JP5446907B2 - Aqueous overcoating composition for paper containers - Google Patents
Aqueous overcoating composition for paper containers Download PDFInfo
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- JP5446907B2 JP5446907B2 JP2010008542A JP2010008542A JP5446907B2 JP 5446907 B2 JP5446907 B2 JP 5446907B2 JP 2010008542 A JP2010008542 A JP 2010008542A JP 2010008542 A JP2010008542 A JP 2010008542A JP 5446907 B2 JP5446907 B2 JP 5446907B2
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- acrylate
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- styrene
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- 239000000203 mixture Substances 0.000 title claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical group CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000007639 printing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- -1 2-ethylhexyl Chemical group 0.000 description 6
- 238000007646 gravure printing Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は紙器用水性オーバーコーティング組成物に関する。より詳しくは、各種印刷用紙にグラビア印刷を行った際に、良好な乾燥性を有し、生産性を阻害する事なく、優れた品質の印刷物を得るのに適した紙器用水性オーバーコーティング組成物に関する。 The present invention relates to an aqueous overcoating composition for paper containers. More specifically, when performing gravure printing on various printing papers, the water-based overcoating composition for paper containers has good drying properties and is suitable for obtaining excellent quality printed matter without impeding productivity. About.
有機溶剤による大気汚染等の環境問題、作業環境の安全衛生問題、防災といった観点から、印刷インキや塗料の分野では古くから脱有機溶剤化・水性化が検討されてきた。
しかし、実用化されている水性オーバーコーティングワニスは、乾燥性の問題から、コーティングワニス中にアルコールを多く含有させ、生産性を上げている場合が殆どである。
また、２０１０年に大気汚染防止法の施行により、揮発性有機化合物の排出濃度が制限され、各印刷メーカーは、その対応を迫られている。それに伴い、水性コーティングワニスに対して、含有する揮発性有機化合物の低減が要求されるようになってきている。
From the viewpoint of environmental problems such as air pollution caused by organic solvents, safety and health problems in the work environment, and disaster prevention, removal of organic solvents and water-based solutions have long been studied in the field of printing inks and paints.
However, most of the aqueous overcoating varnishes that have been put into practical use have a high productivity by containing a large amount of alcohol in the coating varnish because of the problem of drying.
In addition, due to the enforcement of the Air Pollution Control Act in 2010, the emission concentration of volatile organic compounds is limited, and each printing manufacturer is forced to take measures. Accordingly, reduction of the volatile organic compounds contained in the aqueous coating varnish has been demanded.
本発明は、各種印刷用紙にグラビア印刷を行った際に、揮発性有機化合物を極力含有しないまたはまったく含有しない溶剤組成であっても、良好な乾燥性を有し、生産性を阻害させる事なく、優れた品質の印刷物を得るのに適した紙器用水性オーバーコーティング組成物を得ることにある。 The present invention, when performing gravure printing on various printing papers, has a good drying property even without a volatile organic compound as much as possible or does not impair productivity. An object of the present invention is to obtain an aqueous overcoating composition for paper containers suitable for obtaining an excellent quality printed matter.
本発明は、シェルがスチレン、（メタ）アクリル酸、および炭素数１２〜２０の長鎖アルキル（メタ）アクリレート１％〜１０％有し、コアがスチレンと（メタ）アクリレートからなるコア／シェル構造を有するアクリルエマルジョンを含有し、溶媒がアルコールを含まないことを特徴とする紙器用オーバーコーテイング組成物である。
また、上記アクリルエマルジョンのコア／シェル比が１０：９０〜５０：５０であることを特徴とする紙器用オーバーコーテイング組成物に関する。
また、長鎖アルキル（メタ）アクリレートがラウリルアクリレート、パルミチルアクリレート、ステアリルアクリレートから選ばれる少なくとも1種のアクリレートであることを特徴とする紙器用オーバーコーテイング組成物に関する。
加えて、印刷紙基材にオーバーコーティング組成物を印刷した印刷物に関する。
The present invention provides a core / shell structure in which the shell has styrene, (meth) acrylic acid, and 1 to 10% of a long-chain alkyl (meth) acrylate having 12 to 20 carbon atoms, and the core is made of styrene and (meth) acrylate. An overcoating composition for paper containers, characterized in that it contains an acrylic emulsion having a water content and the solvent does not contain alcohol.
