JP2016196560A - Gravure printing ink composition for surface printing - Google Patents
Gravure printing ink composition for surface printing Download PDFInfo
- Publication number
- JP2016196560A JP2016196560A JP2015076759A JP2015076759A JP2016196560A JP 2016196560 A JP2016196560 A JP 2016196560A JP 2015076759 A JP2015076759 A JP 2015076759A JP 2015076759 A JP2015076759 A JP 2015076759A JP 2016196560 A JP2016196560 A JP 2016196560A
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- mass
- printed
- vinyl chloride
- gravure
- 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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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000003854 Surface Print Methods 0.000 title claims abstract description 33
- 238000007646 gravure printing Methods 0.000 title claims abstract description 29
- -1 diol compound Chemical class 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000000049 pigment Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 22
- 229920002678 cellulose Polymers 0.000 claims description 19
- 239000001913 cellulose Substances 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 16
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 8
- 229940090181 propyl acetate Drugs 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 abstract description 30
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- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 10
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- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000011156 evaluation Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
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- 238000000034 method Methods 0.000 description 7
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- 125000003277 amino group Chemical group 0.000 description 5
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- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- 239000011888 foil Substances 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- PPKVREKQVQREQD-UHFFFAOYSA-N antimony pentasulfide Chemical compound S=[Sb](=S)S[Sb](=S)=S PPKVREKQVQREQD-UHFFFAOYSA-N 0.000 description 1
- 229960001283 antimony pentasulfide Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 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 1
- 235000008429 bread Nutrition 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CNLVKRYETIVYNZ-UHFFFAOYSA-J butyl phosphate;titanium(4+) Chemical compound [Ti+4].CCCCOP([O-])([O-])=O.CCCCOP([O-])([O-])=O CNLVKRYETIVYNZ-UHFFFAOYSA-J 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、表刷り用グラビア印刷インキ組成物に関する。より詳細には、本発明は、塩化ビニルシートに対するブロッキング性（以下、耐塩ビブロッキング性ともいう）および耐アルコール性等の各種皮膜物性の優れる表刷り用グラビア印刷インキ組成物に関する。 The present invention relates to a gravure printing ink composition for surface printing. More specifically, the present invention relates to a gravure printing ink composition for surface printing, which is excellent in various film properties such as blocking property (hereinafter also referred to as vinyl chloride blocking property) and alcohol resistance to a vinyl chloride sheet.
従来、パン、おにぎり、お菓子等の商品の包装には、装飾や表面保護のために表刷りグラビア印刷インキをプラスチックフィルムの表側に印刷し、食品と接触する裏側には印刷しない簡単な構成（表刷り印刷方式といわれる）の印刷物が利用されている。表刷りグラビア印刷インキは、プラスチックフィルムの表側に印刷されるため、インキ皮膜は、外部に直接曝される。そのため、インク皮膜は、強靭な皮膜物性が要求される。 Traditionally, packaging of products such as bread, rice balls, and confectionery has a simple structure in which surface gravure printing ink is printed on the front side of the plastic film for decoration and surface protection and not printed on the back side that comes in contact with food ( Printed material of the surface printing method is used. Since the surface printing gravure printing ink is printed on the front side of the plastic film, the ink film is directly exposed to the outside. Therefore, the ink film is required to have strong film properties.
また、食品メーカーや印刷会社等からは、プラスチックフィルムへの接着性、耐熱性（プラスチックフィルムを製袋する時のヒートシールの熱板が当たる部分においてインキ皮膜が熱板に付着しないための性能）、耐油性（食品中に含有される油分が印刷面に触れた場合でも、それに侵されないための性能）、耐ブロッキング性（印刷面同士あるいは印刷面とフィルムの裏面とが密着しても接着しないための性能）、耐塩ビブロッキング性（テーブル上に置かれたときに、印刷面がテーブルクロス等に用いられている軟質塩化ビニルシートと接着しないための性能）、延伸性（袋を開けるときにフィルムが伸びてフィルムに印刷された印刷面が追随する性能）、耐アルコール性（アルコールが印刷面に触れた場合でも、それにおかされないための性能）等が求められている。 In addition, from food manufacturers and printing companies, adhesiveness to plastic film, heat resistance (performance to prevent the ink film from adhering to the hot plate at the part where the hot plate of the heat seal hits when making plastic film) , Oil resistance (performance to prevent the oil contained in food from touching the printed surface even when it touches it), blocking resistance (printed surfaces or the printed surface and the back of the film do not adhere even if they are in close contact with each other) Performance), PVC blocking resistance (performance to prevent the printed surface from adhering to the soft vinyl chloride sheet used for tablecloths when placed on a table), stretchability (when opening a bag) The film stretches and follows the printed surface printed on the film), alcohol resistance (even if alcohol touches the printed surface, it is not affected by it) Of performance), and the like are required.
これらの強靭な皮膜物性を確保するために、バインダー樹脂として、ポリウレタン樹脂とセルロース誘導体とを使用した表刷り用グラビア印刷インキが提案されている（たとえば、特許文献１および特許文献２）。また、バインダー樹脂としてポリウレタン樹脂と塩化ビニル／酢酸ビニル共重合体とを併用し、さらに、ロジンマレイン酸もしくはロジンエステルおよび／またはチタンキレートを含有する表刷り用グラビアインキ組成物が提案されている（たとえば、特許文献３および特許文献４）。 In order to ensure these tough film properties, gravure printing ink for surface printing using a polyurethane resin and a cellulose derivative as a binder resin has been proposed (for example, Patent Document 1 and Patent Document 2). In addition, a gravure ink composition for surface printing that uses a polyurethane resin and a vinyl chloride / vinyl acetate copolymer in combination as a binder resin and further contains rosin maleic acid or rosin ester and / or titanium chelate has been proposed ( For example, Patent Document 3 and Patent Document 4).
近年、種々の塩化ビニル製製品（たとえばテーブルクロス）が開発されている。これらに対し、特許文献１〜４において提案されているインキ組成物は、いずれもそれらの種々の塩化ビニル製製品に対して充分な塩ビブロッキング性と耐アルコール性とを有していない。特に、耐塩ビブロッキング性の劣るインキ組成物が印刷された印刷物は、インキが塩化ビニル製製品に移るという問題がある。 In recent years, various vinyl chloride products (for example, tablecloths) have been developed. On the other hand, none of the ink compositions proposed in Patent Documents 1 to 4 has sufficient vinyl chloride blocking properties and alcohol resistance for these various vinyl chloride products. In particular, a printed matter on which an ink composition having inferior PVC blocking resistance is printed has a problem that the ink is transferred to a product made of vinyl chloride.
本発明は、このような従来の課題に鑑みてなされたものであり、耐塩ビブロッキング性および耐アルコール性等の皮膜物性の優れる表刷り用グラビア印刷インキ組成物を提供することを目的とする。 The present invention has been made in view of such conventional problems, and an object of the present invention is to provide a gravure printing ink composition for surface printing having excellent film properties such as polyvinyl chloride blocking resistance and alcohol resistance.
上記課題を解決する本発明の表刷り用グラビア印刷インキ組成物には、以下の構成が主に含まれる。 The following composition is mainly contained in the gravure printing ink composition for front printing of the present invention which solves the above-mentioned subject.
（１）顔料と、バインダー樹脂と、硬化剤と、有機溶剤とを含み、前記バインダー樹脂は、ジオール化合物と有機ジイソシアネート化合物とが反応したポリウレタン樹脂を含み、前記硬化剤は、多官能イソシアネート化合物を含み、前記硬化剤の含有量は、３〜１０質量％である、表刷り用グラビア印刷インキ組成物。 (1) A pigment, a binder resin, a curing agent, and an organic solvent are included. The binder resin includes a polyurethane resin in which a diol compound and an organic diisocyanate compound are reacted. The curing agent includes a polyfunctional isocyanate compound. A gravure printing ink composition for surface printing, wherein the content of the curing agent is 3 to 10% by mass.
このような構成によれば、表刷り用グラビアインキ組成物は、充分な接着性、耐熱性、耐油性、耐ブロッキング性、延伸性、耐アルコール性を保持しつつ、種々の塩化ビニル製製品（たとえばテーブルクロス）に対する耐塩ビブロッキング性が優れる。 According to such a structure, the gravure ink composition for surface printing has various vinyl chloride products (while maintaining sufficient adhesion, heat resistance, oil resistance, blocking resistance, stretchability, and alcohol resistance). For example, the polyvinyl chloride blocking resistance to table cloth) is excellent.
（２）前記バインダー樹脂は、さらに、（Ｂ）セルロース誘導体および塩化ビニル／酢酸ビニル共重合体から選ばれる少なくともいずれか１種を含み、（Ａ）および（Ｂ）の少なくともいずれか１種は、多官能イソシアネート化合物と反応する反応基を有している、（１）記載の表刷り用グラビア印刷インキ組成物。 (2) The binder resin further contains at least one selected from (B) a cellulose derivative and a vinyl chloride / vinyl acetate copolymer, and at least one of (A) and (B) is: The gravure printing ink composition for surface printing according to (1), which has a reactive group that reacts with a polyfunctional isocyanate compound.
