JPH04361688A - Sizing agent composition for papermaking - Google Patents
Sizing agent composition for papermakingInfo
- Publication number
- JPH04361688A JPH04361688A JP13292391A JP13292391A JPH04361688A JP H04361688 A JPH04361688 A JP H04361688A JP 13292391 A JP13292391 A JP 13292391A JP 13292391 A JP13292391 A JP 13292391A JP H04361688 A JPH04361688 A JP H04361688A
- Authority
- JP
- Japan
- Prior art keywords
- ketene dimer
- sizing
- paper
- sizing agent
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 125000002091 cationic group Chemical group 0.000 abstract description 10
- 239000000084 colloidal system Substances 0.000 abstract description 10
- 230000001681 protective effect Effects 0.000 abstract description 10
- 150000002561 ketenes Chemical class 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 29
- 230000005476 size effect Effects 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 hexadecenyl Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=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])[H] 0.000 description 2
- 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 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 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 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 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 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical class OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 241000212749 Zesius chrysomallus Species 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 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
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- DXTCFKRAUYBHRC-UHFFFAOYSA-L iron(2+);dithiocyanate Chemical compound [Fe+2].[S-]C#N.[S-]C#N DXTCFKRAUYBHRC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- SBIDUCNDVPSWQT-UHFFFAOYSA-N n-ethyl-n-(oxiran-2-ylmethyl)ethanamine Chemical compound CCN(CC)CC1CO1 SBIDUCNDVPSWQT-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 229920001592 potato starch Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は製紙用サイズ剤組成物に
関する。更に詳しくは、サイズ性能の立ち上がりが良く
、優れたサイズ性能効果を示すケテン二量体系製紙用サ
イズ剤組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing composition for paper manufacturing. More specifically, the present invention relates to a ketene dimer-based paper sizing agent composition that has a good rise in size performance and exhibits excellent size performance effects.
【０００２】0002
【従来の技術】従来より紙及び板紙のサイジング方法と
してロジンもしくは強化ロジン（マレイン化ロジン）と
硫酸アルミニウムを併用する酸性サイジングが一般的に
行われてきた。これに対して、近年、抄紙工程での白水
のクローズド化、填料として安価で白色度の高い炭酸カ
ルシウムの利用及びこれを含む損紙の利用とコートブロ
ーク処理等の観点から中性サイジングが導入されてきて
いる。BACKGROUND OF THE INVENTION Conventionally, acid sizing using a combination of rosin or reinforced rosin (maleated rosin) and aluminum sulfate has been commonly used as a sizing method for paper and paperboard. In response to this, in recent years, neutral sizing has been introduced from the viewpoints of closing white water in the papermaking process, using calcium carbonate, which is inexpensive and has high whiteness, as a filler, and using waste paper containing calcium carbonate and coat-broke treatment. It's coming.
【０００３】この中性サイジングに用いられるサイズ剤
としては、ケテン二量体系サイズ剤、置換環状ジカルボ
ン酸無水物系サイズ剤等か知られているが、使用上の簡
便性及び少量添加で強サイズ性が期待できることから、
ケテン二量体系サイズ剤が広く用いられている。Known sizing agents used for this neutral sizing include ketene dimer-based sizing agents and substituted cyclic dicarboxylic acid anhydride-based sizing agents, but they are easy to use and can be added to a strong size by adding a small amount. Because sex can be expected,
Ketene dimer-based sizing agents are widely used.
【０００４】0004
【発明が解決しようとする課題】しかしながら、ケテン
二量体系サイズ剤には、サイズ効果の発現に時間がかか
るという欠点が依然としてある。However, the ketene dimer sizing agent still has the drawback that it takes time to develop its sizing effect.
