JP2012172277A - Oil-resistant paper - Google Patents
Oil-resistant paper Download PDFInfo
- Publication number
- JP2012172277A JP2012172277A JP2011035119A JP2011035119A JP2012172277A JP 2012172277 A JP2012172277 A JP 2012172277A JP 2011035119 A JP2011035119 A JP 2011035119A JP 2011035119 A JP2011035119 A JP 2011035119A JP 2012172277 A JP2012172277 A JP 2012172277A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- paper
- resistant
- meth
- acrylate
- 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.)
- Granted
Links
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- 238000000034 method Methods 0.000 claims abstract description 23
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- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 238000010009 beating Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
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- 229910052708 sodium Inorganic materials 0.000 description 6
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- 229920002472 Starch Polymers 0.000 description 2
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000016019 chocolate confectionery Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical class FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011088 parchment paper Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CTYRPMDGLDAWRQ-UHFFFAOYSA-N phenyl hydrogen sulfate Chemical class OS(=O)(=O)OC1=CC=CC=C1 CTYRPMDGLDAWRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- OWHUYYOLMQBAHA-UHFFFAOYSA-M sodium octadecanoate prop-2-enamide Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Na+].C(C=C)(=O)N OWHUYYOLMQBAHA-UHFFFAOYSA-M 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
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 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
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
本発明は、動植物油等の油分の浸透を抑制する耐油紙に関するものである。 The present invention relates to an oil-resistant paper that suppresses permeation of oil such as animal and vegetable oils.
従来より耐油紙は、洗剤、菓子、乾燥食品等の包装容器用素材として広く使用されていた。その用途としては様々なものがあるが、耐油性を付与した板紙については菓子等の食品用の箱、とりわけ油脂分を大量に含むチョコレート菓子等の箱としてや、薄葉紙に耐油性を付与したものについてはハンバーガーや揚げ物等のファーストフードを包装する容器やデパート、コンビニエンスストアなどでのテイクアウト食材の包装容器等に多く使用されている。 Conventionally, oil-resistant paper has been widely used as a material for packaging containers such as detergents, confectionery, and dried foods. There are various uses, but for paperboard with oil resistance, it is used as a box for food such as confectionery, especially as a box for chocolate confectionery containing a large amount of oils and fats. Is widely used in containers for packaging fast food such as hamburgers and fried foods, and containers for take-out foods in department stores and convenience stores.
紙に耐油性を付与する手段としては、優れた耐油性を有するフッ素樹脂系の耐油剤が従来使用されており、例えば、紙、板紙の表面にフッ素樹脂系耐油剤を塗工して耐油層を設けたクッキングシートまたは紙層間にフッ素樹脂系耐油剤層を設けた菓子箱用の耐油板紙等が存在した。しかし、フッ素樹脂系耐油剤を使用した紙は、１００〜１８０℃の食品調理温度で加熱した場合、Ｃ８〜Ｃ１０のフッ素系アルコール化合物等、長期に残留しやすい成分が生成することが確認されている。また、これらフッ素樹脂系耐油剤を使用した紙を使用後焼却した際には、前記フッ素樹脂が熱分解してパーフルオロオクタン酸やパーフルオロスルホン酸等のフッ素化合物が生成し、健康または環境に悪影響を及ぼすことが懸念されるため、フッ素樹脂系耐油剤を使用しない耐油紙が求められている。 As a means for imparting oil resistance to paper, a fluororesin-based oil-resistant agent having excellent oil resistance has been conventionally used. For example, by applying a fluororesin-based oil-resistant agent on the surface of paper or paperboard, an oil-resistant layer There existed a cooking sheet provided with an oil-resistant paperboard for a confectionery box provided with a fluororesin-based oilproofing agent layer between paper sheets. However, it has been confirmed that papers using fluororesin-based oilproofing agents are likely to remain in the long term, such as C8-C10 fluoroalcohol compounds, when heated at a food cooking temperature of 100-180 ° C. Yes. In addition, when the paper using these fluororesin-based oilproofing agents is incinerated after use, the fluororesin is thermally decomposed to produce fluorine compounds such as perfluorooctanoic acid and perfluorosulfonic acid, which is healthy or environmental. Since there is concern about adverse effects, there is a demand for oil-resistant paper that does not use a fluororesin-based oil-resistant agent.
前記した熱分解するフッ素系樹脂代替の耐油紙としては紙基材にアクリル樹脂系耐油剤を塗布したもの、ポリエチレンフィルム貼合紙、及びポリエチレン樹脂を塗布したもの、シリコーン系、ワックス系耐油剤を使用したもの、熱を加えても不活性ガスを発生させないように製法が改良されたフッ素系樹脂を使用したもの等々の耐油紙ならびに製造技術が開示されるに至っているが、それぞれ長短所があるため一部実用化されてはいるものの依然として使用者からの改善要望は根強い。 As the above-mentioned oil-resistant paper as an alternative to fluorine resin that thermally decomposes, a paper base coated with an acrylic resin-based oil-resistant agent, a polyethylene film-bonded paper, a paper coated with a polyethylene resin, a silicone-based, wax-based oil-resistant agent Oil-resistant paper and manufacturing technologies such as those used and those using fluorine-based resins whose production method has been improved so that inert gas is not generated even when heat is applied have been disclosed, but each has advantages and disadvantages For this reason, although it has been put into practical use, there is still a strong demand for improvement from users.
ところで、耐油紙の中でも比較的低坪量の耐油紙については、ファーストフードハンバーガーの包装紙、揚げ物を包装する容器やデパート、コンビニエンスストアなどでのテイクアウト食材の包装容器等に多く使用されている。しかし、前記耐油紙は製袋時に生じる折り目部分の耐油性が低下し、油脂成分の滲出が生じる現象が生じやすい。また、包装時に生じるシワの部分も耐油性低下を引き起こす要因となる。 By the way, among oil-resistant papers, oil-resistant paper having a relatively low basis weight is often used for packaging paper for fast food hamburgers, containers for packaging fried foods, department stores, packaging containers for take-out foods at convenience stores, and the like. However, the oil-resistant paper tends to have a phenomenon in which the oil resistance of the crease portion generated during bag making is reduced and the oil and fat component is oozed out. Moreover, the wrinkle part produced at the time of packaging also becomes a factor which causes oil resistance fall.
耐油紙の中でも、撥油性によって外部への油脂成分の滲出を防止していたフッ素系樹脂を用いた耐油紙では、製袋時に生じる折り目部分の耐油性は比較的高く保つことが可能である。 Among oil-resistant papers, oil-resistant paper using a fluororesin that has prevented oil and fat components from exuding to the outside due to oil repellency can maintain a relatively high oil resistance at the folds produced during bag making.
一方、アクリル系樹脂エマルジョンの塗工により製造した耐油紙は、耐油層をピンホールなく成膜させることで外部への油脂成分の滲出を防止することにより耐油性を発現させているため、フッ素系樹脂と比較すると、折り目部分では成膜した耐油塗工層の割れが生じる場合があり、前記折り目部分の耐油性が低下し易い傾向にあった。 On the other hand, the oil-resistant paper produced by coating acrylic resin emulsion is oil-free by preventing oil and fat components from leaching to the outside by forming an oil-resistant layer without pinholes. In comparison with the resin, the oil-resistant coating layer formed on the crease may be cracked, and the oil resistance of the crease tends to be lowered.
特に、アクリル系樹脂エマルジョン耐油剤に顔料を添加し、耐油層のブロッキング性能を向上させた耐油紙は、顔料成分が耐油層の耐折強度を低下させ、割れが生じやすくなることから、折部の耐油性が著しく低下することが知られている。
そこで、従来は耐油剤単独、もしくは樹脂成分のみで耐油層で構成し、折り部の耐油性を向上させる方法が採られてきた。
ただし、アクリル系樹脂エマルジョン耐油剤は成膜性の観点から、ガラス転移温度（以下Ｔｇと略記する）が低い化合物が多用されており、Ｔｇが低い耐油剤単独では、耐油層の耐ブロッキング性能が劣り、実用上重送などの問題が生じる可能性があった。
In particular, oil-resistant paper that improves the blocking performance of the oil-resistant layer by adding a pigment to the acrylic resin emulsion oil-resistant agent reduces the folding strength of the oil-resistant layer and the cracking tends to occur. It is known that the oil resistance of the oil significantly decreases.
