の状態で測定したガラス転移温度の値と、下記式（２）より求めたガラス転移温度の値は概ね一致する。
１００％モジュラス＝Ｗ１×Ｍ１＋Ｗ２×Ｍ２＋・・・＋Ｗｎ×Ｍｎ ・・・（１）
ガラス転移温度＝Ｗ１×Ｔｇ１＋Ｗ２×Ｔｇ２＋・・・＋Ｗｎ×Ｔｇｎ ・・・（２）
式（１）中、Ｗ１、Ｗ２、・・・Ｗｎはｎ種の水性ウレタン樹脂の質量分率であり、Ｍ１、Ｍ２、・・・Ｍｎはそれぞれの水性ウレタン樹脂の１００％モジュラスである。
式（２）中、Ｗ１、Ｗ２、・・・Ｗｎはｎ種の水性ウレタン樹脂の質量分率であり、Ｔｇ１、Ｔｇ２、・・・Ｔｇｎはそれぞれの水性ウレタン樹脂のガラス転移温度である。
When measuring the 100% modulus and the glass transition temperature independently, instead of the state of the mixture containing the water-based urethane resin (A11) and the water-based urethane resin (A12), the respective 100% modulus and glass transition temperature values The 100% modulus and the glass transition temperature when the water-based urethane resin (A1) is formed into a film may be obtained by weighted average from the above. Specifically, the value obtained from the following formula (1) is the 100% modulus when the water-based urethane resin (A1) is formed, and the value obtained from the following formula (2) is the glass of the water-based urethane resin (A1). Let it be the transition temperature. The 100% modulus value measured in the state of the mixture and the 100% modulus value obtained from the following formula (1) approximately agree. Similarly, the value of the glass transition temperature measured in the state of the mixture and the value of the glass transition temperature obtained from the following formula (2) approximately match.
100 % modulus=W1*M1+W2 * M2 +...+ Wn*Mn ... ( 1 )
Glass transition temperature = W 1 ×Tg 1 +W 2 ×Tg 2 + + W n ×Tg n (2)
In formula ( 1 ), W 1 , W 2 , . % modulus.
In formula ( 2 ), W 1 , W 2 , . is the transition temperature.
水性ウレタン樹脂（Ａ１１）及び水性ウレタン樹脂（Ａ１２）は、多価イソシアネート化合物とポリオール化合物との反応生成物である。
多価イソシアネート化合物は、１分子中に少なくとも２つのイソシアネート基を有する有機化合物であり、例えば脂肪族、脂環式、芳香族等の多価イソシアネート化合物が挙げられる。
多価イソシアネート化合物としては、例えばトリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、２，４，４－又は２，２，４－トリメチルヘキサメチレンジイソシアネート、２，６－ジイソシアネートメチルカプロエート等の脂肪族ジイソシアネート；水添化ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３－シクロペンタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート、３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（イソホロンジイソシアネート）、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、１，４－ビス（イソシアネートメチル）シクロヘキサン、１，３－ビス（イソシアネートメチル）シクロヘキサン等の脂環式ジイソシアネート；ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、４，４’－ジフェニルジイソシアネート、１，５－ナフタレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、２，４－又は２，６－トリレンジイソシアネート、４，４’－トルイジンジイソシアネート、ジアニシジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート；上記ジイソシアネートを用いて、アロファネート構造、ヌレート構造、ビウレット構造等を有する多量体化した多価イソシアネート系化合物；１，３，５－トリイソシアネートベンゼン、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートヘキサン等のトリイソシアネート；４，４’－ジフェニルジメチルメタン－２，２’－５，５’－テトライソシアネート等のポリイソシアネートなどが挙げられる。これらの多価イソシアネート化合物は１種を単独で用いてもよく２種以上を併用してもよい。
The aqueous urethane resin (A11) and the aqueous urethane resin (A12) are reaction products of polyvalent isocyanate compounds and polyol compounds.
The polyvalent isocyanate compound is an organic compound having at least two isocyanate groups in one molecule, and examples thereof include polyvalent isocyanate compounds such as aliphatic, alicyclic and aromatic compounds.
Examples of polyvalent isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. diisocyanates, aliphatic diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate; hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3 -cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4′-methylenebis(cyclohexyl isocyanate), methyl alicyclic diisocyanates such as -2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane; m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, diani Aromatic diisocyanates such as cysidine diisocyanate and 4,4′-diphenyl ether diisocyanate; Polymerized polyvalent isocyanate compounds having an allophanate structure, a nurate structure, a biuret structure, etc. using the above diisocyanates; 1,3,5-tri Triisocyanates such as isocyanatobenzene, 2,4,6-triisocyanatotoluene, and 1,3,5-triisocyanatohexane; 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate and the like and polyisocyanate. These polyvalent isocyanate compounds may be used alone or in combination of two or more.
ポリオール化合物としては、例えば、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン等の低分子量ポリオールを開始剤として用いて、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を重合して得られるポリエーテルポリオール；エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、ペンタンジオール、３－メチル－１，５－ペンタンジオール、オクタンジオール、１，９－ノナンジオール、１，８－ノナンジオール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、ビスフェノールＡ、水添ビスフェノールＡ等の飽和又は不飽和のグリコール類と、アジピン酸、マレイン酸、フマル酸、無水フタル酸、イソフタル酸、テレフタル酸、コハク酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、アゼライン酸、セバシン酸、スベリン酸等の二塩基酸又はこれらに対応する酸無水物やダイマー酸等とを脱水縮合して得られるポリエステルポリオール；ポリエチレンポリオール、ポリプロピレンポリオール等のポリオレフィンポリオール；前記二塩基酸又はそれらのジアルキルエステルと、前記ポリエーテルポリオールとを反応させて得られるポリエーテルエステルポリオール；前記グリコール類と、メチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲン等とを反応させて得られるポリカーボネートポリオールなどが挙げられる。これらのポリオール化合物は１種を単独で用いてもよく２種以上を併用してもよい。 Examples of polyol compounds include polyols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low-molecular-weight polyols such as ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators. Ether polyol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, octanediol, 1,9-nonanediol, 1,8-nonanediol, 1,4- Saturated or unsaturated glycols such as cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid , oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid or other dibasic acids, or their corresponding acid anhydrides, dimer acids, etc., polyester polyols obtained by dehydration condensation; polyethylene polyols, polyolefin polyols such as polypropylene polyols; polyether ester polyols obtained by reacting the dibasic acids or their dialkyl esters with the polyether polyols; the glycols, methyl carbonate, diphenyl carbonate, ethylene carbonate, Examples thereof include polycarbonate polyols obtained by reacting with phosgene and the like. These polyol compounds may be used alone or in combination of two or more.
水性ウレタン樹脂（Ａ１）は、多価イソシアネート化合物とポリオール化合物とを公知の方法により反応させることで得られる。
また、多価イソシアネート化合物とポリオール化合物との反応生成物に対して、加水分解性ケイ素基含有化合物を反応させて、シラノール基を導入してもよい。本明細書において、シラノール基を導入した水性ウレタン樹脂を「シラノール基含有水性ウレタン樹脂」ともいう。
加水分解性ケイ素基含有化合物は、加水分解性ケイ素基を含有する化合物であり、加水分解性ケイ素基に加えて活性水素基をさらに含有することが好ましい。
加水分解性ケイ素基としては、シラノール縮合触媒の存在下又は非存在下で、加水分解を受けたときに生じる加水分解性基がケイ素基原子に結合している基が挙げられる。加水分解性基としては、例えば水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などが挙げられる。通常、加水分解性基は、１つのケイ素原子に１～３つの範囲で結合している。
活性水素基としては、例えばアミノ基、ヒドロキシ基、メルカプト基などが挙げられる。
The aqueous urethane resin (A1) is obtained by reacting a polyvalent isocyanate compound and a polyol compound by a known method.
