JP6150133B2 - 印刷インキ組成物 - Google Patents
印刷インキ組成物 Download PDFInfo
- Publication number
- JP6150133B2 JP6150133B2 JP2014039019A JP2014039019A JP6150133B2 JP 6150133 B2 JP6150133 B2 JP 6150133B2 JP 2014039019 A JP2014039019 A JP 2014039019A JP 2014039019 A JP2014039019 A JP 2014039019A JP 6150133 B2 JP6150133 B2 JP 6150133B2
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- printing ink
- ink composition
- parts
- acid
- 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.)
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- 238000007639 printing Methods 0.000 title claims description 69
- 239000000203 mixture Substances 0.000 title claims description 48
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 59
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 56
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 56
- 229920005749 polyurethane resin Polymers 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 27
- 238000010030 laminating Methods 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 24
- 239000012948 isocyanate Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000003086 colorant Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000565 sealant Substances 0.000 claims description 8
- 238000007646 gravure printing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 239000012939 laminating adhesive Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 70
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
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- -1 for example Substances 0.000 description 19
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 239000000758 substrate Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 229940097275 indigo Drugs 0.000 description 5
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
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- 239000004576 sand Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 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 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 229940063673 spermidine Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
ポリウレタン樹脂を用いた印刷インキにおいて、ラミネート適性やボイル・レトルト適性に対する検討は以前から盛んに行われている。例えば、特開2013−194121号公報では、ポリウレタン樹脂および高酸価のロジン類を含有する顔料分散体と、ポリウレタン樹脂とを含有する白インキ組成物について検討している。
ロジン類(d)と、
ポリウレタン樹脂(b)と、
有機溶剤(c)とを混合してなる印刷インキ組成物であって、
ロジン類(d)が、
酸価が120mgKOH/g以上の、ロジン(d−1)および/またはロジン誘導体(d−2)
であることを特徴とする印刷インキ組成物に関する。
(1)水素化ロジン:共役二重結合に水素を付加(水素添加)させて、耐候性を向上させたロジンである。
(2)不均化ロジン: 不均化とは、二分子のロジンが反応し、共役二重結合を持った二分子のアビエチン酸が、一方は芳香族へ、もう一方は単独二重結合の分子となる変性である。一般に水添ロジンよりは耐候性が劣るが、未処理よりは向上する。
(3)ロジン変性フェノール樹脂:オフセット印刷のインキには、メインバインダーとしてロジン変性フェノール樹脂が使われることが多い。ロジン変性フェノール樹脂は公知の製造法で得ることができる。
(4)ロジンエステル:ロジンから誘導されるエステル樹脂であり、古くから粘着・接着剤の粘着付与剤(タッキファイヤー)として用いられる。
(5)ロジン変性マレイン酸樹脂:ロジンに無水マレイン酸を付加反応させたもので、必要に応じてグリセリンなどの水酸基含有化合物を、無水酸基とエステル化させグラフトさせたものも含まれる。
(6)重合ロジン:天然樹脂のロジンから誘導される二量化された樹脂酸を含む誘導体である。
その他、公知のロジン、ロジン誘導体も用いることが可能であり、これらは単独だけでなく併用するこができる。
試料を0.5〜2g精秤する。(試料量:Sg)精秤した試料に中性エタノール(BDG中性)30mLを加え溶解させる。得られた溶液を0.2mol/Lエタノール性塩酸溶液(力価:f)で滴定を行なう。溶液の色が緑から黄に変化した点を終点とし、この時の滴定量(AmL)を用い次の(式1)によりアミン価を求めた。
アミン価=(A×f×0.2×56.108)/S [mgKOH/g]
[合成例1]
攪拌機、温度計、還流冷却器および窒素ガス導入管を備えた四つ口フラスコに、分子量2000のポリ(3−メチル−1,5−ペンタンアジペート)ジオール(PMPA2000:水酸基価56.1mgKOH/g)160.41部、分子量2000のポリ(1,2−プロピレングリコール)(PPG2000:水酸基価56.1mgKOH/g)68.75部、イソホロンジイソシアネート50.93部、2−エチルヘキサン酸スズ(II)0.