Therefore, conventionally, a method of improving the oil resistance of the folded portion by forming an oil-resistant layer with an oil-resistant agent alone or a resin component alone has been employed.
However, from the viewpoint of film formability, acrylic resin emulsion oil proofing agents often use compounds having a low glass transition temperature (hereinafter abbreviated as Tg), and an oil proofing agent having a low Tg alone has the anti-blocking performance of the oil-resistant layer. Inferior, there was a possibility that problems such as double feeding would occur in practice.
一方、Ｔｇが高いアクリル系樹脂エマルジョン耐油剤は、層自体が硬くなってしまうことから、耐油層自体の耐折強度が低下してしまう問題点があった。 On the other hand, the acrylic resin emulsion oil proofing agent having a high Tg has a problem that the folding strength of the oil resistant layer itself is lowered because the layer itself becomes hard.
前記問題点を解決するために、先行技術文献に示す方法が知られているが、アクリル系樹脂エマルジョン耐油剤を使用した際、耐油層の耐折強度を保ちつつ、実用上効果的に耐油性を発現させることが困難であるというのが現状である。 In order to solve the above problems, the method shown in the prior art document is known, but when using an acrylic resin emulsion oil resistance agent, the oil resistance is effectively and practically maintained while maintaining the folding resistance of the oil resistance layer. The present situation is that it is difficult to express.
例えば、特許文献１にはアクリル系樹脂のＴｇについて、比較的低いＴｇの樹脂をアンダーコート層に用いることで製函時の罫線割れを防ぎ、比較的高いＴｇの樹脂をオーバーコート層に用いることで、ブロッキングを防止する技術が開示されているが、幾層にもわたり塗布することにより耐油性は確保できるもののその手間の多さからコストが極端に高くなる。 For example, Patent Document 1 discloses that Tg of an acrylic resin uses a relatively low Tg resin for the undercoat layer to prevent ruled line cracking during box making, and uses a relatively high Tg resin for the overcoat layer. Although a technique for preventing blocking is disclosed, the oil resistance can be ensured by applying it over several layers, but the cost becomes extremely high due to the large amount of labor.
また、特許文献２にはアクリル樹脂系エマルジョンの耐油剤と浸透剤を混合し、塗布する技術が開示されているが、単独塗工の場合は、耐油剤として比較的Ｔｇの低い耐油剤を塗布することで、ブロッキングが生じやすくなるため好ましくない。また、原紙に浸透させて耐油性を発現させていることから、耐油剤の塗布量が増加してしまう。
すなわち、アクリル系樹脂エマルジョン耐油剤を使用した場合、耐油層の耐折強度を適正に保ちつつ、効果的に耐油性を発現させることが困難であるというのが現状である。
Patent Document 2 discloses a technique of mixing and applying an oil resistant agent and a penetrant of an acrylic resin emulsion, but in the case of single coating, an oil resistant agent having a relatively low Tg is applied as an oil resistant agent. This is not preferable because blocking is likely to occur. Further, since the oil resistance is expressed by infiltrating the base paper, the amount of the oil resistant agent applied increases.
That is, when an acrylic resin emulsion oil proofing agent is used, it is difficult to effectively exhibit oil resistance while maintaining the folding strength of the oil resistant layer properly.
本発明は、耐油性樹脂層としてアクリル樹脂系エマルジョンを使用した際、紙支持体の透気度を高く制御することにより、フッ素系化合物を用いないで環境面での問題が少なく、折り部の耐油性を向上させた耐油紙を提供することを目的とする。 In the present invention, when an acrylic resin emulsion is used as the oil-resistant resin layer, by controlling the air permeability of the paper support to be high, there are few environmental problems without using a fluorine compound, and An object is to provide an oil-resistant paper with improved oil resistance.
本発明は、以下の各発明を包含する。
（１）坪量が２０〜７０ｇ／ｍ２、ＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．５−２：２０００に準じて測定した王研式透気度が７０秒以上である紙支持体の少なくとも片面に耐油層を設けた耐油紙であって、耐油層を構成する耐油剤が重量平均分子量５万〜２００万、ガラス転移温度３０℃未満のアクリル系樹脂であり、かつ折り目部分におけるＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．４１：２０００に準じて測定したキット法による耐油度が４級以上である耐油紙。
The present invention includes the following inventions.
(1) Basis weight is 20 to 70 g / m 2 , JAPAN TAPPI Paper Pulp Test Method No. 5-2: Oil-resistant paper having an oil-resistant layer provided on at least one side of a paper support having a paper permeability of 70 seconds or more measured according to 2000, wherein the oil-resistant agent constituting the oil-resistant layer is a weight average. It is an acrylic resin having a molecular weight of 50,000 to 2,000,000 and a glass transition temperature of less than 30 ° C., and the JAPAN TAPPI paper pulp test method no. Oil-resistant paper whose oil resistance measured by the kit method measured according to 41: 2000 is grade 4 or higher.
（２）前記紙支持体を構成する原料パルプのＪＩＳ Ｐ ８１２１−１９９５に準じて測定した叩解度（カナダ標準フリーネス）が３００ｍｌ以下である（１）に記載の耐油紙。 (2) The oil-resistant paper according to (1), wherein the beating degree (Canadian standard freeness) measured according to JIS P 8121-1995 of the raw material pulp constituting the paper support is 300 ml or less.
（３）前記紙支持体の密度が０．８〜１．２ｇ／ｃｍ３である（１）または（２）に記載の耐油紙。 (3) The oil resistant paper according to (1) or (2), wherein the density of the paper support is 0.8 to 1.2 g / cm 3 .
本発明により、製袋時や、包装時に生じる折り目、およびシワ部の耐油性の低下を抑制した耐油紙を提供することができる。 According to the present invention, it is possible to provide an oil-resistant paper that suppresses a decrease in oil resistance of creases and wrinkles generated during bag making or packaging.
本発明の耐油紙において、紙支持体を構成する木材パルプとしては、通常製紙用として使用されるあらゆるものが使用できる。例えば、広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒クラフトパルプ（ＮＢＫＰ）、広葉樹晒サルファイトパルプ（ＬＢＳＰ）、針葉樹晒サルファイトパルプ（ＮＢＳＰ）等の化学パルプ、ストーングランドパルプ（ＧＰ）、加圧ストーングランドパルプ（ＰＧＷ）、リファイナーグランドパルプ（ＲＧＰ）、ケミグランドパルプ（ＣＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミサーモメカニカルパルプ（ＣＴＭＰ）等の未晒、半晒、あるいは晒パルプ、亜硫酸パルプ、古紙パルプ等が使用できる。
紙支持体のパルプ配合においては、寸法安定性に優れるＬＢＫＰを多く配合することが好ましく、全パルプ１００質量％のうち６０〜１００質量％配合するのが好ましい。
In the oil-resistant paper of the present invention, as wood pulp constituting the paper support, any of those usually used for papermaking can be used. For example, chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood bleached sulfite pulp (LBSP), softwood bleached sulfite pulp (NBSP), stone grand pulp (GP), pressure stone Unbleached, semi-bleached or bleached pulp, sulfite pulp, waste paper such as ground pulp (PGW), refiner ground pulp (RGP), chemiground pulp (CGP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP) Pulp etc. can be used.
In the pulp blending of the paper support, it is preferable to blend a large amount of LBKP having excellent dimensional stability, and it is preferable to blend 60 to 100% by weight out of 100% by weight of the total pulp.