Alternatively, silanol groups may be introduced by reacting a hydrolyzable silicon group-containing compound with the reaction product of the polyvalent isocyanate compound and the polyol compound. In the present specification, the aqueous urethane resin into which silanol groups are introduced is also referred to as "silanol group-containing aqueous urethane resin".
The hydrolyzable silicon group-containing compound is a compound containing a hydrolyzable silicon group, and preferably further contains an active hydrogen group in addition to the hydrolyzable silicon group.
Hydrolyzable silicon groups include groups in which hydrolyzable groups generated upon hydrolysis in the presence or absence of a silanol condensation catalyst are bonded to silicon base atoms. Hydrolyzable groups include, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group, and an alkenyloxy group. Generally, hydrolyzable groups are bonded to one silicon atom in the range of 1 to 3.
Examples of active hydrogen groups include amino groups, hydroxy groups, and mercapto groups.
水性ウレタン樹脂（Ａ１）としては、市販品を用いてもよい。市販品としては、例えば日華化学株式会社製の商品名「ネオステッカー４００」、「ネオステッカー２００」；第一工業製薬株式会社製の商品名「スーパーフレックス５００Ｍ」；三井化学株式会社製の商品名「タケラックＷ－６０１０」、「タケラックＷＳ－５１００」、「タケラックＷＳ－４０００」、「タケラックＷ－６３５」などが挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。 A commercially available product may be used as the aqueous urethane resin (A1). Commercially available products include, for example, trade names "Neo Sticker 400" and "Neo Sticker 200" manufactured by Nicca Chemical Co., Ltd.; trade name "Superflex 500M" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; and products manufactured by Mitsui Chemicals, Inc. Names "Takelac W-6010", "Takelac WS-5100", "Takelac WS-4000", "Takelac W-635" and the like. These may be used individually by 1 type, and may use 2 or more types together.
水性ウレタン樹脂（Ａ１）の含有量は、水性インキの総質量に対して５～３０質量％が好ましく、６～２５質量％がより好ましく、７～２０質量％がさらに好ましい。水性ウレタン樹脂（Ａ１）の含有量が上記下限値以上であれば、基材フィルムに対する密着性、版洗浄性及び再溶解性がより向上する。水性ウレタン樹脂（Ａ１）の含有量が上記上限値以下であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。 The content of the aqueous urethane resin (A1) is preferably 5 to 30% by mass, more preferably 6 to 25% by mass, even more preferably 7 to 20% by mass, relative to the total mass of the aqueous ink. If the content of the water-based urethane resin (A1) is at least the above lower limit, the adhesion to the substrate film, plate washability and resolubility are further improved. When the content of the water-based urethane resin (A1) is at most the above upper limit, the blocking resistance of the coating film can be easily maintained within an allowable range.
（水性アクリル樹脂（Ａ２））
水性アクリル樹脂（Ａ２）は、（メタ）アクリレート単位を含む樹脂である。
水性アクリル樹脂（Ａ２）としては、（メタ）アクリレートの単独重合体、２種以上の（メタ）アクリレートの共重合体、（メタ）アクリレートと（メタ）アクリレート以外の単量体との共重合体などが挙げられる。これらの水性アクリル樹脂（Ａ２）は１種を単独で用いてもよく２種以上を併用してもよい。
水性アクリル樹脂（Ａ２）を構成する全ての単量体単位の総質量に対する（メタ）アクリレート単位の割合は、１０～１００質量％が好ましく、２０～１００質量％がより好ましい。
(Aqueous acrylic resin (A2))
The water-based acrylic resin (A2) is a resin containing (meth)acrylate units.
The water-based acrylic resin (A2) includes a (meth)acrylate homopolymer, a copolymer of two or more (meth)acrylates, and a copolymer of (meth)acrylate and a monomer other than (meth)acrylate. etc. These water-based acrylic resins (A2) may be used alone or in combination of two or more.
The ratio of (meth)acrylate units to the total mass of all monomer units constituting the water-based acrylic resin (A2) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass.
（メタ）アクリレートとしては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート等のシクロアルキル（メタ）アクリレート；フェニル（メタ）アクリレート等のアリール（メタ）アクリレート；ベンジル（メタ）アクリレート等のアラルキル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートなどが挙げられる。これらの（メタ）アクリレートは１種を単独で用いてもよく２種以上を併用してもよい。 Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl ( Alkyl (meth)acrylates such as meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; Cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate; ) aryl (meth)acrylates such as acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more.
（メタ）アクリレート以外の単量体としては、例えば１，３－ブタジエン、イソプレン、クロロプレン等の共役ジエン化合物；スチレン、α－メチルスチレン、ハロゲン化スチレン、ジビニルベンゼン等の芳香族ビニル化合物；アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物；Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド等のアクリルアミド；（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸等の不飽和カルボン酸；マレイン酸ジエチル、マレイン酸ジブチル、フマル酸ジブチル、イタコン酸ジエチル、イタコン酸ジブチル等の不飽和カルボン酸エステルなどが挙げられる。これらの単量体は１種を単独で用いてもよく２種以上を併用してもよい。 Examples of monomers other than (meth)acrylate include conjugated diene compounds such as 1,3-butadiene, isoprene, and chloroprene; aromatic vinyl compounds such as styrene, α-methylstyrene, halogenated styrene, and divinylbenzene; acrylonitrile, vinyl cyanide compounds such as methacrylonitrile; acrylamides such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; Saturated carboxylic acids; unsaturated carboxylic acid esters such as diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate and dibutyl itaconate. These monomers may be used singly or in combination of two or more.
水性アクリル樹脂（Ａ２）の質量平均分子量は、２０００～１０００００が好ましく、３０００～８００００がより好ましく、４０００～６００００がさらに好ましい。水性アクリル樹脂（Ａ２）の質量平均分子量が上記下限値以上であれば、塗膜の耐ブロッキング性がより向上する。水性アクリル樹脂（Ａ２）の質量平均分子量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を許容範囲で容易に維持できる。
水性アクリル樹脂（Ａ２）の質量平均分子量は、水性ウレタン樹脂（Ａ１１）の質量平均分子量と同様の方法により測定することができる。
The weight average molecular weight of the water-based acrylic resin (A2) is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, even more preferably 4,000 to 60,000. If the weight average molecular weight of the water-based acrylic resin (A2) is at least the above lower limit, the anti-blocking property of the coating film will be further improved. If the weight average molecular weight of the water-based acrylic resin (A2) is at most the above upper limit, the adhesion of the coating film to the substrate film can be easily maintained within an allowable range.
The weight average molecular weight of the aqueous acrylic resin (A2) can be measured by the same method as for the weight average molecular weight of the aqueous urethane resin (A11).
水性アクリル樹脂（Ａ２）のガラス転移温度は、－１０～９０℃が好ましく、０～９０℃がより好ましく、１０～９０℃がさらに好ましい。水性アクリル樹脂（Ａ２）のガラス転移温度が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。水性アクリル樹脂（Ａ２）のガラス転移温度が上記上限値以下であれば、塗膜の基材に対する密着性を許容範囲で容易に維持できる。
水性アクリル樹脂（Ａ２）のガラス転移温度は、水性ウレタン樹脂（Ａ１１）のガラス転移温度と同様の方法により測定することができる。
The glass transition temperature of the water-based acrylic resin (A2) is preferably -10 to 90°C, more preferably 0 to 90°C, even more preferably 10 to 90°C. When the glass transition temperature of the water-based acrylic resin (A2) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the glass transition temperature of the water-based acrylic resin (A2) is at most the above upper limit, the adhesion of the coating film to the substrate can be easily maintained within an allowable range.