03部、酢酸エチル82.50部を仕込み、窒素気流下に90℃で3時間反応させ、末端イソシアネートプレポリマーの溶液362.62部を得た。次いでイソホロンジアミン18.54部、2−ヒドロキシエチルエチレンジアミン1.07部、ジ−n−ブチルアミン0.30部、酢酸エチル327.50部、イソプロピルアルコール289.97部を混合したものへ、得られた末端イソシアネートプレポリマーの溶液を室温で徐々に添加し、次に50℃で1時間反応させ、固形分30.0%、重量平均分子量40000、アミン価6.0mgKOH/gのポリウレタン樹脂(PU01)を得た。
攪拌機、温度計、還流冷却器および窒素ガス導入管を備えた四つ口フラスコに、分子量2000のポリ(3−メチル−1,5−ペンタンアジペート)ジオール(PMPA2000:水酸基価56.1mgKOH/g)160.87部、分子量2000のポリ(1,2−プロピレングリコール)(PPG2000:水酸基価56.1mgKOH/g)68.95部、イソホロンジイソシアネート51.08部、2−エチルヘキサン酸スズ(II)0.
03部、酢酸エチル82.50部を仕込み、窒素気流下に90℃で3時間反応させ、末端イソシアネートプレポリマーの溶液363.43部を得た。次いでイソホロンジアミン17.79部、2−ヒドロキシエチルエチレンジアミン1.03部、ジ−n−ブチルアミン0.28部、酢酸エチル327.50部、イソプロピルアルコール289.97部を混合したものへ、得られた末端イソシアネートプレポリマーの溶液を室温で徐々に添加し、次に50℃で1時間反応させ、固形分30.0%、重量平均分子量85000、アミン価1.5mgKOH/gのポリウレタン樹脂(PU02)を得た。
各ロジン類20部を酢酸エチル80部に溶解させ、固形分20.0%のロジン溶液(R1〜R6)を得た。それぞれのロジン類の酸価は以下の通りである。
R1:ハリエスターMSR−4
(ハリマ化成社製・ロジン誘導体)酸価120〜150mgKOH/g
R2:パインクリスタルKR−612
(荒川化学工業社製・ロジン)酸価165〜175mgKOH/g
R3:ハリマックT−80
(ハリマ化成社製・ロジン誘導体)酸価170〜200mgKOH/g
R4:ハリマックAS−5
(ハリマ化成社製・ロジン誘導体)酸価185〜210mgKOH/g
R5:パインクリスタルKE−604
(荒川化学工業社製・ロジン誘導体)酸価230〜245mgKOH/g
R6:パインクリスタルKE−359
(荒川化学工業社製・ロジン誘導体)酸価10〜20mgKOH/g
[実施例1]
チタニックスJR−805(テイカ社製・酸化チタン)35.0部、ポリウレタン樹脂(PU01)10.0部、n−プロピルアセテート5.0部、イソプロピルアルコール5.0部を撹拌混合しサンドミルで練肉した後、ポリウレタン樹脂(PU01)30.0部、酢酸エチル6.0部、イソプロピルアルコール4.0部、ロジン類溶液(R1)5.0部を撹拌混合し、白色印刷インキ組成物(W01)を得た。得られた白色印刷インキ組成物100部に、n−プロピルアセテート:イソプロピルアルコール混合溶剤(質量比75:25)50部を希釈溶剤として添加混合し、希釈インキを得た。
実施例1と同様の操作で、表1および表2の仕込み比にて、白色印刷インキ組成物(W02〜10およびW12〜13)を得た。ただし、比較例1ではロジン類溶液は添加しない。また、実施例1と同様の操作で希釈インキも得た。
チタニックスJR−805(テイカ社製・酸化チタン)30.0部、ポリウレタン樹脂(PU01)10.0部、n−プロピルアセテート5.0部、イソプロピルアルコール5.0部を撹拌混合しサンドミルで練肉した後、ポリウレタン樹脂(PU01)30.0部、酢酸エチル6.0部、イソプロピルアルコール4.0部、ロジン類溶液(R2)5.0部を撹拌混合し、さらにLPスーパー硬化剤(東洋インキ社製・イソシアネート系硬化剤)3.0部を添加し、白色印刷インキ組成物(W11)を得た。得られた白色印刷インキ組成物103部に、n−プロピルアセテート:イソプロピルアルコール混合溶剤(質量比75:25)50部を希釈溶剤として添加混合し、希釈インキを得た。
実施例11と同様の操作で、表2の仕込み比にて、白色印刷インキ組成物(W16)を得た。また、実施例11と同様の操作で希釈インキも得た。
