JP6699389B2 - 包装体 - Google Patents
包装体 Download PDFInfo
- Publication number
- JP6699389B2 JP6699389B2 JP2016122669A JP2016122669A JP6699389B2 JP 6699389 B2 JP6699389 B2 JP 6699389B2 JP 2016122669 A JP2016122669 A JP 2016122669A JP 2016122669 A JP2016122669 A JP 2016122669A JP 6699389 B2 JP6699389 B2 JP 6699389B2
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- JP
- Japan
- Prior art keywords
- resin
- acid
- printing
- article
- ink
- 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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- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 63
- 229920003002 synthetic resin Polymers 0.000 claims description 46
- 239000000057 synthetic resin Substances 0.000 claims description 46
- 239000004925 Acrylic resin Substances 0.000 claims description 44
- 229920000178 Acrylic resin Polymers 0.000 claims description 44
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 30
- 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 28
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 28
- 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 27
- 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 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 229920006026 co-polymeric resin Polymers 0.000 claims description 22
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 125000005442 diisocyanate group Chemical group 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
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- 238000003786 synthesis reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- 238000013461 design Methods 0.000 description 8
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- 238000007646 gravure printing Methods 0.000 description 8
- 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 8
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229920006257 Heat-shrinkable film Polymers 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
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- 229920000298 Cellophane Polymers 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 5
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- 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