The glass transition temperature of the water-based acrylic resin (A2) can be measured by the same method as the glass transition temperature of the water-based urethane resin (A11).
水性アクリル樹脂（Ａ２）は、（メタ）アクリレートと、必要に応じて（メタ）アクリレート以外の単量体とを含む単量体成分を重合することで得られる。
重合方法としては特に限定されないが、例えば、従来公知のラジカル重合開始剤の存在下で、単量体成分を溶液重合法、塊状重合法、乳化重合法等で重合する方法が挙げられる。
The water-based acrylic resin (A2) is obtained by polymerizing a monomer component containing (meth)acrylate and optionally a monomer other than (meth)acrylate.
The polymerization method is not particularly limited, but examples thereof include a method of polymerizing a monomer component by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like in the presence of a conventionally known radical polymerization initiator.
水性アクリル樹脂（Ａ２）としては、市販品を用いてもよい。市販品としては、例えば星光ＰＭＣ株式会社製の商品名「Ｘ－４３６」；アイカ工業株式会社製の商品名「ウルトラゾールＡ－３５」、「ウルトラゾールＫＪ－１」；ＢＡＳＦジャパン株式会社製の商品名「ジョンクリルＰＤＸ－７６９６」などが挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。 A commercially available product may be used as the water-based acrylic resin (A2). Commercially available products include, for example, the product name “X-436” manufactured by Seiko PMC Co., Ltd.; the product names “Ultrasol A-35” and “Ultrasol KJ-1” manufactured by Aica Kogyo Co., Ltd.; Trade name "Joncryl PDX-7696" and the like can be mentioned. These may be used individually by 1 type, and may use 2 or more types together.
水性アクリル樹脂（Ａ２）の含有量は、水性インキの総質量に対して０～３０質量％が好ましく、０～２５質量％がより好ましく、０～２０質量％がさらに好ましい。水性アクリル樹脂（Ａ２）の含有量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を許容範囲で容易に維持できる。
水性樹脂（Ａ）が水性アクリル樹脂（Ａ２）を含有する場合、水性アクリル樹脂（Ａ２）の含有量は、水性インキの総質量に対して１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましい。水性アクリル樹脂（Ａ２）の含有量が上記下限値以上であれば、塗膜の耐ブロッキング性及び再溶解性がさらに向上する。
The content of the aqueous acrylic resin (A2) is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, even more preferably 0 to 20% by mass, relative to the total mass of the aqueous ink. If the content of the water-based acrylic resin (A2) is equal to or less than the above upper limit, the adhesion of the coating film to the substrate film can be easily maintained within an allowable range.
When the water-based resin (A) contains the water-based acrylic resin (A2), the content of the water-based acrylic resin (A2) is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total mass of the water-based ink. , more preferably 5% by mass or more. If the content of the water-based acrylic resin (A2) is at least the above lower limit, the blocking resistance and re-solubility of the coating film are further improved.
（水性ウレタンアクリル樹脂（Ａ３））
水性ウレタンアクリル樹脂（Ａ３）としては、多価イソシアネート化合物とポリオール化合物とヒドロキシ基含有（メタ）アクリレートとの反応生成物、又は多価イソシアネート化合物とヒドロキシ基含有（メタ）アクリレートとの反応生成物などが挙げられる。
多価イソシアネート化合物としては、水性ウレタン樹脂（Ａ１）の説明において先に例示した多価イソシアネート化合物が挙げられる。
ポリオール化合物としては、水性ウレタン樹脂（Ａ１）の説明において先に例示したポリオール化合物が挙げられる。
ヒドロキシ基含有（メタ）アクリレートとしては、水性アクリル樹脂（Ａ２）の説明において先に例示したヒドロキシアルキル（メタ）アクリレートが挙げられる。
また、水性ウレタンアクリル樹脂（Ａ３）として、例えばコア部にアクリル樹脂を有し、シェル部にウレタン樹脂を有するコアシェル型の樹脂を用いてもよい。
(Aqueous urethane acrylic resin (A3))
As the water-based urethane acrylic resin (A3), a reaction product of a polyvalent isocyanate compound, a polyol compound and a hydroxy group-containing (meth)acrylate, or a reaction product of a polyvalent isocyanate compound and a hydroxy group-containing (meth)acrylate, etc. is mentioned.
Examples of the polyvalent isocyanate compound include the polyvalent isocyanate compounds exemplified above in the description of the aqueous urethane resin (A1).
Examples of the polyol compound include the polyol compounds exemplified above in the description of the water-based urethane resin (A1).
The hydroxy group-containing (meth)acrylates include the hydroxyalkyl (meth)acrylates exemplified above in the description of the water-based acrylic resin (A2).
Further, as the water-based urethane acrylic resin (A3), for example, a core-shell type resin having an acrylic resin in the core portion and a urethane resin in the shell portion may be used.
水性ウレタンアクリル樹脂（Ａ３）の質量平均分子量は、５０００～１０００００が好ましく、６０００～９００００がより好ましく、６０００～８００００がさらに好ましい。水性ウレタンアクリル樹脂（Ａ３）の質量平均分子量が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。水性ウレタンアクリル樹脂（Ａ３）の質量平均分子量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を許容範囲で容易に維持できる。
水性ウレタンアクリル樹脂（Ａ３）の質量平均分子量は、水性ウレタン樹脂（Ａ１１）の質量平均分子量と同様の方法により測定することができる。
The weight average molecular weight of the aqueous urethane acrylic resin (A3) is preferably 5,000 to 100,000, more preferably 6,000 to 90,000, even more preferably 6,000 to 80,000. If the weight average molecular weight of the water-based urethane acrylic resin (A3) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the weight average molecular weight of the water-based urethane acrylic resin (A3) is at most the above upper limit, the adhesion of the coating film to the substrate film can be easily maintained within an allowable range.
The weight average molecular weight of the aqueous urethane acrylic resin (A3) can be measured by the same method as for the weight average molecular weight of the aqueous urethane resin (A11).
水性ウレタンアクリル樹脂（Ａ３）のガラス転移温度は、－３０～１００℃が好ましく、－３０～９０℃がより好ましく、－２０～９０℃がさらに好ましい。水性ウレタンアクリル樹脂（Ａ３）のガラス転移温度が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。水性ウレタンアクリル樹脂（Ａ３）のガラス転移温度が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を許容範囲で容易に維持できる。
水性ウレタンアクリル樹脂（Ａ３）のガラス転移温度は、水性ウレタン樹脂（Ａ１１）のガラス転移温度と同様の方法により測定することができる。
The glass transition temperature of the water-based urethane acrylic resin (A3) is preferably -30 to 100°C, more preferably -30 to 90°C, even more preferably -20 to 90°C. If the glass transition temperature of the water-based urethane acrylic resin (A3) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the glass transition temperature of the water-based urethane acrylic resin (A3) is at most the above upper limit, the adhesion of the coating film to the substrate film can be easily maintained within an allowable range.
The glass transition temperature of the aqueous urethane acrylic resin (A3) can be measured by the same method as for the glass transition temperature of the aqueous urethane resin (A11).