このような構成によれば、表刷り用グラビアインキ組成物は、充分な接着性、耐熱性、耐油性、耐ブロッキング性、延伸性、耐アルコール性を保持しやすく、種々の塩化ビニル製製品（たとえばテーブルクロス）に対する耐塩ビブロッキング性がより優れる。 According to such a structure, the gravure ink composition for surface printing is easy to maintain sufficient adhesiveness, heat resistance, oil resistance, blocking resistance, stretchability, and alcohol resistance, and various vinyl chloride products ( For example, the polyvinyl chloride blocking resistance to table cloth is more excellent.
（３）さらにキレート化剤、脂肪酸アミドおよびハードレジンを含む、（１）または（２）記載の表刷り用グラビア印刷インキ組成物。 (3) The gravure printing ink composition for surface printing according to (1) or (2), further comprising a chelating agent, a fatty acid amide, and a hard resin.
このような構成によれば、表刷り用グラビアインキ組成物は、充分な接着性、耐熱性、耐油性、耐ブロッキング性、延伸性、耐アルコール性をより安定的に保持しつつ、種々の塩化ビニル製製品（たとえばテーブルクロス）に対する耐塩ビブロッキング性が優れる。 According to such a configuration, the gravure ink composition for surface printing has various chlorides while maintaining sufficient adhesion, heat resistance, oil resistance, blocking resistance, stretchability, and alcohol resistance more stably. Excellent PVC blocking resistance for vinyl products (eg table cloth).
（４）前記有機溶剤は、芳香族炭化水素系有機溶剤を含まず、かつ、酢酸プロピルを含む、（１）〜（３）のいずれかに記載の表刷り用グラビア印刷インキ組成物。 (4) The gravure printing ink composition for surface printing according to any one of (1) to (3), wherein the organic solvent does not include an aromatic hydrocarbon organic solvent and includes propyl acetate.
このような構成によれば、表刷り用グラビアインキ組成物は、環境面に配慮されており、かつ、印刷適性が優れる。 According to such a configuration, the gravure ink composition for surface printing is environmentally friendly and has excellent printability.
本発明によれば、耐塩ビブロッキング性および耐アルコール性等の皮膜物性の優れる表刷り用グラビア印刷インキ組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the gravure printing ink composition for surface printing which is excellent in film physical properties, such as vinyl chloride blocking resistance and alcohol resistance, can be provided.
＜表刷り用グラビア印刷インキ組成物＞
本発明の一実施形態の表刷り用グラビアインキ組成物（以下、単にインキ組成物ともいう）は、顔料と、バインダー樹脂と、硬化剤と、有機溶剤とを含む。以下、それぞれの構成について説明する。
<Gravure printing ink composition for surface printing>
A gravure ink composition for surface printing (hereinafter also simply referred to as an ink composition) according to an embodiment of the present invention includes a pigment, a binder resin, a curing agent, and an organic solvent. Hereinafter, each configuration will be described.
（顔料）
顔料は、一般に有機溶剤を含有するグラビア印刷インキ組成物で使用され得る無機、有機および体質顔料が例示される。無機顔料としては、酸化チタン、ベンガラ、アンチモンレッド、カドミウムレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛等が例示される。有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等が例示される。体質顔料としては、炭酸カルシウム、カオリンクレー、硫酸バリウム、水酸化アルミニウム、タルク等が例示される。
(Pigment)
Examples of the pigment include inorganic, organic and extender pigments that can be used in a gravure printing ink composition generally containing an organic solvent. Examples of inorganic pigments include titanium oxide, bengara, antimony red, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. Examples of extender pigments include calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
顔料の含有量は、特に限定されない。一例を挙げると、白色顔料は、インキ組成物中に０．５〜５０質量％となるよう含有されてもよい。白色以外の顔料は、インキ組成物中に０．５〜２０質量％となるよう含有されてもよい。白色顔料の含有量が０．５質量％未満である場合、発色が不充分となる傾向がある。一方、白色顔料の含有量が５０質量％を超える場合、印刷適性が不充分となる傾向がある。白色以外の顔料の含有量が０．５質量％未満である場合、発色が不充分となる傾向がある。一方、白色以外の顔料の含有量が２０質量％を超える場合、印刷適性が不充分となる傾向がある。 The content of the pigment is not particularly limited. If an example is given, a white pigment may be contained in an ink composition so that it may become 0.5-50 mass%. Pigments other than white may be contained in the ink composition so as to be 0.5 to 20% by mass. When the content of the white pigment is less than 0.5% by mass, color development tends to be insufficient. On the other hand, when the content of the white pigment exceeds 50% by mass, the printability tends to be insufficient. When the content of the pigment other than white is less than 0.5% by mass, color development tends to be insufficient. On the other hand, when the content of the pigment other than white exceeds 20% by mass, the printability tends to be insufficient.
（バインダー樹脂）
バインダー樹脂は、（Ａ）ポリウレタン樹脂、（Ａ）ポリウレタン樹脂と（Ｂ）セルロース誘導体および塩化ビニル／酢酸ビニル共重合体から選ばれる少なくともいずれか１種との併用系が例示できる。耐塩ビブロッキング性および耐アルコール性が優れる点から、バインダー樹脂が（Ａ）ポリウレタン樹脂である場合は、（Ａ）ポリウレタン樹脂が多官能イソシアネート化合物と反応する反応基（たとえば水酸基、アミノ基等）を有しているものが好ましく、（Ａ）ポリウレタン樹脂と（Ｂ）セルロース誘導体および塩化ビニル／酢酸ビニル共重合体から選ばれる少なくともいずれか１種との併用系である場合は（Ａ）および（Ｂ）の少なくともいずれか１種が多官能イソシアネー化合物と反応する反応基（水酸基、アミノ基等）を有していることが好ましい。
(Binder resin)
Examples of the binder resin include (A) a polyurethane resin, (A) a polyurethane resin and (B) a cellulose derivative and a combination system of at least one selected from vinyl chloride / vinyl acetate copolymers. When the binder resin is (A) a polyurethane resin from the viewpoint of excellent vinyl chloride blocking resistance and alcohol resistance, (A) a reactive group (for example, a hydroxyl group, an amino group, etc.) in which the polyurethane resin reacts with a polyfunctional isocyanate compound is used. In the case of a combined system of (A) polyurethane resin and (B) cellulose derivative and at least one selected from vinyl chloride / vinyl acetate copolymer, (A) and (B ) Preferably has a reactive group (hydroxyl group, amino group, etc.) that reacts with the polyfunctional isocyanate compound.
これらの中でも、バインダー樹脂は、ポリウレタン樹脂（Ａ）とセルロース誘導体との併用系、ポリウレタン樹脂（Ａ）と塩化ビニル／酢酸ビニル共重合体との併用系であることが好ましい。ポリウレタン樹脂（Ａ）とセルロース誘導体との併用系は、ポリウレタン樹脂（Ａ）：セルロース誘導体＝５：９５〜９５：５の質量比率となる量で併用するものである。ポリウレタン樹脂（Ａ）とセルロース誘導体との質量比率は、ポリウレタン樹脂（Ａ）：セルロース誘導体＝５０：５０〜７０：３０であることがより好ましい。ポリウレタン樹脂（Ａ）と塩化ビニル／酢酸ビニル共重合体との併用系は、ポリウレタン樹脂（Ａ）と塩化ビニル／酢酸ビニル共重合体とを、ポリウレタン樹脂（Ａ）：塩化ビニル／酢酸ビニル共重合体＝９５：５〜５：９５の質量比率となる量で併用するものである。ポリウレタン樹脂：塩化ビニル／酢酸ビニル共重合体との質量比率は、ポリウレタン樹脂（Ａ）：塩化ビニル／酢酸ビニル共重合体＝９０：１０〜５０：５０であることが好ましく、８０：３０〜６０：４０であることがより好ましい。 Among these, the binder resin is preferably a combined system of a polyurethane resin (A) and a cellulose derivative, or a combined system of a polyurethane resin (A) and a vinyl chloride / vinyl acetate copolymer. The combined system of a polyurethane resin (A) and a cellulose derivative is used together in an amount that results in a mass ratio of polyurethane resin (A): cellulose derivative = 5: 95 to 95: 5. The mass ratio of the polyurethane resin (A) and the cellulose derivative is more preferably polyurethane resin (A): cellulose derivative = 50: 50 to 70:30. The combined system of polyurethane resin (A) and vinyl chloride / vinyl acetate copolymer is polyurethane resin (A) and vinyl chloride / vinyl acetate copolymer, polyurethane resin (A): vinyl chloride / vinyl acetate copolymer Combined = 95: 5 to 5:95 are used together in an amount of mass ratio. The mass ratio of polyurethane resin: vinyl chloride / vinyl acetate copolymer is preferably polyurethane resin (A): vinyl chloride / vinyl acetate copolymer = 90: 10-50: 50, and 80: 30-60 : 40 is more preferable.
バインダー樹脂が、ポリウレタン樹脂（Ａ）とセルロース誘導体との併用系であるか、または、ポリウレタン樹脂（Ａ）と塩化ビニル／酢酸ビニル共重合体の併用系である場合、インキ組成物は、高速印刷適性が優れる。一方、バインダー樹脂は、樹脂フィルムの酸化防止剤による黄変を回避する点からは、ポリウレタン樹脂（Ａ）と塩化ビニル／酢酸ビニル共重合体の併用系であることが好ましい。 When the binder resin is a combined system of the polyurethane resin (A) and the cellulose derivative, or a combined system of the polyurethane resin (A) and the vinyl chloride / vinyl acetate copolymer, the ink composition can be printed at high speed. Excellent aptitude. On the other hand, the binder resin is preferably a combined system of the polyurethane resin (A) and a vinyl chloride / vinyl acetate copolymer from the viewpoint of avoiding yellowing due to the antioxidant of the resin film.