【０００５】一般にケテン二量体系サイズ剤を使用した
場合、抄造直後のサイズ性能が悪く、使用したサイズ剤
の量に対して充分なサイズ性能を得るためには経時が必
要であると言われている。この問題は一般にはサイズ効
果の立ち上がりが悪いという表現で指摘されているが、
この立ち上がりの悪さは次のような欠点につながること
は容易に想像される。即ち、筆記用紙や包装紙、ミルク
カートンのような最終製品に高いサイズ効果を要する紙
に対しては、乾燥後から使用までの時間や、必要とされ
るサイズ効果の違いによりサイズ剤の使用量を加減せね
ばならず、その品質管理を困難とする。また高いサイズ
効果を得るために、数日を経過して出荷しなければなら
ないが、この出荷までの保存は紙のコスト高になること
は言うまでもない。一方、塗工紙の場合には塗工の工程
における吸液量を制御するために内添サイズ剤が使用さ
れている。現在、塗工は抄紙から連続的に行われること
が多く、この場合には、湿紙が乾燥された直後（抄造直
後）にサイズ効果が発現しないと全く役立たない。Generally, when a ketene dimer type sizing agent is used, the sizing performance immediately after paper making is poor, and it is said that aging is required to obtain sufficient sizing performance for the amount of sizing agent used. There is. This problem is generally pointed out as a slow rise in the size effect, but
It is easy to imagine that this poor start-up leads to the following drawbacks. In other words, for paper that requires a high size effect in the final product such as writing paper, wrapping paper, and milk cartons, the amount of sizing agent used depends on the time from drying to use and the required size effect. This makes quality control difficult. Furthermore, in order to obtain a high size effect, the paper must be shipped after several days have elapsed, but it goes without saying that storage until shipping increases the cost of paper. On the other hand, in the case of coated paper, an internal sizing agent is used to control the amount of liquid absorbed during the coating process. Currently, coating is often carried out continuously from paper making, and in this case, it is completely useless unless the size effect appears immediately after the wet paper is dried (immediately after paper making).
【０００６】ケテン二量体系サイズ剤には、中性領域で
使用できる、低添加量でサイズ効果が現われる、高サイ
ズ紙が得られる等の優れた性能があるにもかかわらず、
上記の理由によりその使用が制限されているのが現状で
ある。[0006] Although ketene dimer-based sizing agents have excellent performance, such as being able to be used in a neutral region, producing a sizing effect with a low addition amount, and being able to obtain high-size paper,
At present, its use is restricted due to the above reasons.
【０００７】そこで、本発明はサイズ性能の立ち上がり
が良く、優れた性能効果を示すケテン二量体系製紙用サ
イズ剤組成物を提供することを目的としている。[0007] Accordingly, the object of the present invention is to provide a ketene dimer-based paper sizing agent composition that has a good rise in sizing performance and exhibits excellent performance effects.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、炭素数が特定範囲に
あるアルキル基、アルケニル基を有するケテン二量体と
、特定のアリール基を有するケテン二量体とを２種類併
用することにより、サイズ性能の立ち上がりが良く、優
れたサイズ性能効果を持つサイズ剤組成物が得られるこ
とを見い出し、本発明を完成させた。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have developed a ketene dimer having an alkyl group or an alkenyl group having a carbon number within a specific range, and a specific aryl group. The present inventors have discovered that by using two types of ketene dimers having the following in combination, a sizing agent composition with a good rise in size performance and excellent size performance effects can be obtained, and the present invention has been completed.
【０００９】即ち、本発明は一般式（１）That is, the present invention is based on the general formula (1)
【００１０】0010
【化３】[Chemical formula 3]
【００１１】（式中、Ｒ１およびＲ２は炭素数８〜２４
のアルキル基、アルケニル基である。）で示されるケテ
ン二量体（ａ） と、一般式（２）(In the formula, R1 and R2 have 8 to 24 carbon atoms.
is an alkyl group or an alkenyl group. ) and the ketene dimer (a) represented by general formula (2)
【００１２】0012
【化４】[C4]
【００１３】（式中、Ｒ３およびＲ４は炭素数６〜２４
のアルキル基又はアルケニル基であり、ｎ ＝０〜１で
ある。）で示されるケテン二量体（ｂ） の水分散物を
含有してなることを特徴とする製紙用サイズ剤組成物を
提供するものである。(In the formula, R3 and R4 have 6 to 24 carbon atoms.
is an alkyl group or alkenyl group, and n = 0 to 1. The present invention provides a paper sizing agent composition comprising an aqueous dispersion of the ketene dimer (b) shown in (b).