水性ウレタンアクリル樹脂（Ａ３）は、多価イソシアネート化合物とポリオール化合物とヒドロキシ基含有（メタ）アクリレート、又は多価イソシアネート化合物とヒドロキシ基含有（メタ）アクリレートとを公知の方法により反応させることで得られる。 Aqueous urethane acrylic resin (A3) is obtained by reacting a polyvalent isocyanate compound, a polyol compound and a hydroxy group-containing (meth)acrylate, or a polyvalent isocyanate compound and a hydroxy group-containing (meth)acrylate by a known method. .
水性ウレタンアクリル樹脂（Ａ３）としては、市販品を用いてもよい。市販品としては、例えば大成ファインケミカル株式会社製の商品名「ＷＥＭ－２００Ｕ」、「ＷＥＭ－５０５Ｃ」、「ＷＥＭ－３０００」などが挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。 A commercially available product may be used as the aqueous urethane acrylic resin (A3). Examples of commercially available products include trade names “WEM-200U”, “WEM-505C” and “WEM-3000” manufactured by Taisei Fine Chemical Co., Ltd. These may be used individually by 1 type, and may use 2 or more types together.
水性ウレタンアクリル樹脂（Ａ３）の含有量は、水性インキの総質量に対して０～３０質量％が好ましく、０～２５質量％がより好ましく、０～２０質量％がさらに好ましい。水性ウレタンアクリル樹脂（Ａ３）の含有量が上記上限値以下であれば、塗膜の基材に対する密着性を許容範囲で容易に維持できる。
水性樹脂（Ａ）が水性ウレタンアクリル樹脂（Ａ３）を含有する場合、水性ウレタンアクリル樹脂（Ａ３）の含有量は、水性インキの総質量に対して１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましい。水性ウレタンアクリル樹脂（Ａ３）の含有量が上記下限値以上であれば、塗膜の耐ブロッキング性及び再溶解性がさらに向上する。
The content of the aqueous urethane acrylic resin (A3) is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, even more preferably 0 to 20% by mass, relative to the total mass of the aqueous ink. If the content of the water-based urethane acrylic resin (A3) is equal to or less than the above upper limit, the adhesion of the coating film to the substrate can be easily maintained within an allowable range.
When the water-based resin (A) contains the water-based urethane acrylic resin (A3), the content of the water-based urethane acrylic resin (A3) is preferably 1% by mass or more, and preferably 3% by mass or more, relative to the total mass of the water-based ink. More preferably, 5% by mass or more is even more preferable. When the content of the water-based urethane acrylic resin (A3) is at least the above lower limit, the anti-blocking property and re-dissolving property of the coating film are further improved.
＜アルカリ性付与剤（Ｂ）＞
アルカリ性付与剤（Ｂ）は、水性インキのｐＨを適切な範囲に維持する化合物である。水性インキのｐＨを適切な範囲に維持することで、塗膜の再溶解性を維持できる。
アルカリ性付与剤（Ｂ）としては、例えばモルホリン、２－ジメチルアミノエタノール、Ｎ－メチルモルホリン、２－アミノ－２－メチル－１－プロパノール、エチレンジアミン、トリエチレンジアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン等の有機アミン；水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩などが挙げられる。これらのアルカリ性付与剤（Ｂ）は１種を単独で用いてもよく２種以上を併用してもよい。
<Alkalinity imparting agent (B)>
The alkalinity-imparting agent (B) is a compound that maintains the pH of the water-based ink within an appropriate range. By maintaining the pH of the water-based ink within an appropriate range, the resolubility of the coating film can be maintained.
Examples of the alkalinity imparting agent (B) include morpholine, 2-dimethylaminoethanol, N-methylmorpholine, 2-amino-2-methyl-1-propanol, ethylenediamine, triethylenediamine, triethylamine, tripropylamine, tributylamine, and the like. organic amines; alkali metal salts such as sodium hydroxide and potassium hydroxide; These alkalinity-imparting agents (B) may be used alone or in combination of two or more.
アルカリ性付与剤（Ｂ）としては、市販品を用いてもよい。市販品としては、例えばＡＮＧＵＳ社製の商品名「ＡＭＰ－９０」、「ＤＭＡＭＰ－８０」；日本乳化剤株式会社製の商品名「アミノアルコールＰＡ」、「アミノアルコール２ＦＡ」などが挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。 A commercially available product may be used as the alkalinity imparting agent (B). Commercially available products include, for example, trade names “AMP-90” and “DMAMP-80” manufactured by ANGUS; trade names “Amino Alcohol PA” and “Amino Alcohol 2FA” manufactured by Nihon Nyukazai Co., Ltd.; These may be used individually by 1 type, and may use 2 or more types together.
アルカリ性付与剤（Ｂ）の含有量は、水性インキの総質量に対して０．１～５質量％が好ましく、０．１～４質量％がより好ましく、０．１～３質量％がさらに好ましい。アルカリ性付与剤（Ｂ）の含有量が上記下限値以上であれば、インキのｐＨを許容範囲で容易に維持できる。アルカリ性付与剤（Ｂ）の含有量が上記上限値以下であれば、適切な乾燥速度を維持できる。 The content of the alkalinity-imparting agent (B) is preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.1 to 3% by mass, relative to the total mass of the aqueous ink. . If the content of the alkalinity-imparting agent (B) is at least the above lower limit, the pH of the ink can be easily maintained within the allowable range. If the content of the alkalinity-imparting agent (B) is equal to or less than the above upper limit, an appropriate drying rate can be maintained.
＜顔料（Ｃ）＞
顔料（Ｃ）としては、有機顔料、無機顔料などが挙げられる。
有機顔料としては、例えばモノアゾ、縮合アゾ等のアゾ系顔料；アントラキノン系、ペリノン系、ペリレン系、チオインジゴ系等のスレン系顔料；フタロシアニンブルー、フタロシアニングリーン等のフタロシアニン系顔料；キナクリドン系顔料；ジオキサジン系顔料；イソインドリノン系顔料；ピロロピロール系顔料；アニリンブラック；有機蛍光顔料などが挙げられる。これらの有機顔料は１種を単独で用いてもよく２種以上を併用してもよい。
無機顔料としては、例えばクレー、バライト、雲母、タルク等の天然物；紺青等のフェロシアン化物、硫化亜鉛等の硫化物；硫酸バリウム等の硫酸塩；酸化クロム、亜鉛華、酸化チタン、酸化鉄等の酸化物；水酸化アルミニウム等の水酸化物；珪酸カルシウム、群青等のケイ酸塩；炭酸カルシウム、炭酸マグネシウム等の炭酸塩；カーボンブラック、グラファイト等の炭素；アルミニウム粉、ブロンズ粉、亜鉛粉等の金属粉；焼成顔料などが挙げられる。これらの無機顔料は１種を単独で用いてもよく２種以上を併用してもよい。
<Pigment (C)>
Examples of the pigment (C) include organic pigments and inorganic pigments.
Examples of organic pigments include azo pigments such as monoazo and condensed azo; threne pigments such as anthraquinone, perinone, perylene and thioindigo; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone pigments; pigments; isoindolinone pigments; pyrrolopyrrole pigments; aniline black; organic fluorescent pigments; These organic pigments may be used alone or in combination of two or more.
Examples of inorganic pigments include natural products such as clay, barite, mica, and talc; ferrocyanides such as Prussian blue; sulfides such as zinc sulfide; sulfates such as barium sulfate; chromium oxide, zinc white, titanium oxide, and iron oxide. Hydroxides such as aluminum hydroxide; silicates such as calcium silicate and ultramarine blue; carbonates such as calcium carbonate and magnesium carbonate; carbon black, graphite and other carbon; aluminum powder, bronze powder, zinc powder metal powders such as; calcined pigments; These inorganic pigments may be used alone or in combination of two or more.