本発明における紙支持体について、坪量が２０ｇ／ｍ２〜７０ｇ／ｍ２であり、かつ王研式透気度が７０秒以上であれば、各種の紙が使用できる。すなわち、本発明に用いる紙支持体としては、少なくとも一方の表面に後述する特定のアクリル系樹脂層を設けることができるものであれば良く、用途に応じて適宜選択することができる。例えば、晒または未晒クラフト紙、上質紙、中質紙、微塗工紙、塗工紙、片艶紙、セミグラシン紙、グラシン紙、パーチメント紙等が挙げられる。紙支持体の坪量が２０ｇ／ｍ２未満になると、耐油剤の塗工時に紙支持体に必要な強度を保持させることが難しく、７０ｇ／ｍ２を超えると、折り目部分で紙支持体の座屈が生じやすくなるため、紙支持体の割れを生じ、折り目の耐油性が低下し易くなる。
また、紙支持体のＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．５−２：２０００に準じて測定した王研式透気度が７０秒未満になると、原紙の折り部の伸びが小さくなり、折り目の耐油性が低下しやすくなる。前記王研式透気度の好ましい範囲としては、７５〜４００ｍｌである。
For a paper support in the invention, having a basis weight of 20g / m 2 ~70g / m 2 , and if the Oken type air permeability than 70 seconds, various papers can be used. That is, the paper support used in the present invention may be any paper support as long as a specific acrylic resin layer described later can be provided on at least one surface, and can be appropriately selected according to the application. For example, bleached or unbleached kraft paper, high quality paper, medium quality paper, finely coated paper, coated paper, glossy paper, semi-glassine paper, glassine paper, parchment paper and the like can be mentioned. When the basis weight of the paper support is less than 20 g / m 2 , it is difficult to maintain the strength required for the paper support during the application of the oil resistant agent, and when the basis weight exceeds 70 g / m 2 , Since buckling tends to occur, the paper support is cracked, and the oil resistance of the crease tends to be lowered.
In addition, the JAPAN TAPPI paper pulp test method no. When the Oken air permeability measured according to 5-2: 2000 is less than 70 seconds, the elongation of the folded portion of the base paper becomes small, and the oil resistance of the fold is likely to be lowered. A preferable range of the Oken type air permeability is 75 to 400 ml.
さらに、紙支持体の透気度を高めるため、使用するパルプの叩解度をＪＩＳ Ｐ ８１２１−１９９５に準じて測定したカナダ標準フリーネスが３００ｍｌ以下とすることが好ましい。叩解度のより好ましい範囲は８０〜２５０ｍｌである。叩解度が３００ｍｌを超えると、紙支持体の透気度を高く保つことが困難となるほか、折り目の座屈が生じやすくなり、折り目の耐油性が低下しやすくなるおそれがある。 Furthermore, in order to increase the air permeability of the paper support, it is preferable that the Canadian standard freeness measured according to JIS P 8121-1995 is 300 ml or less. A more preferable range of beating degree is 80 to 250 ml. When the beating degree exceeds 300 ml, it becomes difficult to keep the air permeability of the paper support high, and fold buckling tends to occur, and the oil resistance of the fold tends to decrease.
なお、使用するパルプは、例えばビーター、ジョルダン、シングルディスク・リファイナー、コニカルリファイナー、円筒型リファイナー、デラックス・ファイナー、ダブル・ディスク・リファイナー（ＤＤＲ）、媒体攪拌ミル、振動式ミル等の叩解機により前記叩解度となるように調整される。叩解の条件は特に限定されないが、各種リファイナーの刃の形状、回転数、パルプの濃度、パルプの繊維長、パルプの粗度等が叩解後のパルプ物性に影響するので、前記所望の叩解度が得られるように適宜叩解条件が選択される。 The pulp to be used is, for example, beaten by a beater such as a beater, Jordan, single disk refiner, conical refiner, cylindrical refiner, deluxe refiner, double disk refiner (DDR), medium stirring mill, vibratory mill or the like. Adjusted to a degree. The beating conditions are not particularly limited, but the shape of the refiner blade, the number of revolutions, the pulp concentration, the fiber length of the pulp, the roughness of the pulp, etc. affect the physical properties of the pulp after beating, so the desired beating degree is The beating condition is appropriately selected so as to obtain it.
また、紙支持体の透気度を高める方法として、密度を上げ、０．８〜１．２ｇ／ｃｍ３とすることが好ましく、より好ましくは０．８５〜１．１ｇ／ｃｍ３である。紙支持体の密度を上げる具体的方法としては、紙支持体の抄造時に湿紙時に使用するブレーカースタックなど、乾燥後にマシンカレンダーやソフトニップカレンダー、グロスカレンダーを使用すること、あるいは紙支持体抄造後にスーパーカレンダーを使用することができる。その中でも、湿紙時に使用するブレーカースタックは乾燥後のカレンダー処理と比較しても、紙水分が高い状態で圧力を与えることが可能であり、効率的に密度を上げることができるため、特に好ましい。
ここで、本発明において使用される抄紙機としては、エアクッションヘッドボックスあるいはハイドロリックヘッドボックスを有する長網抄紙機、ツインワイヤー抄紙機、オントップ型ツインワイヤー抄紙機、ヤンキー抄紙機等を挙げることができる。
Further, as a method for increasing the air permeability of the paper support, the density is preferably increased to 0.8 to 1.2 g / cm 3 , more preferably 0.85 to 1.1 g / cm 3 . Specific methods for increasing the density of the paper support include the use of a machine calendar, soft nip calender, gloss calendar after drying, such as a breaker stack for wet paper when paper support is made, or after paper support is made. A super calendar can be used. Among them, the breaker stack used at the time of wet paper is particularly preferable because it can apply pressure in a state where the paper moisture is high and can efficiently increase the density even when compared with calendering after drying. .
Here, examples of the paper machine used in the present invention include a long net paper machine having an air cushion head box or a hydraulic head box, a twin wire paper machine, an on-top type twin wire paper machine, and a Yankee paper machine. Can do.
次に、耐油層を構成するアクリル系樹脂について説明する。本発明でいうアクリル系樹脂とは、（ａ）エチレン性不飽和カルボン酸含有モノマーを必須成分として含み、（ｂ）（メタ）アクリル酸アルキルエステルモノマー、（ｃ）これらのモノマーと共重合可能な他のモノマーから選択される少なくとも１種のモノマーからなる共重合体である。 Next, the acrylic resin constituting the oil resistant layer will be described. The acrylic resin referred to in the present invention includes (a) an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and (b) a (meth) acrylic acid alkyl ester monomer, (c) copolymerizable with these monomers. It is a copolymer comprising at least one monomer selected from other monomers.
本発明において用いられる（ａ）エチレン性不飽和カルボン酸含有モノマーとしては、例えば（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、モノアルキルマレイン酸、モノアルキルフマル酸、モノアルキルイタコン酸等が挙げられ、これらのうちから少なくとも１種を用いることが必要である。 Examples of the (a) ethylenically unsaturated carboxylic acid-containing monomer used in the present invention include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, monoalkylmaleic acid, monoalkylfumaric acid, and monoalkyl. Itaconic acid and the like can be mentioned, and it is necessary to use at least one of them.
本発明において用いられる（ｂ）（メタ）アクリル酸アルキルエステルモノマーとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル等が挙げられ、これらのうちから少なくとも１種を用いることができる。 Examples of the (b) (meth) acrylic acid alkyl ester monomer used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, ( Meta) dodecyl acrylate, etc., and at least one of them It can be used.