バインダー樹脂の含有量は、インキ組成物中において２．０質量％以上であることが好ましく、４．０質量％以上であることがより好ましい。バインダー樹脂の含有量は、インキ組成物中において２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。バインダー樹脂の含有量が２．０質量％未満である場合、顔料分散が不充分となる傾向がある。一方、バインダー樹脂の含有量が２０質量％を超える場合、耐性が不充分となる傾向がある。 The content of the binder resin is preferably 2.0% by mass or more in the ink composition, and more preferably 4.0% by mass or more. The content of the binder resin is preferably 20% by mass or less, more preferably 15% by mass or less in the ink composition. When the content of the binder resin is less than 2.0% by mass, pigment dispersion tends to be insufficient. On the other hand, when the content of the binder resin exceeds 20% by mass, the resistance tends to be insufficient.
本実施形態において、バインダー樹脂に含まれるポリウレタン樹脂（Ａ）は、ジオール化合物と有機ジイソシアネート化合物とが反応した樹脂である。ジオール化合物と有機ジイソシアネート化合物との反応に際し、鎖伸長剤、反応停止剤等は、適宜使用されてもよい。 In this embodiment, the polyurethane resin (A) contained in the binder resin is a resin in which a diol compound and an organic diisocyanate compound are reacted. In the reaction between the diol compound and the organic diisocyanate compound, a chain extender, a reaction terminator and the like may be used as appropriate.
ジオール化合物としては、数平均分子量が１００以上のアルキレングリコール化合物、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール化合物、および低分子量アルキレングリコールやビスフェノール等のジオール化合物に酸化エチレン、酸化プロピレン等のオキシアルキレンやテトラヒドロフラン等を重付加させて得られるポリエーテルジオール化合物が例示される。また、ジオール化合物としては、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール等の直鎖状グリコール類、１，２−プロパンジオール、ネオペンチルグリコール、３−メチル−１，５−ペンタンジオール、２，４−ジエチル−１，５−ペンタンジオール、エチルブチルプロパンジオール等の分岐グリコール類、ジエチレングリコール、トリエチレングリコール等のエーテル系ジオール類等の低分子ジオール化合物と、コハク酸、アジピン酸、アゼライン酸、セバシン酸、マレイン酸等の飽和および不飽和脂肪族ジカルボン酸、フタル酸等の芳香族ジカルボン酸等のジカルボン酸化合物を、重縮合させて得られるポリエステルジオール化合物、ラクトン等の環状エステル化合物を開環反応させて得られるポリエステルジオール化合物が例示される。 Examples of the diol compound include alkylene glycol compounds having a number average molecular weight of 100 or more, polyalkylene glycol compounds such as polyethylene glycol and polypropylene glycol, diol compounds such as low molecular weight alkylene glycol and bisphenol, oxyalkylenes such as ethylene oxide and propylene oxide, Examples thereof include polyether diol compounds obtained by polyaddition of tetrahydrofuran or the like. Examples of the diol compound include linear glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol, 1,2-propanediol, neopentyl glycol, 3 -Low molecular diol compounds such as branched glycols such as methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and ethylbutylpropanediol, and ether-based diols such as diethylene glycol and triethylene glycol And polyester diols obtained by polycondensation of dicarboxylic acid compounds such as saturated and unsaturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and maleic acid, and aromatic dicarboxylic acids such as phthalic acid Ring-opening reaction of cyclic ester compounds such as compounds and lactones Polyester diol compounds obtained by is exemplified.
ジオール化合物の数平均分子量は、５００を超えることが好ましい。また、ジオール化合物の数平均分子量は、３０００以下であることが好ましく、２０００以下であることがより好ましい。ジオール化合物は、複数が併用されてもよい。ジオール化合物の数平均分子量が５００以下の場合、得られるインキ組成物は、接着性が低下する傾向がある。一方、数平均分子量が３０００を超える場合、得られるインキ組成物は、耐油性が低下する傾向がある。 The number average molecular weight of the diol compound is preferably more than 500. The number average molecular weight of the diol compound is preferably 3000 or less, and more preferably 2000 or less. A plurality of diol compounds may be used in combination. When the number average molecular weight of the diol compound is 500 or less, the obtained ink composition tends to have poor adhesion. On the other hand, when the number average molecular weight exceeds 3000, the resulting ink composition tends to have low oil resistance.
ジイソシアネート化合物としては、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート化合物、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４−シクロヘキシルメタンジイソシアネート等の脂環族ジイソシアネート化合物、キシリレンジイソシアネート、α，α，α’，α’−テトラメチルキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート化合物、トルイレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート化合物が例示される。 Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and alicyclic diisocyanate compounds such as 4,4-cyclohexylmethane diisocyanate, Illustrative are aromatic aliphatic diisocyanate compounds such as xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and aromatic diisocyanate compounds such as toluylene diisocyanate and diphenylmethane diisocyanate.
ポリウレタン樹脂全体の説明に戻り、本実施形態のポリウレタン樹脂（Ａ）は、さらに、直鎖状または側鎖を有するポリカーボネート化合物、およびポリブタジエングリコール化合物等が併用されてもよい。 Returning to the description of the entire polyurethane resin, the polyurethane resin (A) of the present embodiment may be further used in combination with a polycarbonate compound having a linear or side chain, a polybutadiene glycol compound, and the like.
また、ポリウレタン樹脂（Ａ）は、鎖伸長剤や反応停止剤を用いて得られたポリウレタン樹脂であってもよい。鎖伸長剤としては、エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン類、イソホロンジアミン、４，４’−ジシクロヘキシルメタンジアミン等の脂環式ジアミン類、ジエチレントリアミン、トリエチレンテトラトリアミン等のポリアミン類、トルイレンジアミン等の芳香族ジアミン類、キシレンジアミン等の芳香脂肪族ジアミン類、Ｎ−（２−ヒドロキシエチル）エチレンジアミン、Ｎ−（２−ヒドロキシエチル）プロピレンジアミン、Ｎ，Ｎ’−ジ（２−ヒドロキシエチル）エチレンジアミン等の水酸基を有するジアミン類、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、ジエチレングリコール、トリエチレングリコール等のジオール化合物が例示される。反応停止剤としては、メタノール、エタノール等のモノアルコール類、ｎ−プロピルアミン、ｎ−ブチルアミン、ジ−ｎ−ブチルアミン等のアルキルアミン類、モノエタノールアミン、ジエタノールアミン等のアルカノールアミン類、エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン類、イソホロンジアミン、４，４’−ジシクロヘキシルメタンジアミン等の脂環式ジアミン類、ジエチレントリアミン、トリエチレンテトラトリアミン等のポリアミン類、トルイレンジアミン等の芳香族ジアミン類、キシレンジアミン等の芳香脂肪族ジアミン類、Ｎ−（２−ヒドロキシエチル）エチレンジアミン、Ｎ−（２−ヒドロキシエチル）プロピレンジアミン、Ｎ，Ｎ’−ジ（２−ヒドロキシエチル）エチレンジアミン等の水酸基を有するジアミン類等、エチレンジアミン、１，４−ブタンジアミン、イソホロンジアミン、アミノエチルエタノールアミン等の脂肪族ジアミン類等が例示される。 The polyurethane resin (A) may be a polyurethane resin obtained using a chain extender or a reaction terminator. Chain extenders include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine and other aliphatic diamines, isophorone diamine, 4,4'-dicyclohexylmethanediamine and other alicyclic diamines, diethylenetriamine, triethylenetetratriamine Polyamines such as aromatic diamines such as toluylenediamine, araliphatic diamines such as xylenediamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N, N ′ -Di (2-hydroxyethyl) ethylenediamine and other diamines having a hydroxyl group, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, triethylene glycol Diol compound is exemplified in. Reaction stoppers include monoalcohols such as methanol and ethanol, alkylamines such as n-propylamine, n-butylamine and di-n-butylamine, alkanolamines such as monoethanolamine and diethanolamine, ethylenediamine, propylenediamine , Aliphatic diamines such as tetramethylene diamine and hexamethylene diamine, isophorone diamine, alicyclic diamines such as 4,4′-dicyclohexylmethane diamine, polyamines such as diethylenetriamine and triethylenetetratriamine, and toluylenediamine. Aromatic diamines, araliphatic diamines such as xylenediamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N, N′-di (2-hydro) Diamines such as having a hydroxyl group Shiechiru) ethylenediamine, etc., ethylenediamine, 1,4-butanediamine, isophorone diamine, aliphatic diamines such as aminoethyl ethanolamine and the like.