顔料（Ｃ）の含有量は、水性インキの総質量に対して１～５０質量％が好ましく、１～４８質量％がより好ましく、１～４５質量％がさらに好ましい。顔料（Ｃ）の含有量が上記下限値以上であれば、塗膜の耐ブロッキング性を許容範囲で容易に維持できる。顔料（Ｃ）の含有量が上記上限値以下であれば、塗膜の基材フィルムに対する密着性を良好に維持できる。 The content of the pigment (C) is preferably 1 to 50% by mass, more preferably 1 to 48% by mass, even more preferably 1 to 45% by mass, relative to the total mass of the water-based ink. If the content of the pigment (C) is at least the above lower limit, the blocking resistance of the coating film can be easily maintained within an allowable range. If the content of the pigment (C) is equal to or less than the above upper limit, good adhesion of the coating film to the base film can be maintained.
＜溶剤（Ｄ）＞
溶剤（Ｄ）としては、水；水と有機溶剤との混合溶剤などが挙げられる。
有機溶剤としては、水に可溶であれば特に制限されないが、例えばメタノール、エタノール、プロパノール、ｎ－ブタノール、ｉ－ブタノール等のアルコール系溶剤；アセトン等のケトン系溶剤；プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤などが挙げられる。これらの有機溶剤は１種を単独で用いてもよく２種以上を併用してもよい。
溶剤（Ｄ）の総質量に対する水の含有量は、６０～１００質量％が好ましく、７０～１００質量％がより好ましく、８０～１００質量％がさらに好ましい。
<Solvent (D)>
Examples of the solvent (D) include water, a mixed solvent of water and an organic solvent, and the like.
The organic solvent is not particularly limited as long as it is soluble in water. Examples include alcohol solvents such as methanol, ethanol, propanol, n-butanol and i-butanol; ketone solvents such as acetone; propylene glycol monomethyl ether and the like. Glycol ether solvents and the like are included. These organic solvents may be used singly or in combination of two or more.
The water content relative to the total mass of the solvent (D) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass.
溶剤（Ｄ）の含有量は、水性インキの総質量に対して２０～７０質量％が好ましく、３０～７０質量％がより好ましく、３５～６５質量％がさらに好ましい。溶剤（Ｄ）の含有量が上記下限値以上であれば、適切な塗膜の乾燥性、インキの流動性を良好に維持できる。顔料溶剤（Ｄ）の含有量が上記上限値以下であれば、塗膜の強靭性を許容範囲で容易に維持できる。 The content of the solvent (D) is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, even more preferably 35 to 65% by mass, relative to the total mass of the water-based ink. When the content of the solvent (D) is at least the above lower limit, it is possible to maintain good drying properties of the coating film and good fluidity of the ink. If the content of the pigment solvent (D) is equal to or less than the above upper limit, the toughness of the coating film can be easily maintained within an allowable range.
＜任意成分＞
任意成分としては、例えば沈降防止剤、紫外線吸収剤、酸化防止剤、レベリング剤、増粘剤、消泡剤、滑剤、ワックス分散体、分散剤、安定剤などが挙げられる。これらの任意成分は１種を単独で用いてもよく２種以上を併用してもよい。
<Optional component>
Optional components include, for example, anti-settling agents, ultraviolet absorbers, antioxidants, leveling agents, thickeners, defoaming agents, lubricants, wax dispersions, dispersants, stabilizers and the like. These optional components may be used singly or in combination of two or more.
任意成分の含有量は、本発明の効果を損なわない範囲内であれば特に制限されないが、例えば水性インキの総質量に対して０～１０質量％が好ましく、０～７質量％がより好ましく、０～３質量％がさらに好ましい。
水性インキが任意成分を含有する場合、任意成分の含有量は、水性インキの総質量に対して０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．５質量％以上がさらに好ましい。任意成分の含有量が上記下限値以上であれば、任意成分による効果が十分に発現される。
The content of the optional component is not particularly limited as long as it does not impair the effects of the present invention. 0 to 3% by mass is more preferable.
When the aqueous ink contains an optional component, the content of the optional component is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass or more relative to the total mass of the aqueous ink. is more preferred. If the content of the optional component is at least the above lower limit, the effect of the optional component is sufficiently exhibited.
＜製造方法＞
本実施形態の水性インキは、例えば水性樹脂（Ａ）、アルカリ性付与剤（Ｂ）及び顔料（Ｃ）と、必要に応じて任意成分とを溶剤（Ｄ）に溶解又は分散させることで得られる。
各成分の混合方法としては特に限定されず、種々の方法により各成分を混合することができる。
<Manufacturing method>
The water-based ink of the present embodiment is obtained by dissolving or dispersing, for example, the water-based resin (A), the alkalinity-imparting agent (B), the pigment (C), and optional components in the solvent (D).
The method of mixing each component is not particularly limited, and each component can be mixed by various methods.
＜作用効果＞
以上説明した本実施形態の水性インキは、上述した水性ウレタン樹脂（Ａ１）を含む水性樹脂（Ａ）を含有するので、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性に優れる塗膜を形成できる。
<Effect>
Since the water-based ink of the present embodiment described above contains the water-based resin (A) containing the water-based urethane resin (A1) described above, blocking resistance, adhesion to the substrate film, plate washability and re-solubility are improved. An excellent coating film can be formed.
＜用途＞
本発明の水性インキは、軟包装用であり、グラビア印刷やフレキソ印刷により軟包装材料に印刷する際のインキとして好適である。
ここで、「軟包装」とは、柔軟性を有する材料で構成されている包装材、すなわちフレキシブルパッケージのことであり、食品や日用品等の包装に用いられる。
<Application>
The water-based ink of the present invention is for flexible packaging, and is suitable as an ink for printing on flexible packaging materials by gravure printing or flexographic printing.
Here, "flexible packaging" means a packaging material made of a flexible material, that is, a flexible package, and is used for packaging foods, daily necessities, and the like.
軟包装材料としては、ポリオレフィン（例えばポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等）、ポリエステル（例えばポリエチレンテレフタレート（ＰＥＴ）等）、ポリスチレン（ＰＳ）、延伸ポリプロピレン（ＯＰＰ）、ポリアミド（ＮＹ）等のプラスチックフィルム（基材フィルム）が挙げられる。これらのプラスチックフィルムは１種を単独で用いてもよく２種以上を貼り合わせて使用してもよい。 Flexible packaging materials include plastics such as polyolefin (e.g., polyethylene (PE), polypropylene (PP), etc.), polyester (e.g., polyethylene terephthalate (PET), etc.), polystyrene (PS), oriented polypropylene (OPP), polyamide (NY), etc. A film (base film) is mentioned. These plastic films may be used singly or in combination of two or more.