本発明において用いられる（ｃ）これらのモノマーと共重合可能な他のモノマーとしては、スチレン、酢酸ビニル、塩化ビニル、塩化ビニリデン、（メタ）アクリロニトリル、エチレン、プロピレン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリルレート、グリセロールモノ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、１，２−プロピレングリコールジ（メタ）アクリレート、１，３−プロピレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジビニルベンゼン、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジアリル（メタ）アクリレート、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ´−メチレンビス（メタ）アクリルアミド、ビニルスルホン酸ナトリウム、ｐ−スチレンスルホン酸ナトリウム、２−アクリルアミド−２−メチルプロパンスルホン酸、酸ホスホキシエチル（メタ）アクリレートエタノールアミンハーフ塩、３−アリロキシ−２−ヒドロキシプロパンスルホン酸ナトリウム、ポリオキシエチレンスチレン化フェニル硫酸ナトリウム、グリセリンモノアリルエーテルモノスルホコハク酸ナトリウム、２−スルホエチル（メタ）アクリル酸ナトリウム、（メタ）アクリルアミドステアリン酸ナトリウム、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、アクロレイン、ジアセトン（メタ）アクリルアミド、ホルミルスチロール、ビニルメチルケトン、ビニルエチルケトン、（メタ）アクリロオキシアルキルプロペナール、ジアセトン（メタ）アクリレート、アセトニル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、ジアリルフタレート、トリアリルシアヌレート等が挙げられ、これらのうちから少なくとも１種を用いることができる。 (C) Other monomers copolymerizable with these monomers used in the present invention include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, ethylene, propylene, 2-hydroxyethyl (meth) acrylate. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Glycerol mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, diallyl (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-meth Cymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, sodium vinyl sulfonate, sodium p-styrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, acid Phosphoxyethyl (meth) acrylate ethanolamine half salt, sodium 3-allyloxy-2-hydroxypropane sulfonate, sodium polyoxyethylene styrenated phenyl sulfate, sodium glyceryl monoallyl ether monosulfosuccinate, 2-sulfoethyl (meth) acrylic acid Sodium, (meth) acrylamide sodium stearate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxy ester (Meth) acrylate, ethyl carbitol (meth) acrylate, caprolactone-modified (meth) acrylate, acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, (meth) acrylooxyalkylpropenal, Examples include diacetone (meth) acrylate, acetonyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, and the like. Can be used.
本発明において用いられるアクリル系樹脂は公知の乳化重合法によって得ることができる。例えば、所定の反応容器に前記の各種モノマー類、乳化剤および水を仕込み、ラジカル重合開始剤を加え、攪拌下、加温することにより得られる。 The acrylic resin used in the present invention can be obtained by a known emulsion polymerization method. For example, it can be obtained by charging the aforementioned various monomers, emulsifier and water into a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring.
ラジカル重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、ｔ−ブチルハイドロオキサイド、ｔ−ブチルパーオキシベンゾエート等の過酸化物、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系化合物が挙げられる。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤を前記ラジカル重合開始剤と組合せて（レドックス系重合開始剤）用いることができる。 Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides such as hydrogen peroxide, t-butyl hydroxide, and t-butyl peroxybenzoate, and 2,2-azo. Examples thereof include azo compounds such as bisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, and 2,2-azobis (2,4-dimethylvaleronitrile). If acceleration of polymerization rate or low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt is combined with the radical polymerization initiator (redox polymerization initiation). Agent).
重合開始剤の使用量は、モノマー成分１００質量部に対して、通常０．０２〜３質量部であるが、好ましくは０．０５〜１質量部である。 Although the usage-amount of a polymerization initiator is 0.02-3 mass parts normally with respect to 100 mass parts of monomer components, Preferably it is 0.05-1 mass part.
使用する乳化剤としては、特に限定しないが、アニオン性乳化剤、ノニオン性乳化剤、反応性乳化剤が挙げられる。
アニオン性乳化剤としては、オレイン酸カリウム等の脂肪酸金属塩、ラウリル硫酸ナトリウム等のアルキル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸ナトリウム等のアルキルスルホン酸塩、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキルアリルエーテルリン酸エステル等が挙げられる。
ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。
反応性乳化剤としては、種々の分子量（ＥＯ付加モル数の異なる）のポリエチレングリコールモノ（メタ）アクリレート、ポリオキシエチレンアルキルフェノールエーテル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルスルホン酸アンモニウム、ポリエチレングリコールのモノマレイン酸エステルおよびその誘導体、（メタ）アクリロイルポリオキシアルキレンアルキルエーテルリン酸エステル等が挙げられる。
Although it does not specifically limit as an emulsifier to be used, An anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier are mentioned.
Examples of anionic emulsifiers include fatty acid metal salts such as potassium oleate, alkyl sulfates such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfonates such as sodium alkyl naphthalene sulfonate, and dialkyl sulfosuccinates. Examples thereof include sodium acid, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, and the like.
Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like.
As reactive emulsifiers, polyethylene glycol mono (meth) acrylate, polyoxyethylene alkylphenol ether (meth) acrylate, ammonium 2- (meth) acryloyloxyethylsulfonate, polyethylene glycol having various molecular weights (different EO addition mole numbers) Monomaleic acid esters and derivatives thereof, (meth) acryloyl polyoxyalkylene alkyl ether phosphates, and the like.
乳化剤の使用量は、通常、モノマー成分１００質量部に対して、０．１〜１０質量部程度使用すればよく、好ましくは０．２〜５質量部である。乳化剤の使用量がこの範囲にあることによって、凝固物を生じることなく、適度な粒子径のアクリル系樹脂エマルジョンが得られる。 The amount of the emulsifier used is usually about 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the monomer component. By using the amount of the emulsifier within this range, an acrylic resin emulsion having an appropriate particle size can be obtained without producing a coagulated product.
本発明において用いられるアクリル系樹脂は前記のように水媒体中で乳化重合法により得られるが、アクリル系樹脂エマルジョンの固形分濃度を３０〜７５質量％、好ましくは４０〜６５質量％程度として行うことができる。重合反応は単一重合開始剤の場合では通常４０〜９５℃、好ましくは６０〜９０℃程度の反応温度で、１〜１０時間、好ましくは４〜８時間程度行えばよい。また、レドックス系重合開始剤の場合では反応温度はより低く、通常５〜９０℃、好ましくは２０〜７０℃程度である。モノマーの添加方法としては、一括添加法、分割添加法、連続添加法等で、モノマータップ法、モノマープレ乳化タップ法等の方法で行うことができる。好ましくは連続添加法で、モノマープレ乳化タップ法である。 The acrylic resin used in the present invention is obtained by an emulsion polymerization method in an aqueous medium as described above, and the acrylic resin emulsion has a solid content concentration of 30 to 75% by mass, preferably about 40 to 65% by mass. be able to. In the case of a single polymerization initiator, the polymerization reaction is usually carried out at a reaction temperature of about 40 to 95 ° C., preferably about 60 to 90 ° C. for 1 to 10 hours, preferably about 4 to 8 hours. In the case of a redox polymerization initiator, the reaction temperature is lower, usually 5 to 90 ° C, preferably about 20 to 70 ° C. As a monomer addition method, a batch addition method, a divided addition method, a continuous addition method, or the like, such as a monomer tap method or a monomer pre-emulsification tap method can be used. The monomer pre-emulsification tapping method is preferred by the continuous addition method.
本発明において用いられるアクリル系樹脂は、平均粒子径が０．０１〜１．０μｍであるものが好ましい。平均粒子径がこの範囲にあれば水分散性が良好となる。平均粒子径が０．０１μｍ未満であると、塗工時の機械的安定性が悪くなるおそれがあり、１．０μｍを超えるとハイシェア粘度が低く、所望の塗布量が得られなかったり、塗工面にストリーク等の塗工むらが発生するおそれがある。なお、平均粒子径については、乳化剤や重合開始剤の種類および添加量、添加方法、添加速度、攪拌条件等を適宜設定することにより容易に調整することができる。ここで、エマルジョンの平均粒子径は光散乱法粒子径分布測定機（ＨＯＲＩＢＡ社製、商品名：ＬＢ−５５０）で測定したものである。 The acrylic resin used in the present invention preferably has an average particle size of 0.01 to 1.0 μm. If the average particle diameter is within this range, water dispersibility will be good. If the average particle size is less than 0.01 μm, the mechanical stability during coating may be deteriorated. If it exceeds 1.0 μm, the high shear viscosity is low, and a desired coating amount may not be obtained. There is a risk of uneven coating such as streaks. In addition, about an average particle diameter, it can adjust easily by setting suitably the kind and addition amount of an emulsifier and a polymerization initiator, the addition method, the addition speed, stirring conditions, etc. Here, the average particle size of the emulsion is measured with a light scattering particle size distribution analyzer (trade name: LB-550, manufactured by HORIBA).