The present invention also relates to an overcoating composition for paper containers, wherein the acrylic emulsion has a core / shell ratio of 10:90 to 50:50.
The present invention also relates to an overcoating composition for paper containers, wherein the long-chain alkyl (meth) acrylate is at least one acrylate selected from lauryl acrylate, palmityl acrylate, and stearyl acrylate.
In addition, the present invention relates to a printed material obtained by printing an overcoating composition on a printing paper substrate.
本発明の紙器用水性オーバーコーティング組成物は、揮発性有機化合物をまったく含有しない溶剤組成においても、各種印刷用紙にグラビア印刷を行った際に、良好な乾燥性を有し、生産性を阻害する事なく、優れた品質の印刷物を得るのに適した紙用水性オーバーコーティング組成物を得ることが可能になった。 The aqueous overcoating composition for paper containers of the present invention has good drying properties and inhibits productivity when gravure printing is performed on various printing papers even in a solvent composition that does not contain any volatile organic compound. Thus, it has become possible to obtain an aqueous paper overcoating composition suitable for obtaining a print of excellent quality.
本発明の水性オーバーコーティング組成物は、シェルがスチレン、コア／シェル全量に対し炭素数１２〜２２の長鎖アルキル（メタ）アクリレートを１％〜１０％有し、コアがスチレンと（メタ）アクリレートからなるコア／シェル構造を有するアクリルエマルジョン、水、各種添加剤等を配合する事により製造される。
上記コア／シェル構造を有するアクリルエマルジョンを構成するスチレンとしては、スチレン、α−メチルスチレンが挙げられ、これら1種または2種の組み合わせて用いる事ができる。（メタ）アクリル酸はアクリルエマルジョンには水性化能を付与するため使用され、アクリル酸、メタアクリル酸等を1種または2種の組み合わせて用いる事ができる。
炭素数１２〜２０の長鎖アルキル（メタ）アクリレートとしては、ラウリルアクリレート、パルミチルアクリレート、ステアリルアクリレート等があげられ、これら１種または２種以上の組み合わせで用いる事ができる。また、該長鎖アルキル（メタ）アクリレートの含有量は、コア／シェル全量に対し１重量％〜１０重量％であることが必要である。１重量％よりも少ないと乾燥性が劣化し、生産性に影響を与え、１０重量％より多く含まれてもアクリルエマルジョンとして乳化能が低下し、コーティングワニスとしての安定性が悪くなる。
上記コア／シェル構造を有するアクリルエマルジョンを構成する（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレートト等の水酸基を有する（メタ）アクリレート。シクロヘキシル（メタ）アクリレート等の脂環構造を有する（メタ）アクリレートが挙げられ、これら１種または２種以上の組み合わせて用いる事ができる。
本発明においては、アクリルエマルジョンはコア／シェル構造を有していることが必要であり、シェルとしては、スチレン、（メタ）アクリル酸および炭素数１２〜２０の長鎖アルキル（メタ）アクリレートが、コアとしてはスチレン、（メタ）アクリレートが使用される。特にシェルに用いられるスチレン、および炭素数１２〜 ２０の長鎖アルキル（メタ）アクリレートは、コーティング剤としての乾燥性を決める上で重要である。
上記アクリルエマルジョンのコア／シェル重量比率は、１０：９０〜 ５５：４５の範囲内である事が好ましい。コア比率が１０％未満だと、コーティング塗膜の光沢値が低下する傾向であり、５５％より大きいと、乾燥性不良を起こす傾向がある。
アクリルエマルジョンのガラス転移点は２０〜８０℃であることが好ましい。２０〜８０℃の範囲内では、インキへの密着性、アクリルエマルジョンの成膜性が良好である。
本発明である水性オーバーコーティング組成物におけるアクリルエマルジョンは、例えば上記スチレン、（メタ）アクリル酸および長鎖アルキル（メタ）アクリレートとを共重合して得られた高分子乳化剤の存在下において、共重合可能なスチレン及び(メタ)アクリレートを乳化重合して得られる。
重合反応を開始するに当たっては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩またはアゾビス系カチオン塩もしくは水酸基付加物等の水溶性の熱分解型重合開始剤を用いることができる。
またレドックス開始剤を用いることもできる。
レドックス開始剤としては、ｔ−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイドなどの有機過酸化物とロンガリット、メタ重亜硫酸ナトリウムなどの還元剤との組み合わせ、または過硫酸カリウム、過硫酸アンモニウムとロンガリット、チオ硫酸ナトリウムなどとの組み合わせ、過酸化水素水とアスコルビン酸との組み合わせ等が用いられる。
樹脂のカルボキシル基を中和することで水性化できる、中和剤には例えば、にアンモニア、トリエチルアミン、アミノメチルプロパノール、モノエタノールアミン、ジエチルアミノエタノール、水酸化ナトリウム，水酸化カリウム等の塩基類がある。
オーバーコーテイング組成物には、シリカ、アルミナ、ポリエチレンワックス、消泡剤、レベリング剤、粘着性付与剤、防腐剤、抗菌剤、防錆剤等も配合することができる。
以上の材料と製造方法から得られた水性オーバーコーティング組成物は、グラビア印刷方式で、各種印刷用紙に印刷することができる。さらに、グラビア印刷機によって印刷され得られた印刷物は、様々な用途に応じて後加工され、食品など商品の包装に使用される。
The aqueous overcoating composition of the present invention has a shell of styrene, 1 to 10% of a long chain alkyl (meth) acrylate having 12 to 22 carbon atoms based on the total amount of the core / shell , and a core of styrene and (meth) acrylate. It is manufactured by blending an acrylic emulsion having a core / shell structure consisting of water, water, various additives and the like.