上述したプラスチックフィルムに本発明の水性インキを用い、グラビア印刷又はフレキソ印刷により印刷を施す。印刷が施されたプラスチックフィルムの印刷層の表面には、必要に応じてラミネート加工がさらに施され、食品包包装用や日用品包装用等に向けた軟包装パッケージとなる。 The water-based ink of the present invention is used on the plastic film described above, and printing is performed by gravure printing or flexographic printing. If necessary, the surface of the printed layer of the printed plastic film is further laminated to form a flexible packaging package for food packaging, daily necessities packaging, and the like.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
［使用原料］
使用原料として、以下に示す化合物を用いた。
＜水性ウレタン樹脂（Ａ１）＞
（水性ウレタン樹脂（Ａ１１））
・Ａ１－１：水性ウレタン樹脂（日華化学株式会社製、商品名「ネオステッカー４００」、１００％モジュラス：４．１ＭＰａ、ガラス転移温度：－４０℃）。
・Ａ１－２：水性ウレタン樹脂（第一工業製薬株式会社製、商品名「スーパーフレックス５００Ｍ」、１００％モジュラス：６．２ＭＰａ、ガラス転移温度：－３９℃）。
・Ａ１－３：水性ウレタン樹脂（日華化学株式会社製、商品名「ネオステッカー２００」、１００％モジュラス：２．３ＭＰａ、ガラス転移温度：－４０℃）。
[raw materials used]
The following compounds were used as starting materials.
<Aqueous urethane resin (A1)>
(Aqueous urethane resin (A11))
A1-1: Water-based urethane resin (manufactured by Nicca Chemical Co., Ltd., trade name “Neo Sticker 400”, 100% modulus: 4.1 MPa, glass transition temperature: −40° C.).
· A1-2: Water-based urethane resin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Superflex 500M", 100% modulus: 6.2 MPa, glass transition temperature: -39°C).
A1-3: Water-based urethane resin (manufactured by Nicca Chemical Co., Ltd., trade name “Neo Sticker 200”, 100% modulus: 2.3 MPa, glass transition temperature: −40° C.).
（水性ウレタン樹脂（Ａ１２））
・Ａ１－４：水性ウレタン樹脂（三井化学株式会社製、商品名「タケラックＷ－６０１０」、１００％モジュラス：１４ＭＰａ、ガラス転移温度：９０℃）。
・Ａ１－５：水性ウレタン樹脂（三井化学株式会社製、商品名「タケラックＷＳ－５１００」、１００％モジュラス：２８ＭＰａ、ガラス転移温度：１２０℃）。
・Ａ１－６：水性ウレタン樹脂（三井化学株式会社製、商品名「タケラックＷＳ－４０００」、１００％モジュラス：なし（測定不能）、ガラス転移温度：１３６℃）。
・Ａ１－７：水性ウレタン樹脂（三井化学株式会社製、商品名「タケラックＷ－６３５」、１００％モジュラス：１０ＭＰａ、ガラス転移温度：７０℃）。
(Aqueous urethane resin (A12))
A1-4: Water-based urethane resin (manufactured by Mitsui Chemicals, Inc., trade name “Takelac W-6010”, 100% modulus: 14 MPa, glass transition temperature: 90° C.).
A1-5: Water-based urethane resin (manufactured by Mitsui Chemicals, Inc., trade name “Takelac WS-5100”, 100% modulus: 28 MPa, glass transition temperature: 120° C.).
A1-6: Water-based urethane resin (manufactured by Mitsui Chemicals, Inc., trade name “Takelac WS-4000”, 100% modulus: none (unmeasurable), glass transition temperature: 136° C.).
A1-7: Water-based urethane resin (manufactured by Mitsui Chemicals, Inc., trade name “Takelac W-635”, 100% modulus: 10 MPa, glass transition temperature: 70° C.).
＜水性アクリル樹脂（Ａ２）＞
・Ａ２－１：水性アクリル樹脂（アイカ工業株式会社製、商品名「ウルトラゾールＡ－３５」、ガラス転移温度：４６℃）。
・Ａ２－２：水性アクリル樹脂（アイカ工業株式会社製、商品名「ウルトラゾールＫＪ－１」、ガラス転移温度：１９℃）。
<Water-based acrylic resin (A2)>
A2-1: Water-based acrylic resin (manufactured by Aica Kogyo Co., Ltd., trade name “Ultrasol A-35”, glass transition temperature: 46° C.).
A2-2: Water-based acrylic resin (manufactured by Aica Kogyo Co., Ltd., trade name "Ultrasol KJ-1", glass transition temperature: 19°C).
＜水性ウレタンアクリル樹脂（Ａ３）＞
・Ａ３－１：水性ウレタンアクリル樹脂（大成ファインケミカル株式会社製、商品名「ＷＥＭ－２００Ｕ」、ガラス転移温度： ℃）。
<Water-based urethane acrylic resin (A3)>
· A3-1: Water-based urethane acrylic resin (manufactured by Taisei Fine Chemical Co., Ltd., trade name "WEM-200U", glass transition temperature: ° C.).
＜アルカリ性付与剤（Ｂ）＞
・Ｂ－１：２－アミノ－２－メチル－１－プロパノール（ＡＮＧＵＳ社製、商品名「ＡＭＰ－９０」）。
<Alkalinity imparting agent (B)>
· B-1: 2-amino-2-methyl-1-propanol (manufactured by ANGUS, trade name “AMP-90”).
＜顔料（Ｃ）＞
・Ｃ－１：ピグメントレッド１４６（大日精化工業株式会社製、商品名「セイカファーストカーミン３８７０」）。
<Pigment (C)>
· C-1: Pigment Red 146 (manufactured by Dainichiseika Kogyo Co., Ltd., trade name "Seika First Carmine 3870").
＜溶剤（Ｄ）＞
・Ｄ－１：水。
<Solvent (D)>
- D-1: Water.
＜任意成分＞
・消泡剤：サンノプコ株式会社製、商品名「ＳＮデフォーマー７７７」。
・ワックス分散体：ＢＹＫ社製、商品名「ＣＥＲＡＣＯＬ７９」。
<Optional component>
· Defoamer: San Nopco Co., Ltd., trade name "SN Deformer 777".
- Wax dispersion: manufactured by BYK, trade name "CERACOL79".
［測定方法］
＜１００％モジュラスの測定＞
水性ウレタン樹脂の試料溶液を離型紙上に塗工し、乾燥機にて１００℃で１０分間、乾燥させて膜厚が５０μｍの塗工フィルムを作製し、離型紙から剥離した。次いで、引張試験機（株式会社島津製作所製、製品名「ＡＧＳ－Ｊ５００Ｎ」）を用い、温度２５℃、引張速度１００ｍｍ／秒の条件で、塗工フィルムの１００％モジュラスを測定した。
なお、２種以上の水性ウレタン樹脂を併用する場合は、所定の比率で混合した混合物の状態で試料溶液を調製して塗工フィルムを作製し、１００％モジュラスを測定した。塗工フィルムが１００％伸びないものは、測定限界を超える高いモジュラスを持つものとして扱い、「なし（測定不能）」とした。
試料溶液の溶媒としては、水を用いた。
[Measuring method]
<Measurement of 100% modulus>
A sample solution of water-based urethane resin was coated on a release paper and dried in a dryer at 100° C. for 10 minutes to prepare a coating film having a thickness of 50 μm, which was peeled off from the release paper. Then, using a tensile tester (manufactured by Shimadzu Corporation, product name "AGS-J500N"), the 100% modulus of the coated film was measured at a temperature of 25°C and a tensile speed of 100 mm/sec.
When two or more kinds of water-based urethane resins were used in combination, a sample solution was prepared in the form of a mixture in a predetermined ratio, a coating film was produced, and the 100% modulus was measured. When the coated film did not stretch 100%, it was treated as having a high modulus exceeding the limit of measurement, and was evaluated as "none (impossible to measure)".
Water was used as the solvent for the sample solution.