本発明においては種々の塗工方式での塗工適性を確保するため、耐油層塗液の粘度を制御する必要がある。そこで、アクリル系樹脂を乳化重合する際に分子量（重量平均分子量）を反応温度、反応時間、平均粒子径、酸価の制御により適宜調節する。さらに、公知の連鎖移動剤を用いることは好ましい実施態様である。このような連鎖移動剤としては、ブチルメルカプタン、ドデシルメルカプタン、チオグリコール酸オクチル、イソプロピルアルコール、メタノール、四塩化炭素等が挙げられる。その使用量は、モノマー成分１００質量部に対して０．００１〜２．０質量部であり、好ましくは０．０５〜１．０質量部である。 In the present invention, it is necessary to control the viscosity of the oil-resistant layer coating liquid in order to ensure coating suitability in various coating systems. Therefore, when the acrylic resin is emulsion-polymerized, the molecular weight (weight average molecular weight) is appropriately adjusted by controlling the reaction temperature, reaction time, average particle diameter, and acid value. Furthermore, it is a preferred embodiment to use a known chain transfer agent. Examples of such chain transfer agents include butyl mercaptan, dodecyl mercaptan, octyl thioglycolate, isopropyl alcohol, methanol, carbon tetrachloride and the like. The usage-amount is 0.001-2.0 mass parts with respect to 100 mass parts of monomer components, Preferably it is 0.05-1.0 mass part.
本発明において用いられるアクリル系樹脂はモノマー組成が異なる複数のモノマー成分の個々が重合する過程で一体化してなる樹脂複合体、すなわち、モノマーが異なる複数のモノマー成分を各段で用いた多段の乳化重合により容易に得られるものであり、いわゆるコアシェル型のエマルションであることが好ましい（以下コア部を構成する重合体をコア部、シェル部を構成する重合体をシェル部と略す場合がある）。さらに好ましくは、前記コアシェル型のエマルションはそのコア部には低いＴｇの樹脂を配置することが可能で、それにより塗膜形成が容易になり、皮膜自体が強靭になる。また、シェル部に高いＴｇの水溶性樹脂を配置することにより硬度を持たせることが可能になり、耐ブロッキング性が向上する。このようなコアシェル型のエマルジョンは以下のようにして容易に得ることができる。 The acrylic resin used in the present invention is a resin composite formed by integrating a plurality of monomer components having different monomer compositions, that is, a multi-stage emulsification using a plurality of monomer components having different monomers in each stage. It is easily obtained by polymerization, and is preferably a so-called core-shell type emulsion (hereinafter, the polymer constituting the core part may be abbreviated as the core part and the polymer constituting the shell part may be abbreviated as the shell part). More preferably, in the core-shell type emulsion, a resin having a low Tg can be disposed in the core portion, whereby the coating film can be easily formed and the coating itself becomes tough. Moreover, it becomes possible to give hardness by arrange | positioning water-soluble resin of high Tg to a shell part, and blocking resistance improves. Such a core-shell type emulsion can be easily obtained as follows.
アクリル系樹脂をコアシェル型エマルジョンとする場合、モノマー組成の異なる複数のモノマー成分を各段で用いた多段の乳化重合工程を経て製造する。ここで、多段の乳化重合とは、前段までに用いたモノマー成分の８０質量％以上、好ましくは９０質量％以上が重合してから、新たにモノマー成分を加えて次の段の重合を行う重合方法をいう。乳化重合の段数は、特に限定されないが、製造工程を簡略化するためには、２段または３段が好ましい。
本発明のアクリル系樹脂の製造においては、第一段の乳化重合工程ではＴｇが低いモノマー成分を用い、最終段の乳化重合工程ではＴｇが高いモノマー成分を用いる。
When the acrylic resin is made into a core-shell type emulsion, it is produced through a multi-stage emulsion polymerization process in which a plurality of monomer components having different monomer compositions are used in each stage. Here, the multistage emulsion polymerization is a polymerization in which 80% by mass or more, preferably 90% by mass or more of the monomer component used up to the previous stage is polymerized, and then the monomer component is newly added to perform the next stage polymerization. Say the method. The number of stages of emulsion polymerization is not particularly limited, but two or three stages are preferable in order to simplify the production process.
In the production of the acrylic resin of the present invention, a monomer component having a low Tg is used in the first emulsion polymerization step, and a monomer component having a high Tg is used in the final emulsion polymerization step.
いずれにしても、前記したような適切な粒子径と適切な酸価を有することでハイシェア粘度を高く保ちつつ、かつ、皮膜になった時に、各種成分が分離することなく、均質なポリマーに近い状態で製膜されることが好ましい。そのことは、皮膜のＴｇを測定した時に、モノマーの違いに由来する複数のＴｇが観測されないで、一つのＴｇが観測されることが望ましいということである。 In any case, having an appropriate particle size and an appropriate acid value as described above, the high shear viscosity is kept high, and when it becomes a film, various components are not separated and close to a homogeneous polymer. It is preferable to form a film in a state. That is, when the Tg of the film is measured, it is desirable that one Tg is observed without observing a plurality of Tg derived from the difference in monomers.
本発明においてＴｇは、ＪＩＳ Ｋ ７１２１−１９８７ プラスチックの転移温度測定方法に準じて示差走査熱量測定（ＤＳＣ）により得られるものである。 In the present invention, Tg is obtained by differential scanning calorimetry (DSC) according to the transition temperature measurement method of JIS K 7121-1987 plastic.
コア部に適する樹脂としては、概ねＴｇが−５０〜＋２５℃程度とすることが好ましい。重合に使用するモノマーとしては、単独であれば、メチルアクリレート、イソプロピルアクリレート、ヒドロキシプロピルアクリレート、ｎ−ヘキシルメタクリレートなどが使用できるが、前記した好ましいＴｇを有するコア部を重合するためには、低Ｔｇのポリマーを形成できる低Ｔｇモノマーと、高いＴｇ（ここでは２５℃以上）のポリマーを形成できる高Ｔｇモノマーの共重合体が好ましい。 As a resin suitable for the core portion, it is generally preferable that Tg is about −50 to + 25 ° C. As a monomer used for polymerization, methyl acrylate, isopropyl acrylate, hydroxypropyl acrylate, n-hexyl methacrylate, and the like can be used alone, but in order to polymerize the core portion having the above preferable Tg, low Tg A copolymer of a low Tg monomer capable of forming a polymer with a high Tg monomer capable of forming a polymer having a high Tg (here, 25 ° C. or higher) is preferable.
シェル部にはＴｇが４０〜１４０℃ものもが好ましい。前記範囲に調整するためには、メチルメタクリレート（ＭＭＡ）を主成分とする共重合体が好ましく使用できる。共重合の相手のモノマーとしては、前記した各種アクリルモノマーが使用できる。また、シェル部には、後述するように、酸価を有することが好ましく、そのため、アクリル酸またはメタクリル酸を共重合することが好ましい。シェル部を構成する（共）重合体には高いＴｇが好ましいので、酸としてはメタクリル酸が最適である。メタクリル酸は耐油性の向上にも寄与する。さらに、前記した好ましいＴｇを有するシェル部を重合するために、上記以外のモノマー使用することは可能である。 The shell portion preferably has a Tg of 40 to 140 ° C. In order to adjust to the said range, the copolymer which has a methyl methacrylate (MMA) as a main component can be used preferably. The various acrylic monomers described above can be used as monomers for copolymerization. Moreover, it is preferable that a shell part has an acid value so that it may mention later, Therefore, it is preferable to copolymerize acrylic acid or methacrylic acid. Since a high Tg is preferable for the (co) polymer constituting the shell portion, methacrylic acid is optimal as the acid. Methacrylic acid also contributes to improving oil resistance. Furthermore, in order to polymerize the shell part having the above-mentioned preferable Tg, it is possible to use a monomer other than the above.
前記Ｔｇ範囲となるモノマー組成：
（ａ）エチレン性不飽和カルボン酸含有モノマー：１０〜６０質量％、
（ｂ）（メタ）アクリル酸アルキルエステルモノマー：１０〜８０質量％、
（ｃ）これらのモノマーと共重合可能な他のモノマー：０〜７０質量％、が好ましい。
Monomer composition in the Tg range:
(A) ethylenically unsaturated carboxylic acid-containing monomer: 10 to 60% by mass,
(B) (meth) acrylic acid alkyl ester monomer: 10 to 80% by mass,
(C) Other monomers copolymerizable with these monomers: 0 to 70% by mass are preferable.