【００１４】本発明の作用についてはまだ明らかではな
いが、以下のように推定される。即ち、ケテン二量体系
サイズ剤は通常、親水性の高い保護コロイド剤に包含さ
れた微小な粒子を水に分散した形態で用いられる。そし
て、このものをパルプスラリーに添加して抄紙すること
によって、サイジングが行われる。パルプスラリーは順
次脱水、乾燥されて行くが、それに伴ってケテン二量体
粒子の回りの保護コロイド剤層も脱水される。乾燥工程
において、保護コロイド剤層の水がほとんど無くなると
開裂が起こり、同時に中のケテン二量体も溶融してセル
ロース等の上を塗れ広がる。この状態で冷やされたのが
乾燥直後の低いサイズ効果に当たる。その後、ケテン二
量体表面にはその歪んだ構造に起因する鱗片状の結晶が
成長し、空間を効率よく疎水化する。これが、結果的に
高いサイズ効果を示す。この結晶成長の過程で、本発明
の如き比較的自由度が少なく、リジッドな側鎖を持つ一
般式（２） で表されるケテン二量体が結晶核となって
、併用された一般式（１） で表されるケテン二量体の
鱗片状結晶の成長を促進するため、サイズ性能の立ち上
がりがよく、優れたサイズ性能効果を示すものと推察さ
れる。Although the effect of the present invention is not yet clear, it is estimated as follows. That is, the ketene dimer-based sizing agent is usually used in the form of fine particles encapsulated in a highly hydrophilic protective colloid agent dispersed in water. Then, sizing is performed by adding this material to pulp slurry and making paper. As the pulp slurry is sequentially dehydrated and dried, the protective colloid agent layer around the ketene dimer particles is also dehydrated. In the drying process, when most of the water in the protective colloid agent layer disappears, cleavage occurs, and at the same time, the ketene dimer inside also melts and spreads over the cellulose, etc. Cooling in this state corresponds to a low size effect immediately after drying. After that, scale-like crystals due to the distorted structure grow on the surface of the ketene dimer, effectively making the space hydrophobic. This results in a high size effect. In the process of this crystal growth, the ketene dimer represented by the general formula (2) with relatively few degrees of freedom and rigid side chains as in the present invention becomes a crystal nucleus, and the combined general formula ( 1) Since it promotes the growth of scale-like crystals of the ketene dimer represented by the formula, it is presumed that the size performance rises well and exhibits an excellent size performance effect.
【００１５】次に本発明を詳細に説明する。Next, the present invention will be explained in detail.
【００１６】本発明を構成するケテン二量体は、上記一
般式（１） で示された化合物であり、公知のケテン二
量体をいずれでも使用できる。上記一般式（１） 中、
Ｒ１及びＲ２は各種炭素数８〜２４、好ましくは１２〜
２２の同一又は異なるアルキル基又はアルケニル基を示
す。これら炭化水素基としては、例えばオクチル、デシ
ル、ドデシル、テトラデシル、ヘキサデシル、オクタデ
シル、エイコシル基等のアルキル基、オクテニル、デセ
ニル、ドデセニル、テトラデセニル、ヘキサデセニル、
オクタデセニル、エイコセニル基等のアルケニル基が例
示でき、これらのうちアルキル基が好ましい。更に、物
理化学的定数としては該ケテン二量体の融点が２０〜８
０℃が好ましく、このＲ１，Ｒ２が前記の範囲内であれ
ば１種単独でも又２種以上混合しても使用できる。尚、
ここで融点とは上昇融点をいい、毛管法で測定した値で
ある。The ketene dimer constituting the present invention is a compound represented by the above general formula (1), and any known ketene dimer can be used. In the above general formula (1),
R1 and R2 each have 8 to 24 carbon atoms, preferably 12 to 24 carbon atoms.
22 identical or different alkyl or alkenyl groups. Examples of these hydrocarbon groups include alkyl groups such as octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl,
Examples include alkenyl groups such as octadecenyl and eicosenyl groups, and among these, alkyl groups are preferred. Furthermore, as a physicochemical constant, the melting point of the ketene dimer is 20 to 8
The temperature is preferably 0° C., and as long as R1 and R2 are within the above ranges, they can be used singly or in combination of two or more. still,
The melting point here refers to the rising melting point, and is a value measured by the capillary method.