チタニックスJR−805(テイカ社製・酸化チタン)35.0部、ポリウレタン樹脂(PU01)10.0部、n−プロピルアセテート5.0部、イソプロピルアルコール5.0部、ロジン類溶液(R3)3.75部を撹拌混合しサンドミルで練肉した後、ポリウレタン樹脂(PU01)30.8部、酢酸エチル6.2部、イソプロピルアルコール4.2部を撹拌混合し、白色印刷インキ組成物(W14)を得た。得られた白色印刷インキ組成物100部に、n−プロピルアセテート:イソプロピルアルコール混合溶剤(質量比75:25)50部を希釈溶剤として添加混合し、希釈インキを得た。
比較例3と同様の操作で、表2の仕込み比にて、白色印刷インキ組成物(W15)を得た。また、実施例1と同様の操作で希釈インキも得た。
[実施例12]
LIONOL BLUE FG−7330(C.Iピグメントブルー15:3)(トーヨーカラー社製)10部、ポリウレタン樹脂(PU01)15部、n−プロピルアセテート5部、イソプロピルアルコール5部を撹拌混合しサンドミルで練肉した後、ポリウレタン樹脂(PU01)20部、ロジン類溶液(R4)5.0部、酢酸エチル24.0部、イソプロピルアルコール16.0部を撹拌混合し、藍色印刷インキ組成物(C01)を得た。藍色印刷インキ組成物100部に対し、n−プロピルアセテート:イソプロピルアルコール混合溶剤(質量比75:25)を50部添加混合して希釈インキと得た。
実施例12と同様の操作で、表2の仕込み比にて、藍色印刷インキ組成物(C02)を得た。ただし、ロジン類溶液は添加しない。また、実施例12と同様の操作で希釈インキも得た。
上記のOPPフィルムの印刷物に、イミン系のアンカーコート剤(東洋モートン社製・EL420)をNV1wt%メタノール溶液で塗工し、押し出しラミネート機(ムサシノキカイ社製)によってライン速度100m/minにて溶融ポリエチレン(日本ポリエチレン社製・LC600A)を320℃で溶融させて18μmで積層し、VMPET(麗光社製・ダイアラスター H27 #12)と張り合わせた。さらにその上にCPP(フタムラ化学社製・FCMN #20)を同様に張り合わせた。なお、ラミネート工程は印刷工程後、3時間以内に行う。ラミネート工程後、ラミネート物について長さ150mm、幅15mmに切り出し、インキ−フィルム界面で開き、テンシロン引っ張り試験機を用いて90°方向のラミネート強度を測定した。測定は、ラミネート工程後、3時間および1日に行う。なお、判定基準は次の通りとした。
◎:1.5 N/15mm以上
○:1.0 N/15mm以上1.5 N/15mm未満
△:0.5 N/15mm以上1.0 N/15mm未満 (これ以上を実用水準とする)
×:0.5 N/15mm未満
上記のPETフィルムの印刷物に、ポリエステル系接着剤(東洋モートン社製・TM−550/CAT−RT37)をNV30wt%酢酸エチル溶液で塗工し、ドライラミネート機を用いてライン速度40m/minにてCPP(東レ社製・ZK93KM)と張り合わせ、40℃で48時間エージングを行った。その後、CPP面を内側としてヒートシールして袋体を作り、得られた袋体に内容物として食酢:サラダ油:トマトケチャップ=1:1:1(重量比)のスープを充填し、120℃30分のレトルト処理を行った。レトルト処理前後のラミネート物について長さ150mm、幅15mmに切り出し、インキ−フィルム界面で開き、テンシロン引っ張り試験機を用いて90°方向のラミネート強度を測定した。なお、判定基準は次の通りとした。
◎:2.5 N/15mm以上
○:2.0 N/15mm以上2.5 N/15mm未満
△:1.5 N/15mm以上2.0 N/15mm未満 (これ以上を実用水準とする)
×:1.5 N/15mm未満
Claims (4)
- 着色剤(a)、ポリウレタン樹脂(b)、および有機溶剤(c)を含有してなる顔料分散体と、
ロジン類(d)と、
ポリウレタン樹脂(b)と、
有機溶剤(c)とを混合してなる印刷インキ組成物であって、
ロジン類(d)が、
酸価が120mgKOH/g以上の、ロジン(d−1)および/またはロジン誘導体(d−2)
であることを特徴とする印刷インキ組成物。 - 更に、イソシアネート系硬化剤(e)を含有することを特徴とする請求項1記載の印刷インキ組成物。
- プラスチックフィルムに、請求項1または2記載の印刷インキ組成物を、グラビア印刷機を用いて印刷してなる印刷物。
- 請求項3記載の印刷物と、シーラントとを、ラミネート接着剤を介して、ラミネートしてなる積層体。
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