本発明において用いられるアクリル系樹脂は重量平均分子量が５万〜２００万である必要がある。重量平均分子量が５万未満になると耐油剤自体の耐油性能が低下し、耐油性が悪化する。逆に、重量平均分子量が２００万を超えると樹脂の成膜性が低下するため、塗工むらが発生し、耐油性が悪化する。ここで、アクリル系樹脂の重量平均分子量はポリスチレン換算（分析装置：ＴＯＳＯＨ社製の「ＨＬＣ−８１２０ＧＰＣ」、カラム：「ＴＳＫｇｅｌ ＧＭＨ−Ｈ（Ｓ）」）で測定したものである。 The acrylic resin used in the present invention needs to have a weight average molecular weight of 50,000 to 2,000,000. When the weight average molecular weight is less than 50,000, the oil resistance of the oil resistant agent itself is lowered and the oil resistance is deteriorated. On the other hand, if the weight average molecular weight exceeds 2 million, the film formability of the resin is lowered, so that coating unevenness occurs and the oil resistance deteriorates. Here, the weight average molecular weight of the acrylic resin is measured in terms of polystyrene (analyzer: “HLC-8120GPC” manufactured by TOSOH, column: “TSKgel GMH-H (S)”).
さらに、本発明の耐油層塗液には前記アクリル系樹脂エマルジョンの他に、さらにバインダー樹脂、顔料などを含んでもよい。また、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、着色剤等の通常用いられている各種助剤が適宜使用できる。
本発明に使用できるバインダー樹脂としては、カゼイン、澱粉、変性澱粉、ポリビニルアルコールなどの水溶性高分子、または、ポリエステル系樹脂、ポリウレタン系樹脂、スチレン−ブタジエン系樹脂、酢酸ビニル系樹脂、エチレン−酢酸ビニル系樹脂、アクリロニトリル−ブタジエン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、カルボキシメチルセルロース系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂等の水分散液が使用できる。
Furthermore, the oil-resistant layer coating liquid of the present invention may further contain a binder resin, a pigment and the like in addition to the acrylic resin emulsion. Moreover, various auxiliary agents normally used, such as a dispersing agent, a thickener, a water retention agent, an antifoaming agent, and a coloring agent, can be used as needed.
Examples of binder resins that can be used in the present invention include water-soluble polymers such as casein, starch, modified starch, and polyvinyl alcohol, or polyester resins, polyurethane resins, styrene-butadiene resins, vinyl acetate resins, ethylene-acetic acids. Aqueous dispersions such as vinyl resins, acrylonitrile-butadiene resins, polyethylene resins, polypropylene resins, carboxymethyl cellulose resins, polyamide resins, vinyl chloride resins, vinylidene chloride resins can be used.
本発明に使用できる顔料としては、クレー、カオリン、タルク、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、水酸化アルミニウム、アルミナ、シリカ、アルミノ珪酸マグネシウム、珪酸カルシウム、ホワイトカーボン、ベントナイト、ゼオライト、セリサイト、スメクタイト、硫酸カルシウム、硫酸バリウム、合成マイカ、二酸化チタン、酸化亜鉛などの無機顔料、さらにはポリイソプレン、ポリネオプレン、ポリブタジエン等のポリジエン類、ポリブテン、ポリイソブチレン、ポリプロピレン等のポリアルケン類、酢酸ビニル、スチレン、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、（メタ）アクリルアミド、メチルビニルエーテル等のビニル系モノマーの重合体や共重合体類、ポリウレタン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、尿素系樹脂、メラミン系樹脂、ベンゾグアナミン系樹脂等の各種の密実型、中空型、あるいは貫通孔型粒子等の有機顔料１種又は２種以上を使用することができる。 Examples of pigments that can be used in the present invention include clay, kaolin, talc, calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, alumina, silica, magnesium aluminosilicate, calcium silicate, white carbon, bentonite, zeolite, sericite, and smectite. , Calcium sulfate, barium sulfate, synthetic mica, titanium dioxide, zinc oxide and other inorganic pigments, polyisoprene, polyneoprene, polybutadiene and other polydienes, polybutene, polyisobutylene, polypropylene and other polyalkenes, vinyl acetate, styrene, Polymers and copolymers of vinyl monomers such as (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylamide, and methyl vinyl ether, polyurethane resins, polyesters It is possible to use one or more organic pigments such as various solid, hollow or through-hole type particles such as tellurium resin, polyamide resin, urea resin, melamine resin, and benzoguanamine resin. it can.
本発明の耐油層を形成する塗工方法としては、ロール塗工、エアナイフ塗工、グラビア塗工など、必要に応じて任意の方法を採用することができる。オフマシン塗工では特にバー塗工が好適に用いられる。バー塗工によれば、少量の塗工量でも欠点部が少なく、耐油性に優れた皮膜が形成しやすい。また、オンマシン塗工ではゲートロール方式での塗工が好適に用いられる。ゲートロール方式での塗工は高速塗工が可能であり、安価に塗布を行う手段として少ない塗工量で均一な塗膜を形成させることが可能である。 As a coating method for forming the oil-resistant layer of the present invention, any method such as roll coating, air knife coating, and gravure coating can be adopted as necessary. In off-machine coating, bar coating is particularly preferably used. According to the bar coating, even with a small amount of coating, there are few defects and it is easy to form a film excellent in oil resistance. In on-machine coating, gate roll coating is preferably used. Coating by the gate roll method can be applied at high speed, and a uniform coating film can be formed with a small coating amount as a means for applying at low cost.
本発明の耐油層の層構成としては、前記紙支持体の少なくとも片面に少なくとも１層の耐油層を設けるものであるが、同じ塗工量を塗工する場合、多層構成とした方が単層構成よりも耐油性は得られやすい。多層構成の場合、各層は同じ構成（組成）でもよいし、異なっていてもよい。 As the layer structure of the oil-resistant layer of the present invention, at least one oil-resistant layer is provided on at least one side of the paper support, but when applying the same coating amount, a multilayer structure is a single layer. Oil resistance is easier to obtain than the configuration. In the case of a multilayer configuration, each layer may have the same configuration (composition) or may be different.
本発明の耐油層の塗工量は（多層の場合はその合計）２．０〜２０．０ｇ／ｍ2の範囲であることが好ましい。塗工量が２．０ｇ／ｍ2未満の場合は、満足な耐油性能が得られない。また、２０．０ｇ／ｍ2を超える場合は、耐油性能は得られるものの、コストの面で好ましくない。より好ましい範囲は２．３〜１５．０ｇ／ｍ2である。
耐油性樹脂層の耐油度は、キット耐油度で６級以上であることが特徴ではあるが、キット耐油度で１２級以上になっている事がさらに好ましい。
また、高い折り目の耐油性を有する耐油紙としては、キット耐油度で４以上であることが特徴である。
The coating amount of the oil-resistant layer of the present invention is preferably in the range of 2.0 to 20.0 g / m 2 (the total in the case of multiple layers). When the coating amount is less than 2.0 g / m 2 , satisfactory oil resistance cannot be obtained. Moreover, when it exceeds 20.0 g / m < 2 >, although oil resistance performance is obtained, it is not preferable in terms of cost. A more preferable range is 2.3 to 15.0 g / m 2 .
The oil resistance of the oil-resistant resin layer is characterized by a kit oil resistance of 6 or higher, but it is more preferable that the kit oil resistance is 12 or higher.
In addition, the oil-resistant paper having high crease oil resistance is characterized by having a kit oil resistance of 4 or more.
平面部の耐油度：ＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．４１：２０００（キット法）によって塗工面を測定した。耐油紙として使用可能なキット耐油度は６級以上であるが、高い耐油性を有する耐油紙としてはキット耐油度で１２級以上である。 Oil resistance of flat part: JAPAN TAPPI Paper pulp test method No. The coated surface was measured by 41: 2000 (kit method). The oil resistance of the kit that can be used as oil-resistant paper is grade 6 or higher, but the oil-resistant paper having high oil resistance is grade 12 or higher in terms of kit oil resistance.