本実施形態のポリウレタン樹脂（Ａ）は、従来公知の各種合成方法により得られ得る。一例を挙げると、ポリウレタン樹脂（Ａ）は、まず、ジイソシアネート化合物のＮＣＯとジオール化合物のＯＨのモル当量比（ジイソシアネート化合物のＮＣＯのモル当量／ジオール化合物のＯＨのモル当量）を０．５以上、好ましくは１．２以上となるよう反応させる。ジイソシアネート化合物のＮＣＯのモル当量／ジオール化合物のＯＨのモル当量は、３以下であることが好ましく１．５以下であることがより好ましい。次いで、ポリウレタン樹脂は、必要に応じて鎖伸長剤、反応停止剤が添加され、得られる。なお、ジイソシアネート化合物のＮＣＯのモル当量／ジオール化合物のＯＨのモル当量が０．５未満の場合、得られるインキ組成物は、耐熱性、耐油性が低下する傾向がある。一方、ＮＣＯのモル当量／ジオール化合物のＯＨのモル当量が３を超える場合、得られるインキ組成物は、延伸性が低下する傾向がある。 The polyurethane resin (A) of this embodiment can be obtained by various conventionally known synthesis methods. For example, in the polyurethane resin (A), first, the molar equivalent ratio of NCO of the diisocyanate compound and OH of the diol compound (molar equivalent of NCO of diisocyanate compound / molar equivalent of OH of diol compound) is 0.5 or more. The reaction is preferably carried out to 1.2 or more. The molar equivalent of NCO of the diisocyanate compound / the molar equivalent of OH of the diol compound is preferably 3 or less, and more preferably 1.5 or less. Next, the polyurethane resin is obtained by adding a chain extender and a reaction terminator as necessary. In addition, when the molar equivalent of NCO of the diisocyanate compound / the molar equivalent of OH of the diol compound is less than 0.5, the obtained ink composition tends to have poor heat resistance and oil resistance. On the other hand, when the molar equivalent of NCO / the molar equivalent of OH of the diol compound exceeds 3, the resulting ink composition tends to have poor stretchability.
本実施形態において、ポリウレタン樹脂は、得られるインキ組成物の樹脂フィルムに対する接着性、耐ブロッキング性、耐油性、耐熱性、耐塩ビブロッキング性、耐アルコール性等を向上させる点から、水酸基を有するポリウレタン樹脂またはアミノ基を有するポリウレタン樹脂であることが好ましい。 In this embodiment, the polyurethane resin is a polyurethane having a hydroxyl group from the viewpoint of improving the adhesion of the obtained ink composition to the resin film, blocking resistance, oil resistance, heat resistance, vinyl chloride blocking resistance, alcohol resistance, and the like. A polyurethane resin having a resin or an amino group is preferred.
このような水酸基を有するポリウレタン樹脂、および、アミノ基を有するポリウレタン樹脂は、いずれも従来公知の各種方法により得られる。一例を挙げると、水酸基を有するポリウレタン樹脂は、（１）鎖伸長剤や反応停止剤を用いずに、有機ジイソシアネート化合物をポリオール化合物の１．０倍未満のモル比率で反応させる方法、（２）有機ジイソシアネート化合物とポリオール化合物を反応させてウレタンプレポリマーを合成した後、鎖伸長剤としてグリセリン、アミノエチルエタノールアミン等のジアミノアルコール化合物、反応停止剤としてモノエタノールアミン、ジエタノールアミン等のアルカノールアミン化合物を反応させて水酸基を導入する方法等により得られる。また、アミノ基を有するポリウレタン樹脂は、（１）高分子ジオール、および、ポリイソシアネートを反応させて得られる、末端にイソシアネート基を有するウレタンプレポリマーに、鎖伸長剤を加え、鎖伸長を行うことによって末端にイソシアネート基を有するウレタンプレポリマーを得た後、両末端が第１級アミノ基および第２級アミノ基のいずれか一方であるポリアミン化合物以外の反応停止剤を反応させ、次いで、両末端が第１級アミノ基および第２級アミノ基のいずれか一方であるポリアミン化合物である反応停止剤を反応させ、第１級アミノ基および第２級アミノ基のいずれか一方を有するポリウレタン樹脂を得る方法、（２）高分子ジオール、および、ポリイソシアネートを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに、鎖伸長剤を加え、鎖伸長を行い末端にイソシアネート基を有するウレタンプレポリマーを得た後、反応停止剤として、両末端が第１級アミノ基および第２級アミノ基のいずれか一方であるポリアミン化合物を反応させ、鎖伸長と反応停止を同時に行い、第１級アミノ基および／または第２級アミノ基を有するポリウレタン樹脂を得る方法等により製造し得る。 Both the polyurethane resin having such a hydroxyl group and the polyurethane resin having an amino group can be obtained by various conventionally known methods. For example, a polyurethane resin having a hydroxyl group is (1) a method in which an organic diisocyanate compound is reacted at a molar ratio of less than 1.0 times that of a polyol compound without using a chain extender or a reaction terminator, (2) After reacting an organic diisocyanate compound and a polyol compound to synthesize a urethane prepolymer, it reacts with a diamino alcohol compound such as glycerin or aminoethylethanolamine as a chain extender and an alkanolamine compound such as monoethanolamine or diethanolamine as a reaction terminator. For example, by introducing a hydroxyl group. In addition, the polyurethane resin having an amino group is obtained by (1) adding a chain extender to a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polymer diol and a polyisocyanate, thereby performing chain extension. After obtaining a urethane prepolymer having an isocyanate group at the terminal by the reaction, a reaction terminator other than a polyamine compound in which both terminals are either a primary amino group or a secondary amino group is reacted, and then both terminals Is reacted with a reaction terminator which is a polyamine compound which is either a primary amino group or a secondary amino group to obtain a polyurethane resin having either a primary amino group or a secondary amino group Method, (2) a polymer having a isocyanate group at the terminal obtained by reacting a polymer diol and a polyisocyanate. After adding a chain extender to the tan prepolymer to obtain a urethane prepolymer having an isocyanate group at the end by chain extension, either end is either a primary amino group or a secondary amino group as a reaction terminator On the other hand, it can be produced by a method in which a polyamine compound is reacted to carry out chain extension and reaction termination at the same time to obtain a polyurethane resin having a primary amino group and / or a secondary amino group.
次に、本実施形態において、バインダー樹脂に含まれるポリウレタン樹脂（Ａ）と併用することができる（Ｂ）セルロース誘導体、塩化ビニル／酢酸ビニル共重合体について説明する。 Next, in this embodiment, (B) a cellulose derivative and a vinyl chloride / vinyl acetate copolymer that can be used in combination with the polyurethane resin (A) contained in the binder resin will be described.
（塩化ビニル／酢酸ビニル共重合体）
塩化ビニル／酢酸ビニル共重合体としては、従来からインキ組成物に使用されている塩化ビニルモノマーと酢酸ビニルモノマーの共重合体が適宜使用される。塩化ビニル／酢酸ビニル共重合体は、環境面に配慮したインキの有機溶剤系において、インキ組成物の各種皮膜特性をバランスよく向上させる点から、水酸基を有する塩化ビニル／酢酸ビニル共重合体であることが好ましい。
(Vinyl chloride / vinyl acetate copolymer)
As the vinyl chloride / vinyl acetate copolymer, a copolymer of vinyl chloride monomer and vinyl acetate monomer conventionally used in ink compositions is appropriately used. The vinyl chloride / vinyl acetate copolymer is a vinyl chloride / vinyl acetate copolymer having a hydroxyl group from the viewpoint of improving the various film properties of the ink composition in a balanced manner in an organic solvent system of an ink that is environmentally friendly. It is preferable.
このような水酸基を有する塩化ビニル／酢酸ビニル共重合体は、たとえば、酢酸エステル部分の一部をケン化することにより調製し得る。酢酸エステル部分の一部をケン化することにより得られた水酸基を有する塩化ビニル／酢酸ビニル共重合体の場合、分子中の塩化ビニルの反応部位に基づく構成単位（下記式（１））、酢酸ビニルの反応部位に基づく構成単位（下記式（２））および酢酸ビニルの反応部位のケン化に基づく構成単位（下記式（３））の比率により樹脂の皮膜物性や溶解挙動が決定される。すなわち、塩化ビニルの反応部位に基づく構成単位は、樹脂皮膜の強靭さや硬さを付与し、酢酸ビニルの反応部位に基づく構成単位は接着性や柔軟性を付与し、酢酸ビニルの反応部位のケン化に基づく構成単位は環境面に配慮したインキの有機溶剤系への良好な溶解性を付与し得る。
式（１） −ＣＨ2−ＣＨＣｌ−
式（２） −ＣＨ2−ＣＨ（ＯＣＯＣＨ3）−
式（３） −ＣＨ2−ＣＨ（ＯＨ）−
Such a vinyl chloride / vinyl acetate copolymer having a hydroxyl group can be prepared, for example, by saponifying a part of the acetate portion. In the case of a vinyl chloride / vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate portion, a structural unit based on the reaction site of vinyl chloride in the molecule (the following formula (1)), acetic acid The film physical properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the vinyl reaction site (the following formula (2)) and the structural unit based on the saponification of the vinyl acetate reaction site (the following formula (3)). That is, the structural unit based on the reaction site of vinyl chloride provides toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate provides adhesion and flexibility. The structural unit based on the chemical conversion can impart good solubility in the organic solvent system of the ink in consideration of the environment.