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- MHVJRKBZMUDEEV-KRFUXDQASA-N sandaracopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-KRFUXDQASA-N 0.000 description 1
- YZVSLDRKXBZOMY-KNOXWWKRSA-N sandaracopimaric acid Natural products CC(=C)[C@]1(C)CCC[C@]2(C)[C@H]3CC[C@](C)(C=C)C=C3CC[C@@H]12 YZVSLDRKXBZOMY-KNOXWWKRSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 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
- 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 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-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
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
(1)物品が、基材上の一部又は全面に印刷層1を有するものであり、外装体が、合成樹脂フィルム上に印刷層2を有するものであり、かつ印刷層2が少なくとも印刷層1と接触する面に配置されてなる。
(2)印刷層1が、アクリル樹脂、セルロース樹脂およびウレタン樹脂からなる群より選択される1種以上の樹脂を含有する。
(3)印刷層2が、白色顔料を40〜60重量%含有する。
(4)印刷層2が、ポリエステル系ウレタン樹脂と、塩化ビニル/酢酸ビニル共重合体樹脂と、酸変性ロジン樹脂を20〜40重量%含有し、前記、ポリエステル系ウレタン樹脂と、塩化ビニル/酢酸ビニル共重合体樹脂および酸変性ロジン樹脂との固形分重量比が75:25〜45:55である。
また、本発明は、印刷層2は更に、脂肪酸アミドおよび/または平均粒径0.1〜15μmのシリカを含有する、上記包装体に関する。
これらモノマーを1種または2種以上の使用することができる。その他、下記に述べるラジカル重合性モノマーとの共重合体も使用できる。
リシノール酸アルキル等の水酸基含有不飽和脂肪酸エステル類;
水溶性のアクリル系樹脂のエマルジョンは、分子内にカルボキシル基または酸無水物基を有する高分子乳化剤の存在下、スチレン系単量体および/またはメチルメタクリレートに、必要に応じてその他の共重合可能なラジカル重合性単量体を加えて乳化重合して得られる水性樹脂エマルジョンである。本発明の高分子乳化剤としては、アクリル樹脂、スチレン−アクリル樹脂、スチレン−アクリル−マレイン酸樹脂の少なくとも1種を使用することができる。
)アクリルアミド、エチル(メタ)アクリルアミド、 ブチル(メタ)アクリルアミド、ヘキシル(メタ)アクリルアミド、2−ヒド ロキシエチル(メタ)アクリレート等を挙げる
ことができ、上記のアクリルモノマー体も使用することが可能である。
これらのモノマーのうち、エチレンオキサイド変性トリメチロールプロパントリアクリレートがセロハンテープ剥離性、コストの面から特に好ましい。また、エチレンオキサイド変性トリメチロールアクリレートはそのエチレンオキサイドくり返し単位数( モル変性と表現される)が1〜20モルのもの等が挙げられるが、そのうち3〜9モル変性のものが架橋した皮膜の物性に優れ、好ましい。
また、カチオン反応性の成分を紫外線により架橋させる場合には、カチオン系開始剤としては、ルイス酸のジアゾニウム塩、ルイス酸のヨードニウム塩、ルイス 酸のスルホニウム塩、ルイス酸のホスホニウム塩、その他のハロゲン化物、トリアジン系開始剤、ボーレート系開始剤、およびその他の光酸発生剤などが挙げら れる。電子線により架橋させる場合にはこれらを配合しなくても良い。
5ペンタンジオール、ジエチレングリコール、トリエチレングリコール、ポリプロピレングリコール、ジプロピレングリコール、が挙げられる。またグリセリン、トリメチロールプロパン、トリメチロールエタン、1,2,6−ヘキサントリオール、1,2,4−ブタントリオール、ソルビトール、ペンタエスリトールなどのヒドロキシル基を3個以上有する低分子ポリオールも挙げられる。
系及びセルロース系樹脂を含有する印刷インキ2中0.1〜5重量%使用する。前記範囲内であると、物品の基材の表面となる側の印刷層1との耐ブロッキング性、スベリ性向上に対する効果が大きく見られるため好ましい。また、塗膜表面にオイル状に浮き、ヌメリ、意匠性の劣化を防ぐ。
1)あらかじめ外装体を一方のみ開封している袋状に成形し、その中に物品に入れ包み込
む方法
2)あらかじめ外装体を円筒状に成形し、その中に物品に入れ包み込む方法
3)物品の外周に当該外装体を外周に沿って巻きつけて、外装体の両方の端部を重ね合わ
せて包み込む方法