Examples of styrene constituting the acrylic emulsion having the core / shell structure include styrene and α-methylstyrene, and these can be used alone or in combination. (Meth) acrylic acid is used to impart an aqueous ability to the acrylic emulsion, and acrylic acid, methacrylic acid, or the like can be used alone or in combination.
Examples of the long-chain alkyl (meth) acrylate having 12 to 20 carbon atoms include lauryl acrylate, palmityl acrylate, stearyl acrylate, and the like, and these can be used alone or in combination of two or more. Further, the content of the long-chain alkyl (meth) acrylate needs to be 1% by weight to 10% by weight with respect to the total amount of the core / shell . When the amount is less than 1% by weight, the drying property is deteriorated, and the productivity is affected. When the amount is more than 10% by weight, the emulsifying ability is lowered as an acrylic emulsion, and the stability as a coating varnish is deteriorated.
As the (meth) acrylate constituting the acrylic emulsion having the core / shell structure, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (Meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. Examples include (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate, and these can be used alone or in combination of two or more.
In the present invention, the acrylic emulsion needs to have a core / shell structure, and as the shell, styrene, (meth) acrylic acid, and a long-chain alkyl (meth) acrylate having 12 to 20 carbon atoms, Styrene and (meth) acrylate are used as the core. In particular, styrene used for the shell and a long-chain alkyl (meth) acrylate having 12 to 20 carbon atoms are important in determining the drying property as a coating agent.
The core / shell weight ratio of the acrylic emulsion is preferably in the range of 10:90 to 55:45. When the core ratio is less than 10%, the gloss value of the coating film tends to decrease. When the core ratio is more than 55%, the drying property tends to be poor.
The glass transition point of the acrylic emulsion is preferably 20 to 80 ° C. Within the range of 20 to 80 ° C., the adhesion to the ink and the film-forming property of the acrylic emulsion are good.
The acrylic emulsion in the aqueous overcoating composition of the present invention is copolymerized in the presence of a polymer emulsifier obtained by copolymerizing, for example, the above styrene, (meth) acrylic acid and a long chain alkyl (meth) acrylate. It can be obtained by emulsion polymerization of possible styrene and (meth) acrylates.
In starting the polymerization reaction, a water-soluble pyrolytic polymerization initiator such as a persulfate such as potassium persulfate or ammonium persulfate or an azobis cation salt or a hydroxyl adduct can be used.
A redox initiator can also be used.
Redox initiators include combinations of organic peroxides such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and reducing agents such as Rongalite, sodium metabisulfite, or potassium persulfate, ammonium persulfate and A combination with Rongalite, sodium thiosulfate, or the like, or a combination of hydrogen peroxide and ascorbic acid is used.