折り部の耐油度：塗工後の耐油紙を折り、折り目部分にキット液を滴下し、平面部耐油度測定と同様に耐油度を測定した。高い折り目の耐油性を有する耐油紙としては、キット耐油度で４級以上である。 Oil resistance of the fold part: The oil-resistant paper after coating was folded, the kit solution was dropped on the crease part, and the oil resistance was measured in the same manner as the flat part oil resistance measurement. The oil resistance paper having high crease oil resistance is grade 4 or higher in kit oil resistance.
以下に実施例および比較例を挙げて本発明をより具体的に説明するが、勿論本発明はこれらの実施例に限定されるものではない。また、実施例および比較例中の％および部数はそれぞれ質量％、質量部を示す。また、紙支持体上の塗工量は絶乾質量を示す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. Moreover,% and part in an Example and a comparative example show the mass% and the mass part, respectively. Moreover, the coating amount on a paper support shows an absolutely dry mass.
＜耐油層塗料１＞
ＵＷ−Ｙ（カオリン、ＥＣ社製）１００部、ハイドラグロス９０（カオリン、ヒューバー社製）５０部、耐油剤としてＰＤＸ７３２６（コアシェル型スチレン−アクリル樹脂系エマルジョン、ＢＡＳＦ社製）（Ｔｇ：９℃、重量平均分子量：２０万）４１．２部、接着剤として顔料１００部あたりＰＮ−７００Ｓ（リン酸エステル化変性でん粉、三和澱粉社製）２．６部、Ｘ３００Ｂ（スチレン−ブタジエン共重合体ラテックス、ＪＳＲ社製）２０．７部を混合し、塗料濃度４３％の耐油層塗料を調製した。
<Oil-resistant coating 1>
100 parts of UW-Y (Kaolin, manufactured by EC), 50 parts of Hydra gloss 90 (Kaolin, manufactured by Huber), PDX7326 (core-shell styrene-acrylic resin emulsion, manufactured by BASF) as an oil resistance agent (Tg: 9 ° C., Weight average molecular weight: 200,000) 41.2 parts, PN-700S (phosphate esterified modified starch, manufactured by Sanwa Starch Co., Ltd.) 2.6 parts per 100 parts of pigment as an adhesive, X300B (styrene-butadiene copolymer latex) 20.7 parts of JSR Co., Ltd.) were mixed to prepare an oil-resistant layer paint having a paint concentration of 43%.
＜耐油層塗料２＞
耐油剤としてＸＰ８８０８（コアシェル型スチレン−アクリル樹脂系エマルジョン、星光ＰＭＣ社製）（Ｔｇ：２５℃、重量平均分子量：１５万）１００部に対し、ＳＮデフォーマーＪＫ（消泡剤、サンノプコ社製）０．５部塗料を混合し、塗料濃度４５％の耐油層塗料を調製した。
<Oil resistant paint 2>
As an oil-proofing agent, XP deformer (K8) (core shell type styrene-acrylic resin emulsion, manufactured by Seiko PMC) (Tg: 25 ° C., weight average molecular weight: 150,000) 100 parts, SN deformer JK (antifoaming agent, manufactured by San Nopco) 0 .5 parts of paint was mixed to prepare an oil-resistant paint having a paint concentration of 45%.
＜実施例１＞
坪量５０ｇ／ｍ2、密度０．９７ｇ／ｃｍ３のセミグラシン原紙（カナダ標準フリーネス１９５ｍｌ、ＬＢＫＰ１００％、ブレーカースタック３０ｋｇｆ／ｃｍ、マシンカレンダー４０ｋｇｆ／ｃｍ） の抄造パート後のコーターにて、ＰＶＡ１１７Ｋ（ポリビニルアルコール、クラレ社製）０．５ｇ／ｍ2を塗布し、目止め層を設けた紙支持体に、オフコーターで上記耐油層塗料１を片面に８．０ｇ／ｍ2をバーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１２であった。なお、使用した紙支持体の王研式透気度は３１３秒であった。
<Example 1>
PVA117K (polyvinyl chloride) on a coater after the paper making part of a semi-glassine base paper (Canada standard freeness 195 ml, LBKP 100%, breaker stack 30 kgf / cm, machine calendar 40 kgf / cm) having a basis weight of 50 g / m 2 and a density of 0.97 g / cm 3 alcohol, applying the Kuraray Co., Ltd.) 0.5 g / m 2, the paper support provided with the sealing layer, after coating the 8.0 g / m 2 on one side the oil resistant layer coating 1 off coater bar The oil-resistant paper was obtained by drying. The Kit of the coated flat part was 12, and the oil resistance of the fold was 12. The paper support used had a Oken air permeability of 313 seconds.
＜実施例２＞
坪量５５ｇ／ｍ2、密度０．９４ｇ／ｃｍ３のセミグラシン原紙（カナダ標準フリーネス２９５ｍｌ、ＬＢＫＰ１００％、マシンカレンダー４０ｋｇｆ／ｃｍ） に、オフコーターで上記耐油層塗料１を片面に８．１ｇ／ｍ2をバーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１０であった。なお、使用した紙支持体の王研式透気度は１１４秒であった。
<Example 2>
Semi-grasine base paper (Canada standard freeness 295 ml, LBKP 100%, machine calendar 40 kgf / cm) having a basis weight of 55 g / m 2 and a density of 0.94 g / cm 3 , and 8.1 g / m of the oil-resistant layer coating 1 on one side by an off-coater. After coating 2 with a bar, it was dried to obtain an oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 10. The paper support used had a Oken air permeability of 114 seconds.
＜実施例３＞
坪量３０ｇ／ｍ2、密度０．８２ｇ／ｃｍ３の片艶原紙（カナダ標準フリーネス２７０ｍｌ、ＬＢＫＰ１００％、ソフトニップカレンダー４０ｋｇｆ／ｃｍ）に、オフコーターで上記耐油層塗料１を非艶面に８．２ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１０であった。なお、使用した紙支持体の王研式透気度は９５秒であった。
<Example 3>
On the non-glossy surface, the above-mentioned oil-resistant layer paint 1 is applied to a non-glossy surface on a non-glossy base paper (Canada standard freeness 270 ml, LBKP 100%, soft nip calender 40 kgf / cm) having a basis weight of 30 g / m 2 and a density of 0.82 g / cm 3. After coating with a 2 g / m 2 bar, it was dried to obtain an oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 10. The paper support used had a Oken air permeability of 95 seconds.
＜実施例４＞
坪量３０ｇ／ｍ2、密度０．８４ｇ／ｃｍ３の片艶原紙（カナダ標準フリーネス２９０ｍｌ、ＬＢＫＰ１００％、ソフトニップカレンダー３０ｋｇｆ／ｃｍ）に、オフコーターで上記耐油層塗料１を非艶面に８．７ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１０であった。なお、使用した紙支持体の王研式透気度は７９秒であった。
<Example 4>
On the non-glossy surface, the oil-resistant layer paint 1 is applied to a non-glossy surface on a single glossy base paper (Canada standard freeness 290 ml, LBKP 100%, soft nip calender 30 kgf / cm) having a basis weight of 30 g / m 2 and a density of 0.84 g / cm 3. After coating with 0.7 g / m 2 bar, it was dried to obtain oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 10. The paper support used had a Oken air permeability of 79 seconds.
＜実施例５＞
坪量２１ｇ／ｍ2、密度０．８０ｇ／ｃｍ３の片艶原紙（カナダ標準フリーネス１６２ｍｌ、ＬＢＫＰ１００％、ソフトニップカレンダー４０ｋｇｆ／ｃｍ）に、オフコーターで上記耐油層塗料１を非艶面に８．７ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１０であった。なお、使用した紙支持体の王研式透気度は９４秒であった。
<Example 5>
On the non-glossy surface of the above-mentioned oil-resistant layer coating 1 on a non-glossy surface on a glossy base paper (Canada standard freeness 162 ml, LBKP 100%, soft nip calender 40 kgf / cm) having a basis weight of 21 g / m 2 and a density of 0.80 g / cm 3. After coating with 0.7 g / m 2 bar, it was dried to obtain oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 10. The paper support used had a Oken air permeability of 94 seconds.