その後、物品が外装体の中から出ないように、外装体の開封口を溶断シールやヒートシールすることにより合成樹脂フィルムを熱接着させて閉口することが好ましい。
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。
(式1) アミン価=(A×f×0.2×56.108)/S
数平均分子量(Mn)および重量平均分子量(Mw)の測定は、昭和電工社製GPC(ゲルパーミエーションクロマトグラフィー)「ShodexGPC System−21」を用いた。GPCは溶媒に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、溶媒としてはテトロヒドロフラン、重量平均分子量(Mn)の決定はポリスチレン換算で行った。
共栓三角フラスコ中に試料、約1gを精密に量り採り、トルエン/エタノール(容量比:トルエン/エタノール=2/1)混合液100mlを加えて溶解する。更にアセチル化剤(無水酢酸25gをピリジンで溶解し、容量100mlとした溶液)を正確に5ml加え、約1時間攪拌した。これに、フェノールフタレイン試液を指示薬として加え、30秒間持続する。その後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定する。
水酸基価は(式2)により求めた。水酸基価は樹脂の乾燥状態の数値とした(単位:mgKOH/g)。
(式2) 水酸基価(mgKOH/g)=[{(b−a)×F×28.25}/S]/(不揮発分濃度/100)+D
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
b:空実験の0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
D:酸価(mgKOH/g)
共栓三角フラスコ中に試料化合物(B)を、約1gを精密に量り採り、トルエン/エタノール(容積比:トルエン/エタノール=2/1)混合液100mlを加えて溶解した。これに、フェノールフタレイン試液を指示薬として加え、30秒間保持した後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定した。
乾燥状態の樹脂の値として、酸価(mgKOH/g)を(式3)により求めた。
(式3) 酸価(mgKOH/g)={(5.611×a×F)/S}/(不揮発分濃度/100)
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
印刷インキ1の製造に用いたウレタン樹脂、セルロース樹脂、アクリル樹脂を下記に記す。ウレタン樹脂は、印刷インキ2にも用いた。
(ポリエステルジオールの合成例)
攪拌機、温度計、分水器および窒素ガス導入管を備えた丸底フラスコに、2−ブチル−2−エチル−1,3−プロパンジオール(以下BEPGと略す)56.846部、アジピン酸43.152部、テトラブチルチタネート0.002部を仕込み、窒素気流下に230℃で縮合により生じる水を除去しながらエステル化を8時間行った。ポリエステルの酸価が15以下になったことを確認後、真空ポンプにより徐々に真空度を上げ反応を終了した。これにより水酸基価56.1mgKOH/g(水酸基価から算出される数平均分子量2000)、酸価0.3mgKOH/gのポリエステルジオ−ルを得た。
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、先述のポリエステルジオ−ル22.226部、イソホロンジイソシアネート5.434部、酢酸エチル7.500部を仕込み、窒素気流下に120℃で6時間反応させ、酢酸エチル7.500部を加え冷却し、末端イソシアネートプレポリマーの溶液42.663部を得た。次いでイソホロンジアミン2.203部、ジn−ブチルアミン0.138部、酢酸エチル20.000部およびエタノール20.000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剤溶液42.663部を室温で徐々に添加し、次に50℃で1時間反応させ、エタノール15.000部を添加し、固形分30.0%、重量平均分子量24000、アミン価4.0mgKOH/樹脂1gのウレタン樹脂1を得た。
ウレタン樹脂1の合成例と同様にして先述のポリエステルジオ−ル22.226部、イソホロンジイソシアネート5.434部、酢酸エチル7.500部を仕込み、窒素気流下に120℃で6時間反応させ、酢酸エチル7.500部を加え冷却し、末端イソシアネートプレポリマーの溶液42.663部を得た。次いでイソホロンジアミン4.406部、ジn−ブチルアミン0.138部、酢酸エチル20.000部およびエタノール20.000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剤溶液42.663部を室温で徐々に添加し、次に50℃で1時間反応させ、エタノール15.000部を添加し、固形分30.0%、重量平均分子量24000、アミン価8.0mgKOH/樹脂1gのウレタン樹脂2を得た。