Examples of neutralizing agents include bases such as ammonia, triethylamine, aminomethylpropanol, monoethanolamine, diethylaminoethanol, sodium hydroxide, and potassium hydroxide. .
In the overcoating composition, silica, alumina, polyethylene wax, antifoaming agent, leveling agent, tackifier, preservative, antibacterial agent, rust inhibitor and the like can also be blended.
The aqueous overcoating composition obtained from the above materials and production method can be printed on various printing papers by a gravure printing method. Furthermore, the printed matter obtained by printing by the gravure printing machine is post-processed according to various uses and used for packaging of products such as food.
以下，実施例および比較例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、各実施例中の「部」および「％」は「重量部」および「重量％」を表す。
＜アクリルエマルジョンの合成＞
先ず、実施例、比較例に使用するコア／シェル型のアクリルエマルジョンを合成した。合成例中の「部」は上記と同様である。
（合成例１）
窒素ガス置換した四つ口フラスコに、イソプロピルアルコールを１００部仕込み、温度を８０〜８２℃に上げた後、滴下ロートに仕込んだラウリルアクリレート１部、スチレン３０部、アクリル酸１０部、メチルメタクリレート５部、過酸化ベンゾイル１部の混合物を２時間かけて滴下した。滴下終了後、過酸化ベンゾイル０．５部を追加し、更に２時間反応させた。温度を４０℃に下げ、ジメチルエタノールアミン、イオン交換水を添加した。その後、反応フラスコの温度を８０〜８２℃に上げ、ストリッピングを行ない、最終的に固形分３０％の水溶性樹脂を得た。
上記で得た水溶性樹脂に、イオン交換水１０部を反応フラスコに仕込み、温度を８０℃〜８２℃に上げた後、過硫酸カリウムを２部添加し、スチレン２０部、２−エチルヘキシルアクリレート２４部、ブチルアクリレート１０部の混合物を２時間かけて滴下した。滴下終了後、過硫酸カリウム０．２部を添加し、２時間反応させた。このようにして得られたアクリルエマルジョン（樹脂１）の固形分は４０％であった。
合成例２〜１１
合成例２〜１１に付いては合成例１と同様な方法で重合を行い、アクリルエマルジョンである樹脂２〜樹脂１１を得た。それらのモノマーの配合を表１に示す。
実施例１
合成例１で得られたアクリルエマルジョン（樹脂１）５５部（固形４０％）、ポリエチレンワックス ２．５部、シリコーン系消泡剤０．０１部、水４２．４９部を添加し、ディスパーで１０分間攪拌して、水性オーバーコーティングワニス（１）を得た。
実施例２〜８
上記合成例２〜８について、実施例１と同様の配合により、水性コーティングワニス（２）〜水性コーティングワニス（８）を得た。
比較例１〜３
上記合成例９〜１１について、実施例１と同様の配合により、水性コーティングワニス（９）〜水性コーティングワニス（１１）を得た。
実施例および比較例で得られた水性オーバーコーティングワニスについて、乾燥性・光沢を評価した。評価方法及び判定基準は以下のとおりである。
評価法
乾燥性：印刷用紙としてコート紙（CRC２３０ｇ、レンゴー株式会社製）に対し、バーコーターＮｏ．４を用いて塗工した。塗工直後から１０秒毎に指触し、タックがなくなるところを乾燥の終点とし、乾燥性の評価をした。
判定基準：○ ０〜３０秒
△ ３０〜６０秒
× ６０秒以上
本発明で使用するバーコーターは、第一理化株式会社製のＮｏ．４を用いた。
光沢値：印刷用紙としてコート紙（CRC２３０ｇ、レンゴー株式会社製）に対し、グラビ
ア印刷機にて、腐食３０μの版で印刷し、印刷物を得た。印刷物の光沢値を「ヘイズ−グロスリフレクトメーター」〔ビックケミー・ジャパン株式会社〕により６０°−６０°を測定した。
判定基準：○ 光沢値５０以上
△ 光沢値３０〜５０
× 光沢値３０未満
結果を表１、表２に示す。乾燥性および光沢における判定は○〜△が実用範囲である
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”.