＜実施例６＞
坪量５０ｇ／ｍ2、密度０．８２ｇ／ｃｍ３セミグラシン原紙（カナダ標準フリーネス１９５ｍｌ、ＬＢＫＰ１００％、ブレーカースタック３０ｋｇｆ／ｃｍ） に、オンマシンゲートロールで、上記耐油層塗料２を片面に４．５ｇ／ｍ2で塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１１であった。なお、使用した紙支持体の王研式透気度は１５７秒であった。
<Example 6>
Basis weight 50g / m 2 , density 0.82g / cm 3 semi-glassine base paper (Canadian standard freeness 195ml, LBKP 100%, breaker stack 30kgf / cm), on-machine gate roll, 4.5g of oil-resistant layer paint 2 on one side After coating at / m 2, it was dried to obtain oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 11. The paper support used had a Oken air permeability of 157 seconds.
＜実施例７＞
坪量５０ｇ／ｍ2、密度０．８２ｇ／ｃｍ３のセミグラシン原紙（カナダ標準フリーネス１７０ｍｌ、ＬＢＫＰ１００％、ブレーカースタック３０ｋｇ／ｃｍ）に、オンマシンゲートロールで、上記耐油層塗料２を片面に３．５ｇ／ｍ2で塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１１であった。なお、使用した紙支持体の王研式透気度は２４６秒であった。
<Example 7>
2. Semi-glassine base paper (basic weight 50 g / m 2 , density 0.82 g / cm 3 (Canadian standard freeness 170 ml, LBKP 100%, breaker stack 30 kg / cm), on-machine gate roll, oil-resistant layer paint 2 on one side. After coating at 5 g / m 2 , drying was performed to obtain an oil-resistant paper. The Kit of the coated flat part was 12, and the oil resistance of the fold was 11. The paper support used had Oken's air permeability of 246 seconds.
＜比較例１＞
坪量５０ｇ／ｍ2、密度０．８０ｇ／ｃｍ３の上質紙（カナダ標準フリーネス４００ｍｌ、ＬＢＫＰ１００％）に、オフコーターで上記耐油層塗料１を８．５ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は１であった。なお、使用した紙支持体の王研式透気度は２２秒であった。
<Comparative Example 1>
Apply the above oil-resistant coating 1 at 8.5 g / m 2 bar with an off-coater on high-quality paper (Canada standard freeness 400 ml, LBKP 100%) with a basis weight of 50 g / m 2 and a density of 0.80 g / cm 3 and then dry. As a result, oil-resistant paper was obtained. The coating plane portion had a Kit of 12, and the crease had an oil resistance of 1. The paper support used had a Oken air permeability of 22 seconds.
＜比較例２＞
坪量３０ｇ／ｍ2、密度０．７７ｇ／ｃｍ３の片艶原紙（カナダ標準フリーネス３８０ｍｌ、ＬＢＫＰ１００％）に、オフコーターで上記耐油層塗料１を非艶面に１０．３ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は３であった。なお、使用した紙支持体の王研式透気度は３１秒であった。
<Comparative example 2>
The above oil-resistant coating 1 is applied to a non-glossy surface at 10.3 g / m 2 bar on a non-glossy surface on a glossy base paper (Canadian standard freeness 380 ml, LBKP 100%) having a basis weight of 30 g / m 2 and a density of 0.77 g / cm 3 After coating, it was dried to obtain an oil resistant paper. The coating plane part had a Kit of 12, and the crease had an oil resistance of 3. The paper support used had a Oken air permeability of 31 seconds.
＜比較例３＞
坪量２１ｇ／ｍ2、密度０．７０ｇ／ｃｍ３の片艶原紙（カナダ標準フリーネス３００ｍｌ、ＬＢＫＰ１００％）に、オフコーターで上記耐油層塗料１を非艶面に８．７ｇ／ｍ2バーで塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は２であった。なお、使用した紙支持体の王研式透気度は４２秒であった。
<Comparative Example 3>
On the glossy base paper (Canada standard freeness 300 ml, LBKP 100%) with a basis weight of 21 g / m 2 and density of 0.70 g / cm 3 , the oil-resistant coating 1 is applied to the non-glossy surface at 8.7 g / m 2 bar using an off-coater. After coating, it was dried to obtain an oil resistant paper. The coating plane part had a Kit of 12, and the crease had an oil resistance of 2. The paper support used had a Oken air permeability of 42 seconds.
＜比較例４＞
坪量５０ｇ／ｍ2、密度０．８０ｇ／ｃｍ３の上質紙（カナダ標準フリーネス４００ｍｌ、ＬＢＫＰ１００％）に、オンマシンゲートロールで、上記耐油層塗料２を片面に８．５ｇ／ｍ2で塗工後、乾燥して耐油紙を得た。塗工平面部のＫｉｔは１２、折り目の耐油性は３であった。なお、使用した紙支持体の王研式透気度は２２秒であった。
<Comparative example 4>
Apply the above oil-resistant paint 2 to 8.5 g / m 2 on one side with an on-machine gate roll on high-quality paper (Canada standard freeness 400 ml, LBKP 100%) with a basis weight of 50 g / m 2 and density 0.80 g / cm 3. After the work, it was dried to obtain oil-resistant paper. The coating plane part had a Kit of 12, and the crease had an oil resistance of 3. The paper support used had a Oken air permeability of 22 seconds.
前記実施例、比較例を評価したものを以下表１に示す。 Table 1 below shows the evaluation results of the examples and comparative examples.
本発明により、平面部の同一耐油性であっても、原紙の透気度を高めることで、塗工層の伸びを改善し、塗工層の割れを防ぐことが可能となる。 According to the present invention, even if the flat portion has the same oil resistance, it is possible to improve the elongation of the coating layer and prevent the coating layer from cracking by increasing the air permeability of the base paper.
本発明による耐油紙は食品用途にも使用可能であり、実用上極めて有用である。 The oil-resistant paper according to the present invention can be used for food applications and is extremely useful in practice.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016203982A (en) * | 2015-04-15 | 2016-12-08 | 東洋インキＳｃホールディングス株式会社 | Food packaging sheet coating agent, and food packaging sheet |
| JP2017114499A (en) * | 2015-12-22 | 2017-06-29 | 大王製紙株式会社 | Paper material for fibrous casing |
| JP2018505323A (en) * | 2015-02-11 | 2018-02-22 | ウエストロック・エム・ダブリュー・ヴイ・エルエルシー | Oil, grease and moisture resistant paperboard |
| JP2020066805A (en) * | 2018-10-19 | 2020-04-30 | 大王製紙株式会社 | Oil resistant paper |
| US11326308B2 (en) | 2015-02-11 | 2022-05-10 | Westrock Mwv, Llc | Oil and grease resistant paperboard |
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| JP2010013792A (en) * | 2003-08-11 | 2010-01-21 | Tokushu Paper Mfg Co Ltd | Oil-resistant sheet-like material |
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| JPH1112990A (en) * | 1997-06-25 | 1999-01-19 | Oji Paper Co Ltd | Transparent paper |
| JP2002001864A (en) * | 2000-06-23 | 2002-01-08 | Gifu Seratsuku Seizosho:Kk | Oil resistant coating film and method for forming the same and oil resistant paper |
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| JP2018505323A (en) * | 2015-02-11 | 2018-02-22 | ウエストロック・エム・ダブリュー・ヴイ・エルエルシー | Oil, grease and moisture resistant paperboard |
| US11326308B2 (en) | 2015-02-11 | 2022-05-10 | Westrock Mwv, Llc | Oil and grease resistant paperboard |
| JP2016203982A (en) * | 2015-04-15 | 2016-12-08 | 東洋インキＳｃホールディングス株式会社 | Food packaging sheet coating agent, and food packaging sheet |
| JP2017114499A (en) * | 2015-12-22 | 2017-06-29 | 大王製紙株式会社 | Paper material for fibrous casing |
| JP2020066805A (en) * | 2018-10-19 | 2020-04-30 | 大王製紙株式会社 | Oil resistant paper |
| JP7176922B2 (en) | 2018-10-19 | 2022-11-22 | 大王製紙株式会社 | greaseproof paper |
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