【００１７】本発明に係わる上記一般式（１） で示さ
れるケテン二量体を得るには、例えば原料である脂肪酸
混合物を三塩化リンと反応させることにより得られる脂
肪酸塩化物の脱塩酸反応を、３級アミン触媒の存在下で
行う公知の方法を適用すれば良い。In order to obtain the ketene dimer represented by the above general formula (1) according to the present invention, for example, a fatty acid chloride obtained by reacting a fatty acid mixture as a raw material with phosphorus trichloride is subjected to a dehydrochlorination reaction. , a known method carried out in the presence of a tertiary amine catalyst may be applied.
【００１８】本発明を構成するもう一つの成分である自
由度が少なくリジッドな側鎖を持つケテン二量体は、前
記一般式（２） で示される化合物であり、例えばアル
キルベンゼンと２−クロロ−２−メチルチオ酢酸エステ
ルとの反応物より、脱チオメチル化して生成したエステ
ルを更に加水分解して得られるｐ−アルキルフェニル酢
酸やｐ−ヒドロキシフェニル酢酸とアルキルハライドか
ら得られるｐ−アルキルオキシフェニル酢酸を上記のよ
うな公知の方法によって二量体化することにより得られ
るケテン二量体をいずれも使用できる。一般式（２）中
、Ｒ３及びＲ４は各種炭素数６〜２４、好ましくは１２
〜２２の同一又は異なる炭化水素基を示す。炭化水素基
としては、例えばヘキシル、オクチル、デシル、ドデシ
ル、ヘキサデシル、オクタデシル、エイコシル基等のア
ルキル基、ヘキセニル、オクテニル、デセニル、ドデセ
ニル、テトラデセニル、ヘキサデセニル、オクタデセニ
ル、エイコセニル基等のアルケニル基が例示でき、これ
らのうちアルキル基が好ましい。尚、一般式（２） で
表されるケテン二量体１種単独でも又は２種以上混合し
ても使用できる。Another component constituting the present invention, a ketene dimer having a rigid side chain with a small degree of freedom, is a compound represented by the above general formula (2), and includes, for example, alkylbenzene and 2-chloro- From the reaction product with 2-methylthioacetic acid ester, p-alkylphenyl acetic acid obtained by further hydrolyzing the ester produced by dethiomethylation, and p-alkyloxyphenylacetic acid obtained from p-hydroxyphenylacetic acid and an alkyl halide. Any ketene dimer obtained by dimerization by a known method as described above can be used. In general formula (2), R3 and R4 have various carbon atoms of 6 to 24, preferably 12.
-22 identical or different hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups such as hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, and eicosyl groups; alkenyl groups such as hexenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, and eicosenyl groups; Among these, alkyl groups are preferred. Incidentally, the ketene dimer represented by the general formula (2) can be used alone or in combination of two or more.
【００１９】本発明においては、一般式（１） で示さ
れるケテン二量体（ａ） と一般式（２） で示される
特定の側鎖を持つケテン二量体（ｂ） との配合割合も
重要である。即ち、その重量比率は（ａ） ／（ｂ）
＝ ９９．９８／０．０２〜８０／２０、好ましくは９
９．５／０．５ 〜９０／１０の範囲内にあるのが良い
。その重量比率が９９．９８ ／０．０２より大きくな
ると、結晶核として作用するには量が少なすぎるため、
充分なサイズ性能の立ち上がりの促進効果が得られない
。また、８０／２０より小さくなると、経済的に不利で
ある。本発明の製紙用サイズ剤組成物には、ケテン二量
体を安定に分散させるために保護コロイド剤を使用する
のが好ましい。保護コロイド剤としては、カチオン澱粉
、カチオン性ビニルモノマーの共重合物もしくは重合物
、ポリアルキレンポリアミドのエピハロヒドリン変性物
（特開昭４８−４８７０２ 号公報） 、ポリエチレン
イミン、カチオン性ポリウレタン樹脂（特開昭５５−１
３２７９９号公報） 等の化合物を挙げることができる
。尚、これらのカチオン性保護コロイド剤は単独で単一
系として用いてもよいし、又、二種類以上の混合系とし
て用いることも可能である。In the present invention, the blending ratio of the ketene dimer (a) represented by the general formula (1) and the ketene dimer (b) having a specific side chain represented by the general formula (2) is also determined. is important. That is, the weight ratio is (a) / (b)
= 99.98/0.02 to 80/20, preferably 9
It is preferably within the range of 9.5/0.5 to 90/10. When the weight ratio is greater than 99.98/0.02, the amount is too small to act as a crystal nucleus.