Formula (1) —CH 2 —CHCl—
Formula (2) —CH 2 —CH (OCOCH 3 ) —
Formula (3) —CH 2 —CH (OH) —
（セルロース誘導体）
セルロース誘導体としては、従来から表刷り用グラビア印刷インキ組成物に使用されているセルロース誘導体が適宜使用される。セルロース誘導体としては、ニトロセルロース（ニトロ基置換体）、セルロースアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート等の低級アシル基置換体、メチルセルロース、エチルセルロース等の低級アルキル基置換体が例示される。これらセルロース誘導体の分子量や水酸基に対する置換度等は、通常のインキ組成物や塗料で使用される範囲のものが採用され得る。一例を挙げると、水酸基の置換度は、１．３〜２．７程度であることが好ましい。また、セルロース誘導体は、所望する目的に合わせて適宜選択して使用されることが好ましい。セルロース誘導体は、耐熱性の点からはニトロ基置換体が使用されることが好ましく、接着性の点からは低級アシル基置換体および低級アルキル基置換体が使用されることが好ましい。
(Cellulose derivative)
As a cellulose derivative, the cellulose derivative conventionally used for the gravure printing ink composition for surface printing is used suitably. Examples of cellulose derivatives include nitrocellulose (nitro group-substituted products), lower acyl group-substituted products such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, and lower alkyl group-substituted products such as methyl cellulose and ethyl cellulose. The molecular weight of these cellulose derivatives, the degree of substitution with respect to hydroxyl groups, and the like can be employed within the range used in ordinary ink compositions and paints. For example, the hydroxyl group substitution degree is preferably about 1.3 to 2.7. Moreover, it is preferable that a cellulose derivative is suitably selected and used according to the desired purpose. As the cellulose derivative, a nitro group-substituted product is preferably used from the viewpoint of heat resistance, and a lower acyl group-substituted product and a lower alkyl group-substituted product are preferably used from the viewpoint of adhesiveness.
（硬化剤）
硬化剤は、多官能イソシアネート化合物が例示される。この中でも、硬化剤は、架橋構造を形成しやすい点で、平均官能基数が２より大きい多官能イソシアネート化合物であることが好ましい。具体的には、多官能イソシアネート化合物は、デュラネートＴＰＡ−１００（旭化成ケミカルズ（株）製、イソシアヌレート型ＨＤＩ）、デュラネートＰ３０１−７５Ｅ（旭化成ケミカルズ（株）製、トリメチロールプロパンアダクト型ＨＤＩ）、マイテックＮＹ−２１０Ａ（三菱化学（株）製、トリメチロールプロパンアダクト型ＩＰＤＩ）、コロネートＬ（日本ポリウレタン工業（株）製、トリメチロールプロパンアダクト型ＴＤＩ）等が例示される。なお、これら硬化剤は、たとえば印刷時の直前に添加され得る。
(Curing agent)
Examples of the curing agent include polyfunctional isocyanate compounds. Among these, the curing agent is preferably a polyfunctional isocyanate compound having an average functional group number greater than 2 in that it easily forms a crosslinked structure. Specifically, the polyfunctional isocyanate compound includes Duranate TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, isocyanurate type HDI), Duranate P301-75E (manufactured by Asahi Kasei Chemicals Corporation, trimethylolpropane adduct type HDI), My Examples include Tech NY-210A (manufactured by Mitsubishi Chemical Corporation, trimethylolpropane adduct type IPDI), Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd., trimethylolpropane adduct type TDI), and the like. These curing agents can be added, for example, immediately before printing.
硬化剤の含有量は、インキ組成物中に３質量％以上であればよく、５質量％以上であることが好ましい。また、硬化剤の含有量は、インキ組成物中に１０質量％以下であればよく、８質量％以下であることが好ましい。硬化剤の含有量が３質量％未満の場合、インキ組成物は、各種皮膜特性を充足できない傾向がある。一方、硬化剤の含有量が１０質量％を超える場合、印刷後の残肉インキの安定性が低下する傾向がある。 Content of a hardening | curing agent should just be 3 mass% or more in an ink composition, and it is preferable that it is 5 mass% or more. Moreover, content of a hardening | curing agent should just be 10 mass% or less in an ink composition, and it is preferable that it is 8 mass% or less. When the content of the curing agent is less than 3% by mass, the ink composition tends to be unable to satisfy various film properties. On the other hand, when the content of the curing agent exceeds 10% by mass, the stability of the remaining ink after printing tends to decrease.
（有機溶剤）
有機溶剤としては、上記各種成分を適切に配合し得る溶剤であれば特に限定されない。本実施形態では、有機溶剤は、環境面に配慮して、芳香族炭化水素系有機溶剤を含まないことが好ましい。芳香族炭化水素系有機溶剤を含有しない有機溶剤としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ブタノールなどのアルコール系有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系有機溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系有機溶剤、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン等の脂肪族炭化水素系有機溶剤、および、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロヘプタン、シクロオクタン等の脂環族炭化水素系有機溶剤が例示される。これらの有機溶剤は、バインダー樹脂の溶解性や乾燥性等を考慮して、適宜混合して利用し得る。環境面に配慮すると、有機溶剤は、可能な限りケトン系有機溶剤を使用しないことが好ましい。
(Organic solvent)
The organic solvent is not particularly limited as long as it is a solvent capable of appropriately blending the above various components. In the present embodiment, it is preferable that the organic solvent does not contain an aromatic hydrocarbon organic solvent in consideration of the environment. Examples of organic solvents that do not contain aromatic hydrocarbon organic solvents include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol, ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl acetate, Ester organic solvents such as ethyl acetate, propyl acetate and butyl acetate, aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane and n-octane, and cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclohexane Examples include alicyclic hydrocarbon organic solvents such as octane. These organic solvents can be appropriately mixed and used in consideration of the solubility and drying property of the binder resin. In consideration of the environment, it is preferable that the organic solvent is not a ketone organic solvent as much as possible.
有機溶剤の使用量としては、得られるインキ組成物の印刷性が優れる点から、インキ組成物中１５．０質量％以上であることが好ましい。また、有機溶剤の使用量は、９０質量％以下であることが好ましい。有機溶剤の使用量が１５．０質量％未満である場合、印刷適性が低位となる傾向がある。一方、有機溶剤の使用量が９０質量％を超える場合、充分な発色および塗膜物性が得られない傾向がある。この場合において、有機溶剤には、酢酸プロピルが含まれることが好ましい。酢酸プロピルは、インキ組成物中５．０質量％以上含まれることが好ましく、１０．０質量％以上含まれることがより好ましい。 The amount of the organic solvent used is preferably 15.0% by mass or more in the ink composition from the viewpoint of excellent printability of the obtained ink composition. Moreover, it is preferable that the usage-amount of an organic solvent is 90 mass% or less. When the amount of the organic solvent used is less than 15.0% by mass, the printability tends to be low. On the other hand, when the amount of the organic solvent used exceeds 90% by mass, sufficient color development and coating film properties tend not to be obtained. In this case, the organic solvent preferably contains propyl acetate. Propyl acetate is preferably contained in the ink composition in an amount of 5.0% by mass or more, and more preferably 10.0% by mass or more.
次に、本実施形態のインキ組成物において好適に含まれる成分について説明する。インキ組成物は、好適には、キレート化剤、脂肪酸アミドおよびハードレジンから選ばれる少なくとも１種、さらに好適には、キレート化剤、脂肪酸アミドおよびハードレジンを含む。インキ組成物は、耐熱性、耐油性、耐塩ビブロッキング性、耐アルコール性等を向上させるために、好適にはキレート化剤、ハードレジンおよび脂肪酸アミドが併用される。 Next, components suitably contained in the ink composition of the present embodiment will be described. The ink composition preferably includes at least one selected from a chelating agent, a fatty acid amide, and a hard resin, and more preferably includes a chelating agent, a fatty acid amide, and a hard resin. In the ink composition, a chelating agent, a hard resin and a fatty acid amide are preferably used in combination in order to improve heat resistance, oil resistance, vinyl chloride blocking resistance, alcohol resistance and the like.
（キレート化剤）
キレート化剤としては、チタンキレート、ジルコニウムキレート等の金属キレート化剤が好適に使用される。チタンキレートとしては、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラ（２−エチルヘキシル）チタネート、テトラメチルチタネート、テトラステアリルチタネートなどのチタンアルコキシド、トリエタノールアミンチタネート、チタニウムアセチルアセテート、チタニウムエチルアセトアセテート、チタニウムラクテート、オクチレングリコールチタネート、チタンテトラアセチルアセトナート、ｎ−ブチルリン酸エステルチタン、プロパンジオキスチタンビス（エチルアセチルアセテート）等が例示される。ジルコニウムキレートとしては、ジルコニウムプロピオネート、ジルコニウムアセチルアセテート等が例示される。
(Chelating agent)
As the chelating agent, metal chelating agents such as titanium chelate and zirconium chelate are preferably used. Titanium chelates such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate, tetrastearyl titanate, triethanolamine titanate, titanium acetyl acetate, titanium ethyl acetoacetate Examples include acetate, titanium lactate, octylene glycol titanate, titanium tetraacetylacetonate, n-butyl phosphate titanium, propanediox titanium bis (ethylacetylacetate), and the like. Examples of the zirconium chelate include zirconium propionate and zirconium acetyl acetate.
キレート化剤は、環境面に配慮すると、架橋反応後にアセチルアセトンを発生しないキレート化剤であることが好ましい。 In consideration of the environment, the chelating agent is preferably a chelating agent that does not generate acetylacetone after the crosslinking reaction.