ウレタン樹脂1の合成例と同様にして先述のポリエステルジオ−ル22.226部、イソホロンジイソシアネート5.434部、酢酸エチル7.500部を仕込み、窒素気流下に120℃で6時間反応させ、酢酸エチル7.500部を加え冷却し、末端イソシアネートプレポリマーの溶液42.663部を得た。次いでイソホロンジアミン8.812部、ジn−ブチルアミン0.138部、酢酸エチル20.000部およびエタノール20.000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剤溶液42.663部を室温で徐々に添加し、次に50℃で1時間反応させ、エタノール15.000部を添加し、固形分30.0%、重量平均分子量24000、アミン価13.0mgKOH/樹脂1gのウレタン樹脂2を得た。
ニトロセルロース樹脂〔稲畑産業株式会社、規格 L1/2、商品名 DLX30−50〕20部を、イソプロピルアルコールと酢酸エチルを等量ずつ混合した混合溶剤中に溶解させ、固形分20%のニトロセルロース樹脂ワニスを得た。
アクリルモノマーとして、メタクリル酸メチル〔単独重合体のガラス転移温度Tg=+105℃〕37部、およびメタクリル酸ブチル〔単独重合体のガラス転移温度Tg=+20℃〕60部、アクリル酸〔単独重合体のガラス転移温度Tg=+106℃〕3部の組成比となるように共重合し、重量平均分子量50000、Tg50℃となるアクリル樹脂を作製した。作製したアクリル樹脂を、イソプロピルアルコールと酢酸エチルを等量ずつ混合した混合溶剤中に溶解させ、アクリル樹脂固形分が40%のアクリル樹脂を作製した。
顔料タイペークCR67(石原産業(株)製)25.0部、ウレタン樹脂1を15.0部、酢酸エチルを5.0部、エタノールを5.0部撹拌混合しサンドミルで練肉した後、ウレタン樹脂1を10.0部、酢酸エチルを20.0部、エタノールを20.0部攪拌混合し白色希釈印刷インキ(インキ1)を得た。
各原料を表1に記載された通りに変更し、インキ1と同様の方法で、白色希釈印刷インキであるインキ2〜5を得た。なお、表1は溶剤を含む値である。
顔料RAVEN1020(Columbian社製)15.0部、ウレタン樹脂1を11.0部、酢酸エチルを5.0部、エタノールを5.0部撹拌混合しサンドミルで練肉した後、ウレタン樹脂1を14.0部、酢酸エチル25.0部、エタノール25.0部を攪拌混合し黒色希釈印刷インキ(インキ6)を得た。
印刷インキ2の製造に用いた塩化ビニル/酢酸ビニル共重合体樹脂、酸変性ロジン樹脂を下記に示す。
(塩化ビニル/酢酸ビニル共重合体樹脂1)
・ソルバインTAO (信越化学工業社製)、軟化点78℃、数平均分子量15,000、塩化ビニル:酢酸ビニル:ビニルアルコールのモノマー比率は91:2:7
(塩化ビニル/酢酸ビニル共重合体樹脂2)
・VINNOL E15/45(信越化学工業社製)、軟化点75℃、数平均分子量13,000、塩化ビニル:酢酸ビニル:ビニルアルコールのモノマー比率は85:15:0
(酸変性ロジン樹脂1)
・ハリマック4740(ハリマ化成社製)、軟化点115〜125℃、酸価15〜30
(酸変性ロジン樹脂2)
・マルキード3002 (荒川化学社製)、軟化点165〜185℃、酸価90〜110
(酸変性ロジン樹脂3)
・ハリマックT―80(ハリマ化成社製)、軟化点80〜90℃、酸価170〜200
(塩素化PP)
・スーパークロン370M(日本製紙社製)塩素化度30%、固形分50%
(チタンキレート)
・テトライソプロポキシチタン(日本曹達社製)
(脂肪酸アミド)
・パルミチン酸アミド(花王(株)製)
(シリカ)
・サイリシア350(富士シリシア社製)、平均粒子径3.0μm、
(シリコンオイル)
・シンエツシリコンKP−355(信越シリコーン株式会社社製)
(界面活性剤)
・プライサーフA208−15N(第一工業製薬社製)
白色顔料(タイペークCR67、酸化チタン、石原産業(株)製)50部、塩化ビニル/酢酸ビニル共重合体樹脂1を6.0部、酸変性ロジン樹脂1 6.0部、ウレタン樹脂2を30.0部(固形分で9.0部)、混合溶剤(酢酸エチル/エタノール=1/1)40.0部、撹拌混合しサンドミルで練肉した後、ウレタン樹脂2を30.0部(固形分で9.0部)、添加剤として塩素化PP10部(固形分で5.0部)、チタンキレート5部、脂肪酸アミド5部、シリカ5部、および上記混合溶剤146.0部を攪拌混合し白色希釈印刷インキ(インキ7)を得た。固形分30%。
各原料を表2に記載された通りに変更し、インキ7と同様の方法で、インキ8〜28を得た。なお、表2は固形分の値であり、インキ8〜28はいずれも混合溶剤(酢酸エチル/エタノール=1/1)を用いて最終的に固形分30%に調整した。
<物品1の作成方法>
次の印刷条件の下で、物品の基材としてPETフィルムE5100−100μ(東洋紡社製)の処理面にインキ1の印刷を行い、物品1を得た。
印刷機:富士機械工業株式会社製グラビア印刷機
圧胴:ゴム硬度80HsのNBR(ニトリルブタジエンゴム)製
ドクター:刃先の厚みが60μmのセラミックメッキドクターブレード(母材の厚み40μm、片側セラミック層の厚み10μm)
版:東洋プリプレス株式会社製のクロム硬度1050Hvの電子彫刻版(スタイラス角度130度、印刷インキ用:175線/inch、熱接着剤用:100線/inch)