A sufficient effect of promoting the start-up of size performance cannot be obtained. Moreover, if it is smaller than 80/20, it is economically disadvantageous. It is preferable to use a protective colloid agent in the paper sizing composition of the present invention in order to stably disperse the ketene dimer. Examples of protective colloid agents include cationic starch, copolymers or polymers of cationic vinyl monomers, epihalohydrin-modified products of polyalkylene polyamide (Japanese Unexamined Patent Publication No. 48-48702), polyethyleneimine, cationic polyurethane resins (Japanese Unexamined Patent Application Publication No. 1982-48702). 55-1
32799). Incidentally, these cationic protective colloid agents may be used alone as a single system, or may be used as a mixture of two or more types.
【００２０】保護コロイド剤の製造法の一例を挙げると
、カチオン澱粉の場合、原料澱粉として、コーン澱粉、
馬鈴薯澱粉、タピオカ澱粉、小麦澱粉及びそれらの澱粉
を含有する種子粉末又は根茎粉末等を使用し、アルカリ
金属またはアルカリ土類金属の水酸化物等のアルカリ物
質存在下で、２−ジエチルアミノエチルクロライド、３
−ジエチルアミノ−１，２ −エポキシプロパン、３−
ジブチルアミノ−１，２ −エポキシプロパン、２−ク
ロロエチルトリメチルアンモニウムクロライド、グリシ
ジルトリメチルアンモニウムクロライド等のカチオン化
試薬と澱粉とを反応させることにより得られる。又、澱
粉の低分子化はカチオン性の基を導入する反応の前後の
どちらでも構わない。[0020] To give an example of a method for producing a protective colloid agent, in the case of cationic starch, corn starch,
Using potato starch, tapioca starch, wheat starch, and seed powder or rhizome powder containing these starches, in the presence of an alkaline substance such as an alkali metal or alkaline earth metal hydroxide, 2-diethylaminoethyl chloride, 3
-diethylamino-1,2-epoxypropane, 3-
It is obtained by reacting starch with a cationizing reagent such as dibutylamino-1,2-epoxypropane, 2-chloroethyltrimethylammonium chloride, or glycidyltrimethylammonium chloride. Further, starch may be reduced in molecular weight either before or after the reaction of introducing a cationic group.
【００２１】非天然物系のカチオン性ビニルモノマーの
共重合物の場合、溶媒として、エタノール、イソプロパ
ノール、ターシャリーブタノール、メチルエチルケトン
、トルエン、水等を用い、数種類のビニルモノマーを溶
解させ、またラジカル重合開始剤として、溶媒に可溶な
ものを選択して反応させれば良い。例えば、水又は含水
有機溶媒を用いた場合は過硫酸アンモニウム、過硫酸カ
リウム、２，２’−アゾビス（２−アミジノプロパン）
二塩酸塩、４，４’−アゾビス（４−シアノ吉草酸）塩
等が使用できる。また、有機溶媒あるいは含水有機溶媒
を用いた場合は、過酸化ベンゾイル、過酸化ラウロイル
、２，２’−アゾビスイソブチロニトリル、２，２’−
アゾビス（２，４’−ジメチルバレロニトリル）等が使
用できる。In the case of a copolymer of non-natural cationic vinyl monomers, several types of vinyl monomers are dissolved using ethanol, isopropanol, tertiary butanol, methyl ethyl ketone, toluene, water, etc. as a solvent, and radical polymerization is also carried out. As the initiator, an initiator that is soluble in a solvent may be selected and reacted. For example, when water or a water-containing organic solvent is used, ammonium persulfate, potassium persulfate, 2,2'-azobis(2-amidinopropane)
Dihydrochloride, 4,4'-azobis(4-cyanovaleric acid) salt, etc. can be used. In addition, when an organic solvent or a water-containing organic solvent is used, benzoyl peroxide, lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-
Azobis(2,4'-dimethylvaleronitrile) and the like can be used.