キレート化剤の含有量は、インキ組成物中、０．１質量％以上であることが好ましく、１．０質量％以上であることがより好ましい。また、キレート化剤の含有量は、インキ組成物中、８．０質量％以下であることが好ましく、２．０質量％以下であることがより好ましい。キレート化剤の含有量が０．１質量％未満である場合、得られるインキ組成物は、耐熱性、耐油性、耐塩ビブロッキング性、耐アルコール性が低下する傾向がある。一方、キレート化剤の含有量が８．０質量％を超える場合、得られるインキ組成物の経時安定性が低下する傾向がある。 The content of the chelating agent in the ink composition is preferably 0.1% by mass or more, and more preferably 1.0% by mass or more. Further, the content of the chelating agent in the ink composition is preferably 8.0% by mass or less, and more preferably 2.0% by mass or less. When the content of the chelating agent is less than 0.1% by mass, the resulting ink composition tends to decrease in heat resistance, oil resistance, vinyl chloride blocking resistance, and alcohol resistance. On the other hand, when the content of the chelating agent exceeds 8.0% by mass, the temporal stability of the obtained ink composition tends to decrease.
（脂肪酸アミド）
脂肪酸アミドとしては、飽和脂肪酸アミド、不飽和脂肪酸アミド、変性脂肪酸アミド等が例示される。これらの中でも、脂肪酸アミドは、たとえばテーブルクロスに使用される軟質塩化ビニルシートに対する耐塩ビブロッキング性が優れる点から、変性脂肪酸アミドであることが好ましい。
(Fatty acid amide)
Examples of fatty acid amides include saturated fatty acid amides, unsaturated fatty acid amides, and modified fatty acid amides. Among these, the fatty acid amide is preferably a modified fatty acid amide from the viewpoint of excellent vinyl chloride blocking resistance with respect to a soft vinyl chloride sheet used for a table cloth, for example.
脂肪酸アミドの含有量は、インキ組成物中、０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。また、脂肪酸アミドの含有量は、インキ組成物中、３．０質量％以下であることが好ましく、２．０質量％以下であることがより好ましい。脂肪酸アミドの含有量が０．１質量％未満である場合、耐ブロッキング性、接着性が低下する可能性がある。一方、脂肪酸アミドの配合量が３．０質量％を超える場合、得られるインキ組成物は、耐塩ビブロッキング性が低下する可能性がある。 The content of the fatty acid amide in the ink composition is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. Further, the content of the fatty acid amide in the ink composition is preferably 3.0% by mass or less, and more preferably 2.0% by mass or less. When the content of the fatty acid amide is less than 0.1% by mass, blocking resistance and adhesiveness may be lowered. On the other hand, when the blending amount of the fatty acid amide exceeds 3.0% by mass, the resulting ink composition may have a reduced vinyl chloride blocking resistance.
（ハードレジン）
ハードレジンとしては、ダイマー酸系樹脂、ロジン系樹脂、マレイン酸系樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、ダンマー樹脂、コーパル樹脂、塩素化ポリプロピレン、酸化ポリプロピレン等が例示される。これらハードレジンを配合することにより、得られるインキ組成物は、特に表面処理の行なわれていない樹脂フィルムに対して、接着性が向上し得る。
(Hard resin)
Examples of the hard resin include dimer acid resins, rosin resins, maleic resins, petroleum resins, terpene resins, ketone resins, dammar resins, copal resins, chlorinated polypropylene, and polypropylene oxide. By blending these hard resins, the resulting ink composition can have improved adhesion to a resin film that has not been surface-treated.
ハードレジンの含有量は、インキ組成物中、０．１質量％以上であることが好ましい。ハードレジンの含有量は、インキ組成物中、５．０質量％以下であることが好ましい。ハードレジンの含有量は、インキ組成物中、０．１質量％未満である場合、キレート化剤を使用する場合にインキ安定性が不充分となる傾向がある。一方、ハードレジンの含有量がインキ組成物中５．０質量％を超える場合、塗膜耐性が不充分となる傾向がある。 The content of the hard resin is preferably 0.1% by mass or more in the ink composition. The content of the hard resin is preferably 5.0% by mass or less in the ink composition. When the content of the hard resin is less than 0.1% by mass in the ink composition, the ink stability tends to be insufficient when a chelating agent is used. On the other hand, when the content of the hard resin exceeds 5.0% by mass in the ink composition, the coating film resistance tends to be insufficient.
次に、本実施形態のインキ組成物において含まれてもよい任意成分について説明する。インキ組成物は、ワックス、顔料分散剤、レベリング剤、界面活性剤、可塑剤等が含まれてもよい。ワックスは、得られるインキ組成物の耐摩擦性を向上させるために適宜配合され得る。ワックスとしては、ポリオレフィンワックス、パラフィンワックス等の既知の各種ワックスが例示される。 Next, optional components that may be included in the ink composition of the present embodiment will be described. The ink composition may contain a wax, a pigment dispersant, a leveling agent, a surfactant, a plasticizer, and the like. The wax can be appropriately blended in order to improve the friction resistance of the resulting ink composition. Examples of the wax include various known waxes such as polyolefin wax and paraffin wax.
本実施形態のインキ組成物の製造方法は特に限定されない。一例を挙げると、インキ組成物は、顔料、バインダー樹脂、有機溶剤、および必要に応じて顔料分散剤、界面活性剤等を攪拌混合した後、各種練肉機、たとえば、ビーズミル、ボールミル、サンドミル、アトライター、ロールミル、パールミル等を利用して練肉し、さらに、脂肪酸アミド、キレート化剤、ハードレジンおよび残りの材料を添加混合し、印刷時に硬化剤を添加混合する方法により調製され得る。 The manufacturing method of the ink composition of this embodiment is not specifically limited. For example, the ink composition comprises a pigment, a binder resin, an organic solvent, and, if necessary, a pigment dispersant, a surfactant and the like after stirring and mixing, and then various kneaders such as a bead mill, a ball mill, a sand mill, It can be prepared by a method of kneading using an attritor, a roll mill, a pearl mill or the like, further adding and mixing a fatty acid amide, a chelating agent, a hard resin and the remaining materials, and adding and mixing a curing agent during printing.
得られたインキ組成物は、グラビア印刷方式で、表刷り用として各種プラスチックフィルム等の被着体に印刷され得る。プラスチックフィルムとしては、特に、包装材料と一体的な印刷が可能である点において、ポリエチレン、ポリプロピレン等の延伸および無延伸ポリオレフィン、ポリエステル、ナイロン、セロファン、ビニロン等が例示される。得られた印刷物は、製袋され、食品等の包装容器として利用され得る。 The obtained ink composition can be printed on an adherend such as various plastic films for surface printing by a gravure printing method. Examples of the plastic film include stretched and non-stretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, vinylon and the like, particularly in that printing can be performed integrally with the packaging material. The obtained printed matter is made into a bag and can be used as a packaging container for food or the like.
以上、本実施形態のインキ組成物は、被着体に印刷される際に、充分な接着性、耐熱性、耐油性、耐ブロッキング性、延伸性、耐アルコール性を保持しつつ、種々の塩化ビニル製製品（たとえばテーブルクロス）に対する耐塩ビブロッキング性が優れる。そのため、インキ組成物は、各種皮膜特性が優れており、食品メーカーや印刷会社だけでなく、一般家庭において不都合なく取り扱われ得る。特に、得られた印刷物は、塩化ビニル製のテーブルクロス等に置かれたときであっても、印刷面がテーブルクロス等に接着せず、インクがテーブルクロス等に写りにくい。 As described above, the ink composition of the present embodiment has various chlorides while maintaining sufficient adhesion, heat resistance, oil resistance, blocking resistance, stretchability, and alcohol resistance when printed on an adherend. Excellent PVC blocking resistance for vinyl products (eg table cloth). Therefore, the ink composition is excellent in various film properties and can be handled without inconvenience not only in food manufacturers and printing companies but also in general households. In particular, even when the obtained printed matter is placed on a vinyl chloride table cloth or the like, the printed surface does not adhere to the table cloth or the like, and the ink is difficult to appear on the table cloth or the like.
以下、実施例により本発明をより具体的に説明する。本発明は、これら実施例に何ら限定されない。なお、特に制限のない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “parts” means “mass parts”.