＜ガラス転移温度の測定＞
示差走査熱量計（株式会社島津製作所製、製品名「ＤＳＣ－６０ＡＰｌｕｓ」）を用い、水性ウレタン樹脂又は水性アクリル樹脂１０ｍｇを－１００℃から１６０℃まで、２０℃／分の条件で昇温させて得られる曲線（ＤＳＣ曲線）におけるベースラインと吸熱カーブの接線との交点からガラス転移温度を求めた。
なお、２種以上の水性ウレタン樹脂を併用する場合は、所定の比率で混合した混合物の状態でガラス転移温度を測定した。
<Measurement of glass transition temperature>
Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, product name "DSC-60APlus"), 10 mg of water-based urethane resin or water-based acrylic resin is heated from -100 ° C. to 160 ° C. at 20 ° C./min. The glass transition temperature was determined from the intersection of the baseline in the obtained curve (DSC curve) and the tangent line of the endothermic curve.
When two or more water-based urethane resins were used in combination, the glass transition temperature was measured in the state of a mixture in which the resins were mixed at a predetermined ratio.
＜試験用塗工物の作製＞
厚さ１２μｍの片面処理ＰＥＴフィルム（東洋紡株式会社製、商品名「Ｅ－５１００」）の処理面に、水性インキを塗工する直前にコロナ処理を施し、フィルムの処理度をリフレッシュさせたものを基材フィルムとした。
株式会社離合社製のザーンカップ＃４で計測したときの粘度が２５℃で１４秒となるように、水性インキを水道水で希釈して塗工用インキとした。
セルボリューム４．５ｃｍ３／ｍ２のアニロックスロールを搭載したフレキソハンドプルーファーをアプリケーターとして用い、基材フィルム上に塗工用インキを塗工した。次いで、２５℃で２４時間乾燥させて基材フィルム上に塗膜を形成し、試験用塗工物を得た。
<Preparation of coated product for test>
A 12 μm-thick single-side treated PET film (manufactured by Toyobo Co., Ltd., trade name “E-5100”) was subjected to corona treatment on the treated surface immediately before water-based ink was applied to refresh the degree of treatment of the film. A base film was used.
The water-based ink was diluted with tap water to prepare a coating ink so that the viscosity measured with a Zahn cup #4 manufactured by Rigosha Co., Ltd. was 14 seconds at 25°C.
Using a flexo hand proofer equipped with an anilox roll with a cell volume of 4.5 cm 3 /m 2 as an applicator, the coating ink was applied onto the substrate film. Then, it was dried at 25° C. for 24 hours to form a coating film on the base film to obtain a coating for test.
＜全濃度の測定＞
セルボリューム１０ｃｍ３／ｍ２のアニロックスロールを搭載したフレキソハンドプルーファーをアプリケーターとして用い、試験用塗工物の塗膜上にバックアップ用の白インキを重ね刷りした。次いで、２５℃で２４時間乾燥させた後に、基材フィルム面を上にして白台紙の上に載せ、濃度計（エックスライト社製、製品名「ｅＸａｃｔ」）を用いてマゼンダ成分の濃度を測定した。
<Measurement of total concentration>
A flexo hand proofer equipped with an anilox roll with a cell volume of 10 cm 3 /m 2 was used as an applicator to overprint white ink for backup on the coating film of the test coating. Next, after drying at 25° C. for 24 hours, the film was placed on a white backing paper with the base film side up, and the concentration of the magenta component was measured using a densitometer (manufactured by X-Rite, product name “eXact”). did.
＜密着性の評価＞
テストピースの塗膜にセロハンテープ（ニチバン株式会社製）を貼り付けた後、このセロハンテープを速やかに剥がし、基材フィルム上に残った塗膜の状態を目視にて確認し、以下の評価基準にて塗膜の基材フィルムに対する密着性を評価した。◎と〇を使用可能なレベル（合格）とした。
◎：塗膜が全く剥離していない。
〇：テストピースの塗膜の総面積に対して、剥離した塗膜の面積の割合が０％超、３０％未満である。
△：テストピースの塗膜の総面積に対して、剥離した塗膜の面積の割合が３０％以上、７０％未満である。
△×：テストピースの塗膜の総面積に対して、剥離した塗膜の面積の割合が７０％以上、１００％未満である。
×：全ての塗膜が剥離した。
<Evaluation of Adhesion>
After attaching a cellophane tape (manufactured by Nichiban Co., Ltd.) to the coating film of the test piece, the cellophane tape was quickly peeled off, and the state of the coating film remaining on the base film was visually confirmed, and the following evaluation criteria were used. was used to evaluate the adhesion of the coating film to the substrate film. ⊚ and ∘ were defined as usable levels (acceptance).
A: The coating film is not peeled off at all.
○: The ratio of the area of the peeled coating film to the total area of the coating film of the test piece is more than 0% and less than 30%.
Δ: The ratio of the area of the peeled coating film to the total area of the coating film of the test piece is 30% or more and less than 70%.
Δ×: The ratio of the area of the peeled coating film to the total area of the coating film of the test piece is 70% or more and less than 100%.
x: All coating films were peeled off.
＜耐ブロッキング性の評価＞
厚さ１２μｍの片面処理ＰＥＴフィルム（東洋紡株式会社製、商品名「Ｅ－５１００」）の未処理面と、試験用塗工物の塗膜側の面とが重なるように、片面処理ＰＥＴフィルムと試験用塗工物とを重ね合わせ、７ｋｇ／ｃｍ２の荷重をかけた状態で４０℃の恒温槽内で２４時間放置した。次いで、片面処理ＰＥＴフィルムと試験用塗工物とを剥離したときの剥離抵抗力と、試験用塗工物の塗膜の外観変化から、以下の評価基準にて塗膜の耐ブロッキング性を評価した。◎と〇を使用可能なレベル（合格）とした。
◎：未処理面へのインキ転移が認められず、剥離抵抗がない。
〇：未処理面へのインキ転移がほとんど認められないが、剥離抵抗をわずかに感じる。
△：未処理面へのインキ転移がやや認められ、剥離抵抗をやや感じる。
△×：未処理面へのインキ転移が認められ、剥離抵抗を感じる。
×：未処理面へのインキ転移がかなり認められ、剥離抵抗をかなり感じる。
<Evaluation of blocking resistance>
A single-sided treated PET film with a thickness of 12 μm (manufactured by Toyobo Co., Ltd., trade name “E-5100”) and a single-sided treated PET film so that the untreated surface overlaps the surface of the test coating on the coating side. The coated material for test was overlaid and left for 24 hours in a constant temperature bath at 40° C. with a load of 7 kg/cm 2 applied. Then, the blocking resistance of the coating film was evaluated according to the following evaluation criteria from the peel resistance when the single-sided treated PET film and the test coating material were peeled off, and the appearance change of the coating film of the test coating material. did. ⊚ and ∘ were defined as usable levels (acceptance).
⊚: No ink transfer to the untreated surface and no peeling resistance.
◯: Almost no ink transfer to the untreated surface is observed, but peeling resistance is slightly felt.
Δ: Some ink transfer to the untreated surface is observed, and peeling resistance is slightly felt.
Δ×: Ink transfer to the untreated surface was observed, and peeling resistance was felt.
x: Significant transfer of ink to the untreated surface was observed, and considerable peeling resistance was felt.