【００２２】又、重合温度は、ラジカル開始剤の分解温
度（通常５０〜１００ ℃である）に設定されるが、硫
酸第一鉄−過酸化水素、過硫酸カリウム−亜硫酸ナトリ
ウム等のレドックス系開始剤を使用する場合は、より低
温にしても良い。The polymerization temperature is set at the decomposition temperature of the radical initiator (usually 50 to 100°C), but redox system initiators such as ferrous sulfate-hydrogen peroxide, potassium persulfate-sodium sulfite, etc. If an agent is used, the temperature may be lower.
【００２３】本発明のケテン二量体系サイズ剤組成物を
得るには、まず上記のカチオン性の保護コロイド剤を１
〜３０重量％、好ましくは２〜１０重量％水中に溶解し
昇温する。昇温されたカチオン性保護コロイド剤の水溶
液中に、予め融点以上で加温融解して充分に混合したケ
テン二量体と特定の側鎖を持つケテン二量体との混合物
を５〜３５重量％、好ましくは１５〜３０重量％混合分
散する。この分散時の温度は １００℃以下、好ましく
は８０℃以下であることが望ましい。あまり高温である
と、ケテン二量体は水と反応してサイズ効果を有しない
反応生成物を与える可能性がある。又本発明に係るケテ
ン二量体系サイズ剤のサイズ性能の立ち上がり向上と優
れたサイズ性能効果を損なわない範囲内であれば、他の
分散剤あるいは乳化剤を添加することは何ら差し支えな
い。To obtain the ketene dimer-based sizing agent composition of the present invention, first, the above-mentioned cationic protective colloid agent is added to
~30% by weight, preferably 2-10% by weight, is dissolved in water and heated. Into a heated aqueous solution of a cationic protective colloid agent, add 5 to 35 weight of a mixture of a ketene dimer and a ketene dimer having a specific side chain, which have been heated and melted in advance above the melting point and thoroughly mixed. %, preferably 15 to 30% by weight. The temperature during this dispersion is preferably 100°C or less, preferably 80°C or less. At too high a temperature, the ketene dimer can react with water to give reaction products that have no size effect. Further, other dispersants or emulsifiers may be added as long as they do not impair the improvement in the size performance and the excellent size performance effects of the ketene dimer sizing agent of the present invention.
【００２４】既に述べた様に、本発明に係わるケテン二
量体とアリールケテン二量体は水に分散された形態で用
いられるが、水中に分散されたサイズ剤粒子の粒径は５
ミクロン以下、好ましくは１ミクロン以下であることが
望ましい。粒径が５ミクロンより大きい場合には分散液
の安定性が損なわれたり、サイズ効果が劣ったりする恐
れがある。サイズ剤粒子の分散にはホモミキサー、超音
波乳化機、高圧吐出型ホモジナイザー等が使用できる。As already mentioned, the ketene dimer and aryl ketene dimer according to the present invention are used in the form of being dispersed in water, and the particle size of the sizing agent particles dispersed in water is 5.
It is desirable that the thickness be less than a micron, preferably less than 1 micron. If the particle size is larger than 5 microns, the stability of the dispersion may be impaired or the size effect may be poor. A homomixer, an ultrasonic emulsifier, a high-pressure discharge type homogenizer, etc. can be used to disperse the sizing agent particles.
【００２５】本発明のサイズ剤組成物を歩留り良く使用
するためには、定着剤の使用が有効であり、またその定
着剤としてはカチオン性ポリマーが好ましい。定着剤と
して使用されるカチオン性ポリマーの好ましい例として
は、カチオン化澱粉、カチオン化セルロース、ポリアミ
ド−エピハロヒドリン系ポリマー、ポリエチレンイミン
、ポリビニルピリジン及びその四級化物、ポリジメチル
アミノエチルメタクリレート及びその四級化物、ポリジ
エチルアミノエチルメタクリレート及びその四級化物、
またこれらカチオン性モノマーとアクリルアミドとの共
重合物等を挙げることができる。In order to use the sizing composition of the present invention with good yield, it is effective to use a fixing agent, and a cationic polymer is preferred as the fixing agent. Preferred examples of cationic polymers used as fixing agents include cationized starch, cationized cellulose, polyamide-epihalohydrin polymers, polyethyleneimine, polyvinylpyridine and its quaternized products, polydimethylaminoethyl methacrylate and its quaternized products. , polydiethylaminoethyl methacrylate and its quaternized product,
Also included are copolymers of these cationic monomers and acrylamide.