使用した原料および調製方法を以下に示す。
＜顔料＞
白色顔料（酸化チタン）
藍色顔料（ＰＢ１５：４顔料）
＜ポリウレタン樹脂ワニスＡ＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに、数平均分子量１，０００のポリエチレングリコール４００ｇおよびイソホロンジイソシアネート１１５．４ｇ、テトラブチルチタネート０．１ｇを仕込み、窒素ガスを導入しながら１００℃で４時間反応させた。酢酸エチル３７５ｇ、酢酸プロピル５００ｇ、イソプロピルアルコール３７５ｇを加えた後、イソホロンジアミン２０．７ｇを加えて２０分間反応させ、さらにモノエタノールアミン１．２５ｇを加えて反応を停止し、ポリウレタン樹脂ワニスＡ（固形分３０％）を得た。
＜ポリウレタン樹脂ワニスＢ＞
攪拌機、冷却管および窒素ガス導入管を備えた四つ口フラスコに平均分子量２，０００の３−メチル−１，５−ペンチレンアジペートジオール１００質量部、平均分子量２，０００のポリプロピレングリコール１００質量部、およびイソホロンジイソシアネート４４．４質量部を仕込み、窒素ガスを導入しながら１００〜１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル５２１質量部、イソプロピルアルコール９２質量部を加えた後、イソホロンジアミン１５．６質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３１質量部を加え反応させ、その後、イソホロンジアミン２．１８質量部、ジエチレントリアミン０．１７質量部を加えて反応停止させてポリウレタン樹脂ワニスＢ（固形分３０質量％）を得た。
＜塩化ビニル／酢酸ビニル共重合体溶液＞
塩化ビニル／酢酸ビニル樹脂共重合体（商品名：ソルバインＴＡ５Ｒ、日信化学（株）製）の２０部を、メチルエチルケトン４０部、酢酸エチルの２０部、酢酸プロピルの２０部からなる混合有機溶剤中に溶解させて固形分２０％の塩化ビニル／酢酸ビニル樹脂溶液を得た。
＜ニトロセルロース溶液＞
ニトロセルロース（商品名：ＮＣ ＲＳ−２ ＫＣＮＣ、ＫＯＲＥＡ ＣＮＣ ＬＴＤ社製）２０部を、酢酸プロピル３５部およびイソプロピルアルコール４５部からなる混合溶媒に溶解させて固形分２０％のニトロセルロース溶液を得た。
＜硬化剤＞
トリメチロールプロパンのヘキサメチレンジイソシアネートのアダクト品
＜脂肪酸アミド＞
ラウリン酸アミド
＜金属キレート化剤＞
チタニウムアセチルアセテート
＜ハードレジン＞
ハードレジン（商品名：マルキードＮｏ．２ 荒川化学工業（株）製）
The raw materials used and the preparation methods are shown below.
<Pigment>
White pigment (titanium oxide)
Indigo pigment (PB15: 4 pigment)
<Polyurethane resin varnish A>
A four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe was charged with 400 g of polyethylene glycol having a number average molecular weight of 1,000, 115.4 g of isophorone diisocyanate, and 0.1 g of tetrabutyl titanate while introducing nitrogen gas. The reaction was carried out at 100 ° C. for 4 hours. After adding 375 g of ethyl acetate, 500 g of propyl acetate, and 375 g of isopropyl alcohol, 20.7 g of isophoronediamine was added and reacted for 20 minutes, and further 1.25 g of monoethanolamine was added to stop the reaction, and polyurethane resin varnish A (solid 30%).
<Polyurethane resin varnish B>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas introduction tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2,000 and 100 parts by mass of polypropylene glycol having an average molecular weight of 2,000 And 44.4 parts by mass of isophorone diisocyanate were added and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture is allowed to cool to near room temperature, 521 parts by mass of ethyl acetate and 92 parts by mass of isopropyl alcohol are added, then 15.6 parts by mass of isophoronediamine is added to extend the chain, and 0.31 part by mass of monoethanolamine is further added and reacted. Thereafter, 2.18 parts by mass of isophoronediamine and 0.17 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish B (solid content: 30% by mass).
<Vinyl chloride / vinyl acetate copolymer solution>
20 parts of a vinyl chloride / vinyl acetate resin copolymer (trade name: Solvain TA5R, manufactured by Nissin Chemical Co., Ltd.) in a mixed organic solvent comprising 40 parts of methyl ethyl ketone, 20 parts of ethyl acetate, and 20 parts of propyl acetate To obtain a vinyl chloride / vinyl acetate resin solution having a solid content of 20%.
<Nitrocellulose solution>
20 parts of nitrocellulose (trade name: NC RS-2 KCNC, manufactured by KOREA CNC LTD) was dissolved in a mixed solvent consisting of 35 parts of propyl acetate and 45 parts of isopropyl alcohol to obtain a nitrocellulose solution having a solid content of 20%. .
<Curing agent>
Trimethylolpropane hexamethylene diisocyanate adduct <fatty acid amide>
Lauric acid amide <metal chelating agent>
Titanium acetyl acetate <hard resin>
Hard resin (trade name: Marquide No. 2 manufactured by Arakawa Chemical Industries, Ltd.)
＜インキ組成物の調製＞
表１に示される処方に沿って、白色インキ組成物（１）〜（１０）と、藍色インキ組成物（１）〜（１０）を調製した。具体的には、表１に示す材料をペイントコンディショナーで混練し、それぞれのインキ組成物を調製した。
<Preparation of ink composition>
According to the formulation shown in Table 1, white ink compositions (1) to (10) and indigo ink compositions (1) to (10) were prepared. Specifically, the materials shown in Table 1 were kneaded with a paint conditioner to prepare each ink composition.
＜実施例１＞表刷り印刷物の作製
コロナ放電処理した延伸ポリプロピレンフィルム（商品名：ＯＰＰ Ｐ−２１６１、２５μｍ、東洋紡（株）製）に、グラビア校正機を利用して表刷り用グラビア印刷インキ組成物（白色）を下記条件で印刷、乾燥させた後、表刷用グラビア印刷インキ組成物（藍色）を下記条件で印刷、乾燥させて、表刷りグラビア印刷物を作製した。
<Example 1> Production of surface printed matter Gravure printing ink composition for surface printing on a stretched polypropylene film (trade name: OPP P-2161, 25 μm, manufactured by Toyobo Co., Ltd.) subjected to corona discharge treatment using a gravure proofing machine. The product (white) was printed and dried under the following conditions, and then the gravure printing ink composition for surface printing (blue) was printed and dried under the following conditions to prepare a surface printing gravure printed material.
（表刷り用グラビア印刷インキ組成物の塗工方法・条件）
塗工機 ：グラビア校正機
塗工速度 ：１００ｍ／ｍｉｎ
刷版 ：ダイレクト１７５線ベタ版
乾燥温度 ：１００℃（風量８０％）
表刷り用グラビア印刷インキ組成物（藍色）の印刷面積は、表刷り用グラビア印刷インキ組成物（白色）の印刷面積の３０％とした。
(Coating methods and conditions for gravure printing ink composition for surface printing)
Coating machine: Gravure proofing machine Coating speed: 100m / min
Printing plate: Direct 175 line solid plate Drying temperature: 100 ° C (80% air volume)
The printing area of the surface printing gravure printing ink composition (blue) was 30% of the printing area of the surface printing gravure printing ink composition (white).
＜実施例２〜６、比較例１〜４＞
使用した白色インクおよび藍色インクの種類を表２に記載のとおり変更した以外は、実施例１と同様の方法により表刷りグラビア印刷物を作製した。
<Examples 2-6, Comparative Examples 1-4>
A surface-gravure printed matter was produced in the same manner as in Example 1 except that the types of white ink and indigo color ink used were changed as shown in Table 2.
実施例１〜６および比較例１〜４において得られた表刷りグラビア印刷物および印刷後の残肉インクについて、以下の評価方法にしたがって皮膜特性を評価した。結果を表１または表２に示す。 About the surface printing gravure printed matter obtained in Examples 1-6 and Comparative Examples 1-4 and the remaining ink after printing, the film | membrane characteristic was evaluated in accordance with the following evaluation methods. The results are shown in Table 1 or Table 2.
＜接着性＞
実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれの印刷面にセロハンテープを貼り付け、これを急速に剥がしたときの印刷皮膜の剥離する度合いから、以下の評価基準に沿って接着性を評価した。
（評価基準）
Ａ：印刷皮膜の面積比率として、フィルムからの剥離が５％未満であった。
Ｂ：印刷皮膜の面積比率として、５％以上３０未満がフィルムから剥離した。
Ｃ：印刷皮膜の面積比率として、３０％以上がフィルムから剥離した。
<Adhesiveness>
From the degree to which the printed film peels off when the cellophane tape is applied to each printed surface of the surface-printed gravure prints of Examples 1 to 6 and Comparative Examples 1 to 4 and rapidly peeled off, the following evaluation criteria are followed. The adhesion was evaluated.
(Evaluation criteria)
A: As an area ratio of the printed film, peeling from the film was less than 5%.
B: 5% or more and less than 30 peeled off from the film as the area ratio of the printed film.
C: 30% or more peeled from the film as the area ratio of the printed film.
＜耐ブロッキング性＞
実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれの印刷面と非印刷面とを合わせて、バイスでしめこみ、４０℃で１日保管後、手で剥がし、インキの剥離の程度と剥離抵抗の強度から、以下の評価基準に沿って耐ブロッキング性を評価した。
（評価基準）
Ａ：印刷皮膜は、全く剥離しなかった。
Ｂ：印刷皮膜は、少し剥離し、剥離抵抗が強く感じられた。
Ｃ：印刷皮膜は、ほとんど剥離し、剥離抵抗が強く感じられた。
<Blocking resistance>
The printed surface and the non-printed surface of the surface-printed gravure printed materials of Examples 1 to 6 and Comparative Examples 1 to 4 were combined, stuffed with a vise, stored at 40 ° C. for 1 day, then peeled off by hand, and the ink was peeled off. The anti-blocking property was evaluated according to the following evaluation criteria from the degree of the strength and the strength of the peeling resistance.
(Evaluation criteria)
A: The printed film did not peel at all.
B: The printed film was peeled off a little, and peeling resistance was felt strongly.
C: The printed film was almost peeled off, and peeling resistance was felt strongly.