＜版洗浄性の評価＞
セルボリューム４．５ｃｍ３／ｍ２のアニロックスロールを搭載したフレキソハンドプルーファーをアプリケーターとして用い、フレキソ樹脂版の画線部に水性インキを塗工し、そのままの状態で、２５℃で１０分間放置し塗膜を形成した。次いで、台所用洗剤（花王株式会社製、商品名「マジックリン」）を水道水で３倍に希釈した希釈液を塗膜の全体が濡れる程度に吹きかけて、柔らかいブラシで塗膜面をこすり、以下の評価基準にて塗膜の版洗浄性を評価した。〇を使用可能なレベル（合格）とした。
〇：大半の塗膜がフレキソ樹脂版から脱落し、実用上使用可能な洗浄性を有している。
△：フレキソ樹脂版上に残存する塗膜の割合が多く、作業効率がやや悪い。
×：フレキソ樹脂版上にほとんどの塗膜が残存している。
<Evaluation of plate washability>
Using a flexo hand proofer equipped with an anilox roll with a cell volume of 4.5 cm 3 /m 2 as an applicator, water-based ink is applied to the drawing area of the flexo resin plate and left as it is at 25°C for 10 minutes. A coating film was formed. Next, a diluted solution of kitchen detergent (manufactured by Kao Corporation, trade name "Magiclin") diluted 3 times with tap water is sprayed to the extent that the entire coating is wet, and the coating surface is rubbed with a soft brush. The plate washability of the coating film was evaluated according to the following evaluation criteria. ○ was defined as a usable level (pass).
◯: Most of the coating film fell off from the flexo resin plate, and the washability was practically usable.
Δ: A large proportion of the coating film remained on the flexographic resin plate, and the working efficiency was slightly poor.
x: Most of the coating film remains on the flexographic resin plate.
＜再溶解性（印刷適性）の評価＞
セルボリューム４．５ｃｍ３／ｍ２のアニロックスロールを搭載したフレキソハンドプルーファーをアプリケーターとして用い、フレキソ樹脂版の画線部に水性インキを塗工し、そのままの状態で、２５℃で１０分間放置し塗膜を形成した。次いで、ｐＨが８になるように調整した水を１分毎、塗膜にスポイトで１滴滴下し、滴下から１０秒経過した後にガーゼで拭き取り、ガーゼへの塗膜の付着の有無を確認した。塗膜がガーゼへ付着しなくなるまで、すなわち塗膜が水に再溶解しなくなるまで、水の滴下と拭き取りの作業を繰り返した。塗膜が水に再溶解しなくなるまでの所要時間を計測し、以下の評価基準にて塗膜の再溶解性を評価した。◎と〇を使用可能なレベル（合格）とした。
◎：塗膜が水に再溶解しなくなるまでの所要時間が４分以上である。
〇：塗膜が水に再溶解しなくなるまでの所要時間が３分以上、４分未満である。
△：塗膜が水に再溶解しなくなるまでの所要時間が２分以上、３分未満である。
△×：塗膜が水に再溶解しなくなるまでの所要時間が１分以上、２分未満である。
×：塗膜が水に再溶解しなくなるまでの所要時間が１分未満である。
<Evaluation of re-solubility (printability)>
Using a flexo hand proofer equipped with an anilox roll with a cell volume of 4.5 cm 3 /m 2 as an applicator, water-based ink is applied to the drawing area of the flexo resin plate and left as it is at 25°C for 10 minutes. A coating film was formed. Next, one drop of water adjusted to a pH of 8 was dropped on the coating film with a dropper every 1 minute, and after 10 seconds had passed since the dropping, the coating film was wiped off with gauze, and the presence or absence of adhesion of the coating film to the gauze was confirmed. . The operation of dropping water and wiping off was repeated until the coating film stopped adhering to the gauze, that is, until the coating film did not dissolve in water again. The time required for the coating film to stop re-dissolving in water was measured, and the re-solubility of the coating film was evaluated according to the following evaluation criteria. ⊚ and ∘ were defined as usable levels (acceptance).
A: The required time until the coating film no longer dissolves in water is 4 minutes or longer.
Good: The time required for the coating film to stop redissolving in water is 3 minutes or more and less than 4 minutes.
Δ: The time required for the coating film to stop re-dissolving in water is 2 minutes or more and less than 3 minutes.
Δ×: The time required for the coating film to stop re-dissolving in water is 1 minute or more and less than 2 minutes.
x: The required time until the coating film is no longer dissolved in water is less than 1 minute.
［実施例１～１１、比較例１～９］
表１～４に示す配合に従って各材料を混合し、水性インキを得た。
水性インキの調製に用いた水性ウレタン樹脂の全体としての１００％モジュラス及びガラス転移温度を測定した。結果を表１～４に示す。
得られた水性インキを用いて、全濃度を測定し、密着性、耐ブロッキング性、版洗浄性及び再溶解性（印刷適性）を評価した。結果を表１～４に示す。
なお、表中の空欄は、その成分が配合されていないこと（配合量０質量部）を意味する。
[Examples 1 to 11, Comparative Examples 1 to 9]
Each material was mixed according to the formulations shown in Tables 1 to 4 to obtain water-based inks.
The overall 100% modulus and glass transition temperature of the water-based urethane resin used to prepare the water-based ink were measured. The results are shown in Tables 1-4.
Using the water-based ink thus obtained, the total density was measured, and the adhesion, blocking resistance, plate washability and resolubility (printability) were evaluated. The results are shown in Tables 1-4.
A blank in the table means that the component is not blended (0 parts by mass).
表１、２の結果から明らかなように、実施例１～１１で得られた水性インキから形成された塗膜は、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性に優れていた。
一方、表３、４の結果から明らかなように、比較例１～９で得られた水性インキから形成された塗膜は、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性の１つ以上が不十分であった。
As is clear from the results in Tables 1 and 2, the coating films formed from the water-based inks obtained in Examples 1 to 11 had excellent blocking resistance, adhesion to the substrate film, plate washability, and resolubility. was excellent.
On the other hand, as is clear from the results in Tables 3 and 4, the coating films formed from the water-based inks obtained in Comparative Examples 1 to 9 had excellent blocking resistance, adhesion to the substrate film, plate washability, and redissolution. One or more of the genders was inadequate.
本発明の水性インキは、耐ブロッキング性、基材フィルムに対する密着性、版洗浄性及び再溶解性に優れる塗膜を形成でき、グラビア印刷又はフレキソ印刷用のインキとして有用である。 The water-based ink of the present invention is useful as an ink for gravure printing or flexographic printing because it can form a coating film excellent in blocking resistance, adhesion to a base film, plate washability and resolubility.
Claims (5)
前記水性ウレタン樹脂（Ａ１）は、造膜したときの１００％モジュラスが８ＭＰａ未満である水性ウレタン樹脂（Ａ１１）と、造膜したときの１００％モジュラスが８ＭＰａ以上である水性ウレタン樹脂（Ａ１２）とを含み、
前記水性ウレタン樹脂（Ａ１）を造膜したときの１００％モジュラスが２０ＭＰａ未満であり、かつ前記水性ウレタン樹脂（Ａ１）のガラス転移温度が－３０～１３０℃である、軟包装用水性インキ。 Containing an aqueous resin (A) containing an aqueous urethane resin (A1) and an alkalinity-imparting agent (B),
The aqueous urethane resin (A1) includes an aqueous urethane resin (A11) having a 100% modulus of less than 8 MPa when forming a film, and an aqueous urethane resin (A12) having a 100% modulus of 8 MPa or more when forming a film. including
A water-based ink for flexible packaging, wherein the water-based urethane resin (A1) has a 100% modulus of less than 20 MPa when formed into a film, and a glass transition temperature of -30 to 130°C.
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| JPH09291245A (en) * | 1996-04-26 | 1997-11-11 | Toyo Ink Mfg Co Ltd | Method for producing aqueous dispersion of polyurethane resin and aqueous printing ink containing aqueous dispersion of polyurethane resin produced by the method as binder |
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