【００２６】本発明の実施にあたって、本発明のサイズ
剤組成物はパルプ重量に対する固型分として０．０１〜
２重量％、好ましくは０．０５％〜１重量％添加すれば
良い。これらのサイズ剤の添加量の規準は目的とする紙
に要求されるサイズ度に応じて加減しなければいけない
ことはいうまでもない。[0026] In carrying out the present invention, the sizing composition of the present invention has a solid content of 0.01 to 0.01 to pulp weight.
It is sufficient to add 2% by weight, preferably 0.05% to 1% by weight. Needless to say, the amount of these sizing agents added must be adjusted depending on the degree of sizing required for the intended paper.
【００２７】[0027]
【実施例】以下に実施例及び比較例を示して本発明を具
体的に説明するが、本発明はこれらの実施例のみに制限
されるものではない。[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００２８】実施例１〜１０及び比較例１〜５＜サイズ
剤分散液の調整＞表１に示すようなアルキル基の炭素数
分布を有する原料脂肪酸を用いて製造された各種のケテ
ン二量体と表２に示す特定の側鎖を持つケテン二量体と
を７０〜８０℃で融解混合し、表３に示す各種分散剤を
含む温水（７０〜８０℃） を加え、高圧吐出型ホモジ
ナイザーで圧力 ２００ｋｇ／ｃｍ２ にて乳化し、更
に冷却してサイズ剤組成物を得た。得られたサイズ剤組
成の組成及び使用分散剤を表４に示す。Examples 1 to 10 and Comparative Examples 1 to 5 <Preparation of sizing agent dispersion> Various ketene dimers produced using raw fatty acids having the carbon number distribution of alkyl groups as shown in Table 1 and a ketene dimer having a specific side chain shown in Table 2 are melt-mixed at 70 to 80°C, hot water (70 to 80°C) containing various dispersants shown in Table 3 is added, and the mixture is mixed with a high-pressure discharge homogenizer. The mixture was emulsified at a pressure of 200 kg/cm 2 and further cooled to obtain a sizing agent composition. Table 4 shows the composition of the obtained sizing agent and the dispersant used.
【００２９】[0029]
【表１】[Table 1]
【００３０】[0030]
【表２】[Table 2]
【００３１】[0031]
【表３】[Table 3]
【００３２】１） ＰＯ：プロピレンオキシド、ＥＯ
：エチレンオキシド、数字は付加モル数を意味する。1) PO: propylene oxide, EO
: Ethylene oxide, the number means the number of moles added.
【００３３】[0033]
【表４】[Table 4]
【００３４】＜抄紙条件＞本試験に用いた成紙は次に示
す条件下で製造した。
パ ル プ：ＬＢＫＰ（カナディアンスタンダード
フリーネス４００ｍｌ）
填 料 ：軽質炭酸カルシウム（タマパール１
２１ 、奥多摩工業製） 、紙中炭酸カルシウムが１２
％になるように調節して添加
定 着 剤：カチオン化澱粉（ＣＡＴＯＦ、王子ナ
ショナル製） 、パルプ重量に対する固形分 ０．５％
サイズ剤 ：表４記載のケテン二量体系サイズ剤、パ
ルプ重量に対する固形分０．１％
歩留向上剤：カチオン性ポリアクリルアミド系高分子（
パーコール４７、協和産業製） 、パルプ重量に対する
固形分０．０２％
定着時ｐＨ ：８．０
添加順序 ：パルプ→填料→定着剤→サイズ剤→歩留
向上剤
抄 造 ：タッピー角型手抄き機プ レ
ス：３．５ｋｇｗ／ｃｍ２ ×２分間乾 燥
：回転式ドライヤー、９０℃／４０秒間秤 量
：７０ｇ／ｍ２
＜サイズ度試験＞サイズ度試験は次に示す方法にて行っ
た。
サイズ度試験：
ステキヒト法（ＪＩＳ Ｐ−８１２２） による。すな
わち、試験紙の四方を上方に折り曲げて舟型にし、２％
ＮＨ４ＳＣＮ水溶液上に浮かべる。浮かべると同時に上
方より１％ＦｅＣｌ３ 水溶液を一滴試験紙上に落とし
、両水溶液が紙に浸透して接しチオシアン酸鉄の赤い斑
点が３つ出現するまでの時間（秒）を測定した。抄造直
後のサイズ度は、サイズ効果の立ち上がりの良否を示し
、数値の高い物程良である。上記の条件にて抄造した紙
のサイズ度を抄造直後、１日調湿（２０℃×６０％）後
に測定した結果を表５に示す。<Paper Making Conditions> The paper used in this test was produced under the following conditions. Pulp: LBKP (Canadian Standard Freeness 400ml) Filler: Light calcium carbonate (Tama Pearl 1
21, manufactured by Okutama Kogyo), calcium carbonate in paper is 12
Fixing agent: Cationized starch (CATOF, manufactured by Oji National), solid content 0.5% based on pulp weight.