＜耐塩ビブロッキング性＞
実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれと同じ大きさに切った軟質塩化ビニルシートＡ〜Ｂと、印刷面とを重ね合わせ、０．５ｋｇ／ｃｍ2の荷重をかけ、５０℃８０％の雰囲気下で２４時間放置後、印刷面と軟質塩化ビニルシートとを引き剥がし、インキの剥離の程度から、以下の評価基準に沿って耐塩ビブロッキング性を評価した。なお、軟質塩化ビニルシートの詳細は、以下のとおりである。
軟質塩化ビニルシートＡ：透明マット（塩化ビニル樹脂、（株）ニトリ販売）
軟質塩化ビニルシートＢ：透明抗菌テーブルマット（明和グラビア（株）製）
（評価基準）
Ａ：印刷皮膜は、全く剥離しなかった。
Ｂ：フィルムから剥離した印刷皮膜の面積は、２０〜５０％であった。
Ｃ：フィルムから剥離した印刷皮膜の面積は、５０％を超えた。
<PVC blocking resistance>
The soft vinyl chloride sheets AB cut into the same size as each of the surface-printed gravure prints of Examples 1 to 6 and Comparative Examples 1 to 4 are overlaid with the printed surface, and a load of 0.5 kg / cm 2 is applied. Then, after leaving for 24 hours in an atmosphere of 50 ° C. and 80%, the printed surface and the soft vinyl chloride sheet were peeled off, and the vinyl chloride blocking resistance was evaluated according to the following evaluation criteria from the degree of ink peeling. The details of the soft vinyl chloride sheet are as follows.
Soft vinyl chloride sheet A: Transparent mat (vinyl chloride resin, sold by Nitori Co., Ltd.)
Soft vinyl chloride sheet B: Transparent antibacterial table mat (manufactured by Meiwa Gravure)
(Evaluation criteria)
A: The printed film did not peel at all.
B: The area of the printed film peeled from the film was 20 to 50%.
C: The area of the printed film peeled from the film exceeded 50%.
＜耐熱性＞
８０〜２００℃の熱傾斜を有する熱板を備えたヒートシール試験機を用いて、実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれの印刷面と、アルミ箔とを２．０ｋｇ／ｃｍ2の圧力で、１秒間押圧した。同様に、印刷面と印刷面とを押圧した。印刷面のインキが押圧された素材（アルミ箔または印刷面）に転移する最低温度を測定し、以下の評価基準に沿って耐熱性を評価した。
（印刷面のインキがアルミ箔に転移する最低温度の評価基準）
Ａ：最低温度は、１６０℃以上であった。
Ｂ：最低温度は、１４０℃以上、１６０℃未満であった。
Ｃ：最低温度は、１４０℃未満であった。
（印刷面のインキが印刷面に転移する最低温度の評価基準）
Ａ：最低温度は、１００℃以上であった。
Ｂ：最低温度は、８０℃以上、１００℃未満であった。
Ｃ：最低温度は、８０℃未満であった。
<Heat resistance>
Using a heat seal tester equipped with a hot plate having a thermal gradient of 80 to 200 ° C., each of the printed surfaces of the surface printed gravure prints of Examples 1 to 6 and Comparative Examples 1 to 4 and aluminum foil 2 It was pressed for 1 second at a pressure of 0.0 kg / cm 2 . Similarly, the printing surface and the printing surface were pressed. The minimum temperature at which the ink on the printed surface was transferred to the pressed material (aluminum foil or printed surface) was measured, and the heat resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria for the minimum temperature at which the ink on the printed surface is transferred to the aluminum foil)
A: The minimum temperature was 160 ° C. or higher.
B: The minimum temperature was 140 ° C. or higher and lower than 160 ° C.
C: The minimum temperature was less than 140 ° C.
(Evaluation criteria for the minimum temperature at which ink on the printed surface is transferred to the printed surface)
A: The minimum temperature was 100 ° C. or higher.
B: The minimum temperature was 80 ° C. or higher and lower than 100 ° C.
C: The minimum temperature was less than 80 ° C.
＜耐油性＞
実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれの印刷面を、学振型耐摩擦試験機を用いて、サラダ油をしみ込ませたあて布で２００ｇの荷重下１００回摩擦し、印刷面の変化から、以下の評価基準に沿って耐油性を評価した。
（評価基準）
Ａ：印刷面は、変化がなかった。
Ｂ：印刷面に、筋状の傷が認められた。
Ｃ：印刷面に、面状の傷が認められた。
<Oil resistance>
The printed surfaces of the surface printed gravure prints of Examples 1 to 6 and Comparative Examples 1 to 4 were rubbed 100 times under a load of 200 g with a cloth impregnated with salad oil using a Gakushin type anti-friction tester. From the change of the printed surface, oil resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The printed surface was not changed.
B: Streaky scratches were observed on the printed surface.
C: Planar scratches were observed on the printed surface.
（耐アルコール性）
実施例１〜６および比較例１〜４の表刷りグラビア印刷物のそれぞれの印刷面を、エタノールに浸した綿棒で擦り、以下の評価基準に沿って耐アルコール性を評価した。
（評価基準）
Ａ：インキは、５０回以上擦ってもとれなかった。
Ｂ：インキは、１０〜５０回擦ることによりとれた。
Ｃ：インキは、１〜１０回擦ることによりとれた。
(Alcohol resistance)
The printed surfaces of the surface printed gravure prints of Examples 1 to 6 and Comparative Examples 1 to 4 were rubbed with a cotton swab soaked in ethanol, and the alcohol resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The ink could not be removed even after rubbing 50 times or more.
B: The ink was removed by rubbing 10 to 50 times.
C: The ink was removed by rubbing 1 to 10 times.
（安定性）
実施例１〜６、比較例１〜４、表刷り用グラビア印刷インキ組成物を用いた印刷後の残肉インクの２５℃で１日経過後の安定性を評価した。
（評価基準）
Ａ：残肉インクは、粘度上昇がほとんどなかった。
Ｂ：残肉インクは、粘度上昇が見られた。
Ｃ：残肉インクは、ゲル化した。
(Stability)
Examples 1 to 6, Comparative Examples 1 to 4, and the stability of the remaining ink after printing using the gravure printing ink composition for front printing at 25 ° C after 1 day was evaluated.
(Evaluation criteria)
A: The residual ink had almost no increase in viscosity.
B: An increase in viscosity was observed in the remaining ink.
C: The remaining ink was gelled.
実施例１〜６の表刷りグラビア印刷物は、多官能イソシアネート化合物である硬化剤が３〜１０質量％となるよう配合されたインキ組成物を使用した結果、表２に示されるように、いずれの皮膜特性も良好であり、接着性等と耐塩ビブロッキング性を両立できることがわかった。また、これら実施例１〜６に使用されたそれぞれのインキ組成物は、表１に示されるように、残肉インクの安定性が優れており、たとえば次回使用時に取扱易いことがわかった。 As shown in Table 2, the surface-printed gravure prints of Examples 1 to 6 were obtained by using an ink composition that was blended so that the curing agent, which is a polyfunctional isocyanate compound, was 3 to 10% by mass. It was found that the film characteristics were also good, and it was possible to achieve both adhesion and vinyl chloride blocking resistance. In addition, as shown in Table 1, each ink composition used in Examples 1 to 6 was excellent in the stability of the remaining ink, and it was found that the ink composition was easy to handle at the next use, for example.
一方、比較例１および比較例３の表刷りグラビア印刷物は、上記硬化剤が適量配合されていなかったため、表２に示されるように、種々の塩化ビニルシートに対する耐塩ビブロッキング性を示すことができなかった。また、比較例２および比較例４の表刷りグラビア印刷物は、皮膜特性は良好であったものの、これらに使用されたインキ組成物は、表１に示されるように、残肉インクの安定性が悪く、たとえば次回使用時に取り扱いにくいことがわかった。 On the other hand, the surface printed gravure prints of Comparative Example 1 and Comparative Example 3 did not contain an appropriate amount of the above-mentioned curing agent, and as shown in Table 2, can exhibit polyvinyl chloride blocking resistance against various vinyl chloride sheets. There wasn't. In addition, although the surface printed gravure prints of Comparative Example 2 and Comparative Example 4 had good film properties, the ink composition used for them had the stability of the remaining ink as shown in Table 1. It turned out to be difficult to handle for the next time, for example.
Claims (4)
前記バインダー樹脂は、（Ａ）ジオール化合物と有機ジイソシアネート化合物とが反応したポリウレタン樹脂を含み、
前記硬化剤は、多官能イソシアネート化合物を含み、
前記硬化剤の含有量は、３〜１０質量％である、表刷り用グラビア印刷インキ組成物。 Including a pigment, a binder resin, a curing agent, and an organic solvent,
The binder resin includes (A) a polyurethane resin in which a diol compound and an organic diisocyanate compound are reacted,
The curing agent includes a polyfunctional isocyanate compound,
The gravure printing ink composition for surface printing, wherein the content of the curing agent is 3 to 10% by mass.
（Ａ）および（Ｂ）の少なくともいずれか１種は、多官能イソシアネート化合物と反応する反応基を有している、請求項１記載の表刷り用グラビア印刷インキ組成物。 The binder resin further contains at least one selected from (B) a cellulose derivative and a vinyl chloride / vinyl acetate copolymer,
The gravure printing ink composition for front printing according to claim 1, wherein at least one of (A) and (B) has a reactive group that reacts with a polyfunctional isocyanate compound.
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