<Synthesis of acrylic emulsion>
First, core / shell type acrylic emulsions used in Examples and Comparative Examples were synthesized. The “part” in the synthesis example is the same as described above.
(Synthesis Example 1)
A four-necked flask purged with nitrogen gas was charged with 100 parts of isopropyl alcohol, the temperature was raised to 80-82 ° C., and then 1 part of lauryl acrylate, 30 parts of styrene, 10 parts of acrylic acid, and methyl methacrylate 5 were charged into the dropping funnel. A mixture of 1 part and benzoyl peroxide 1 part was added dropwise over 2 hours. After completion of the dropwise addition, 0.5 part of benzoyl peroxide was added, and the mixture was further reacted for 2 hours. The temperature was lowered to 40 ° C., and dimethylethanolamine and ion exchange water were added. Thereafter, the temperature of the reaction flask was raised to 80 to 82 ° C., and stripping was performed to finally obtain a water-soluble resin having a solid content of 30%.
To the water-soluble resin obtained above, 10 parts of ion-exchanged water was charged into a reaction flask, the temperature was raised to 80 ° C. to 82 ° C., 2 parts of potassium persulfate was added, 20 parts of styrene, and 2-ethylhexyl acrylate 24 Part and a mixture of 10 parts of butyl acrylate were added dropwise over 2 hours. After completion of dropping, 0.2 part of potassium persulfate was added and reacted for 2 hours. The acrylic emulsion (resin 1) thus obtained had a solid content of 40%.
Synthesis Examples 2 to 11
About the synthesis examples 2-11, it superposed | polymerized by the method similar to the synthesis example 1, and obtained the resin 2-resin 11 which is an acrylic emulsion. Table 1 shows the composition of these monomers.
Example 1
55 parts (solid 40%) of the acrylic emulsion (resin 1) obtained in Synthesis Example 1, 2.5 parts of polyethylene wax, 0.01 part of a silicone-based antifoaming agent and 42.49 parts of water are added, and 10 parts are added with a disper. Stirring for minutes gave an aqueous overcoating varnish (1).
Examples 2-8
About the said synthesis examples 2-8, the aqueous | water-based coating varnish (2)-the aqueous | water-based coating varnish (8) were obtained by the mixing | blending similar to Example 1. FIG.
Comparative Examples 1-3
About the said synthesis examples 9-11, the aqueous | water-based coating varnish (9)-the aqueous | water-based coating varnish (11) were obtained by the mixing | blending similar to Example 1. FIG.
The aqueous overcoating varnishes obtained in the examples and comparative examples were evaluated for dryness and gloss. Evaluation methods and criteria are as follows.
Evaluation method Drying property: For coated paper (CRC 230 g, manufactured by Rengo Co., Ltd.) as printing paper, bar coater No. 4 was used for coating. Touching was performed every 10 seconds immediately after coating, and the point at which tack disappeared was regarded as the end point of drying, and the drying property was evaluated.
Judgment criteria: ○ 0 to 30 seconds
△ 30-60 seconds
X The bar coater used in the present invention for 60 seconds or longer is No. 4 was used.
Gloss value: Coated paper (CRC 230 g, manufactured by Rengo Co., Ltd.) as a printing paper was printed with a 30 μm corrosive plate with a gravure printing machine to obtain a printed matter. The gloss value of the printed material was measured at 60 ° -60 ° with a “Haze-Gloss Reflectometer” [Bic Chemie Japan Co., Ltd.].
Judgment criteria: ○ Gloss value of 50 or more
△ Gloss value 30 ~ 50
X Tables 1 and 2 show the results of gloss values less than 30. Judgment in dryness and gloss is in the practical range from ○ to △
Claims (3)
ただし、コア／シェル重量比は１０：９０〜５５：４５である。 Shell styrene, from (meth) having 1% to 10% by weight of long chain alkyl (meth) acrylate having 12 to 22 carbon atoms to acrylic acid and the core / shell total amount, the core is a styrene (meth) acrylate comprising core / containing acrylic emulsion having a shell structure, folding cartons for overcoated I ing composition a solvent is characterized in that it is free of alcohol.
However, the core / shell weight ratio is 10:90 to 55:45.
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