Sizing agent: Ketene dimer type sizing agent listed in Table 4, solid content 0.1% based on pulp weight Retention aid: Cationic polyacrylamide polymer (
Percoll 47, manufactured by Kyowa Sangyo), solid content 0.02% based on pulp weight pH at fixing: 8.0 Addition order: Pulp → filler → fixing agent → sizing agent → retention improver Paper making: Tappy square hand paper machine play
Drying: 3.5kgw/cm2 x 2 minutes
: Rotary dryer, 90℃/40 seconds weighing
:70g/m2 <Sizing test> The sizing test was conducted using the method shown below. Sizing test: Based on Stekicht method (JIS P-8122). In other words, fold the four sides of the test paper upwards to form a boat shape, and add 2%
Float on an aqueous NH4SCN solution. At the same time as floating, a drop of 1% FeCl3 aqueous solution was dropped onto the test paper from above, and the time (seconds) until both aqueous solutions penetrated the paper and came into contact with it and three red spots of iron thiocyanate appeared was measured. The size degree immediately after papermaking indicates the quality of the rise of the size effect, and the higher the value, the better. Table 5 shows the results of measuring the sizing degree of paper made under the above conditions immediately after paper making and after one day of humidity conditioning (20° C. x 60%).
【００３５】[0035]
【表５】[Table 5]
Claims (2)
又はアルケニル基である。）で示されるケテン二量体（
ａ） と、一般式（２） 【化２】 （式中、Ｒ３およびＲ４は炭素数６〜２４のアルキル基
又はアルケニル基であり、ｎ ＝０〜１である。）で示
されるケテン二量体（ｂ） の水分散物を含有してなる
ことを特徴とする製紙用サイズ剤組成物。Claim 1: A ketene dimer represented by the general formula (1):
a) and a ketene dimer represented by the general formula (2) [Formula 2] (wherein R3 and R4 are an alkyl group or an alkenyl group having 6 to 24 carbon atoms, and n = 0 to 1) A paper sizing agent composition comprising an aqueous dispersion of body (b).
体（ａ） と、一般式（２） で示されるケテン二量体
（ｂ） の重量比が （ａ）／（ｂ） ＝９９．９８
／０．０２〜８０／２０である請求項１記載の製紙用サ
イズ剤組成物。Claim 2: The weight ratio of the ketene dimer (a) represented by the general formula (1) and the ketene dimer (b) represented by the general formula (2) is (a)/(b) = 99. .98
2. The paper sizing agent composition according to claim 1, wherein the sizing agent composition has a ratio of /0.02 to 80/20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13292391A JPH04361688A (en) | 1991-06-04 | 1991-06-04 | Sizing agent composition for papermaking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13292391A JPH04361688A (en) | 1991-06-04 | 1991-06-04 | Sizing agent composition for papermaking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04361688A true JPH04361688A (en) | 1992-12-15 |
Family
ID=15092671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13292391A Pending JPH04361688A (en) | 1991-06-04 | 1991-06-04 | Sizing agent composition for papermaking |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04361688A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7311801B2 (en) | 2003-02-21 | 2007-12-25 | Nippon Paper Industries Co., Ltd. | Newsprint papers |
-
1991
- 1991-06-04 JP JP13292391A patent/JPH04361688A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7311801B2 (en) | 2003-02-21 | 2007-12-25 | Nippon Paper Industries Co., Ltd. | Newsprint papers |
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