印圧:2kg/cm2
ドクター圧:2kg/cm2
印刷速度:60m/分
乾燥温度:F100℃
同様な条件で合成樹脂フィルムであるOPPフィルムFOH−30μ(フタムラ化学社製)の処理面にインキ7の印刷を行い外装体1を得た。
得られた外装体1を7.5cm×10.5cmで2枚切り出し、それぞれの印刷面を内側にして合わせ端3辺を幅1cmの単動式ヒートシーラーにより次の条件で熱接着し、一方のみ開封した袋を作った。その後、物品1を5cm×8cmで切り出し、前述の袋に入れ、開封部分を単動式ヒートシーラーにより熱接着し、閉口することにより包装体1を得た。
熱接着条件 熱接着温度:130℃
熱接着条件 :1.0秒
熱接着圧力 :2kg/cm2
<物品2〜7の作成方法>
表3に記載された通りに、それぞれインキ2〜6をPETフィルムE5100−100μ(東洋紡社製)、またはインキ6をコート紙(リューオーコート紙(大王製紙株式会社製))に印刷を行い、物品7を得た。印刷条件は実施例1と同様にする。
表3に記載された通り、外装体1の作成方法と同様に、OPPフィルムFOH−30μ(フタムラ化学社製)の処理面に、それぞれインキ7〜23の印刷を行い、外装体2〜17を得た。
表3に記載された通り、包装体1の作成方法と同様に、物品1〜7および外装体2〜17を積層し、実施例2〜23(包装体2〜23)を得た。
物品は、実施例で得た物品1、物品7を用いた。
<外装体18〜23の作成方法>
表4に記載された通り、外装体1の作成方法と同様に、OPPフィルムFOH−30μ(フタムラ化学社製)の処理面に、それぞれインキ24〜28の印刷を行い、外装体18〜23を得た。
表4に記載された通り、包装体1の作成方法と同様に、物品1、もしくは物品7に外装体18〜23を積層し、比較例1〜6(包装体24〜29)を得た。
得られた包装体の物品と外装体について、学振型耐摩擦試験機にてそれぞれの印刷層を重ね合わせて、0.5kg/cm2の荷重をかけ100回擦った後、物品と外装体のイン
キの剥離の程度から耐摩擦性を評価した。
○:インキが剥離した面積が0〜20%のもの
△:インキが剥離した面積が20〜50%のもの(実用レベル以上)
×:インキが剥離した面積が50〜75%のもの
得られた包装体の物品と外装体について、同じ大きさに切ったそれぞれの印刷物の印刷層を重ね合わせて、1.0kg/cm2の荷重をかけ、50℃、80%RHの雰囲気で48時間放置後、物品と外装体の印刷層同士を引き剥がし、インキの剥離の程度から耐ブロッキング性を評価した。
○:インキが剥離した面積が0〜20%のもの
△:インキが剥離した面積が20〜50%のもの(実用レベル以上)
×:インキが剥離した面積が50〜75%のもの
得られた包装体の外装体について、印刷面にセロハンテープを圧着し、その後テープを剥が時の印刷面の剥離状態を観察する。
○:インキが剥離した面積が0〜20%のもの
△:インキが剥離した面積が20〜50%のもの(実用レベル以上)
×:インキが剥離した面積が50〜75%のもの
得られた包装体の物品と外装体について、25mm×60mmの短冊状に打ち抜き、印刷層同士を合わせ単動式ヒートシーラーにより次の条件で熱接着したあとすぐにはがした時のインキの剥離の程度から耐熱ブロッキング性を評価した。
熱接着条件 熱接着温度:140℃
熱接着条件 :1.0秒
熱接着圧力 :2.5kg/cm2
○:インキが剥離した面積が0〜20%のもの
△:インキが剥離した面積が20〜50%のもの(実用レベル以上)
×:インキが剥離した面積が50〜75%のもの
Claims (6)
- 物品と、その外側に外装体を有する包装体であって、下記(1)〜(4)を特徴とする包装体。
(1)物品が、基材上の一部又は全面に印刷層1を有するものであり、外装体が、合成樹
脂フィルム上に印刷層2を有するものであり、かつ印刷層2が少なくとも印刷層1と接触
する面に配置されてなる。
(2)印刷層1が、アクリル樹脂、セルロース樹脂およびウレタン樹脂から選択される1種以上の樹脂を含有する。
(3)印刷層2が、白色顔料を40〜60重量%含有する。
(4)印刷層2が、ポリエステル系ウレタン樹脂と、塩化ビニル/酢酸ビニル共重合体樹脂と、酸変性ロジン樹脂を20〜40重量%含有し、前記ポリエステル系ウレタン樹脂と、塩化ビニル/酢酸ビニル共重合体樹脂および酸変性ロジン樹脂との固形分重量比が75:25〜45:55である。 - 印刷層2は更に、脂肪酸アミドおよび/または平均粒径0.1〜15μmのシリカを含有する、請求項1に記載の包装体。
- 印刷層2が、さらにチタンキレート、および塩素化ポリオレフィンを含有することを特徴とする請求項1または2に記載の包装体。
- 印刷層2が、さらに界面活性剤、および/またはシリコンオイルを含有することを特徴とする請求項1〜3いずれか記載の包装体。
- 物品の基材が紙であることを特徴とする請求項1〜4いずれか記載の包装体。
- 外装体が熱収縮されたものであることを特徴とする請求項1〜5いずれか記載の包装体。
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