CN101052765B - 生产皱纹纸的方法 - Google Patents
生产皱纹纸的方法 Download PDFInfo
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- CN101052765B CN101052765B CN2005800374564A CN200580037456A CN101052765B CN 101052765 B CN101052765 B CN 101052765B CN 2005800374564 A CN2005800374564 A CN 2005800374564A CN 200580037456 A CN200580037456 A CN 200580037456A CN 101052765 B CN101052765 B CN 101052765B
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- Prior art keywords
- vinyl
- polymer
- paper
- adhesive
- amine unit
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- 238000004519 manufacturing process Methods 0.000 title abstract description 3
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- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 39
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims description 23
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 13
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 229920005613 synthetic organic polymer Polymers 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
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- 241000209094 Oryza Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
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- 235000009566 rice Nutrition 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- RCIGJWIFCYIQCQ-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.C(=C)N1C=NC=C1 Chemical compound N1=CC=CC2=CC=CC=C12.C(=C)N1C=NC=C1 RCIGJWIFCYIQCQ-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
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- 239000011248 coating agent Substances 0.000 description 3
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- 229920000578 graft copolymer Polymers 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001409 amidines Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 239000000839 emulsion Substances 0.000 description 2
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- MMFCEMSIUPCRLD-UHFFFAOYSA-N 1-ethenyl-4-methylimidazole Chemical compound CC1=CN(C=C)C=N1 MMFCEMSIUPCRLD-UHFFFAOYSA-N 0.000 description 1
- SHVBLBWXKTWTAK-UHFFFAOYSA-N 1-ethenyl-5-methylimidazole Chemical compound CC1=CN=CN1C=C SHVBLBWXKTWTAK-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
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- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
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Abstract
公开了一种通过借助有机合成聚合物或包含所述聚合物的混合物将纸幅粘结到起皱烘缸上、压缩纸幅并从起皱烘缸上移走起皱纸而生产皱纹纸的方法，其中将至少一种包含乙烯基胺单元的聚合物用作有机合成聚合物。
Description
本发明涉及一种通过借助有机合成聚合物作为起皱助剂将湿纸幅粘结到起皱烘缸上、压缩并从起皱烘缸上移走起皱纸而生产皱纹纸的方法。
用于清洁目的或用于干燥的纸，例如手巾纸、餐巾纸、薄纸、厨房用纸巾、厕纸或工业用清洁纸巾，必须柔软和柔韧，贴合不平坦部分，并且能够通过施用于大面积而迅速地吸收液体。为此所需的纸柔软度通过选择合适的纤维、通过借助机械手段来处理纸或者通过合适的造纸方法来获得。
用于软化纸产品的经证实的机械手段是起皱。在该工序中，将湿纸幅送入大型磨光烘缸中，即起皱烘缸中，进行干燥，这通常在造纸过程中进行，其中所述纸幅借助起皱助剂或其混合物轻微粘结到所述起皱烘缸上。在现代方法中，例如在TAD(槽空气干燥)法中，将已经干燥的纸幅送入磨光的金属烘缸中，并借助起皱助剂(这在下文中也指粘合剂)或包含这种助剂的混合物而轻微粘结。在某一点，将锐刀或锐边，即刮刀刀片，压向烘缸。在这里，纸幅被压缩，从烘缸上起下来，并且以减少的张力和减少的速度向前输送以卷起来。取决于所需程度，所述压缩赋予纸以所需尺寸的横向皱褶，即，起皱。该纸的挺度因此降低，建立所需的柔软度。
纸的起皱通常在造纸过程中进行。然而，也可以将已经烘干的纸起皱。因而，起皱还可以独立于造纸通过例如用合适粘合剂的水溶液将纸润湿来进行。
不存在问题且最佳的起皱取决于多个因素，如纸浆的性能，例如所用化学品和纤维的表面电荷，取决于起皱烘缸的表面和温度，取决于机器速度，以及取决于刮刀刀片的锐度和导料角。起皱需要在造纸工部分具有非常高水平的经验。尤其是，它必须可以将纸粘结到烘缸上，使得它在高机器速度下不会因为离心力而飞脱，在没有压缩的情况下不会因刮刀刀片而被起下，并且另一方面，不会在烘缸上过强地粘结，并因此通过刮刀刀片不能从烘缸上完整无缺且干净地移走。另外，不允许起皱助剂形成削弱磨光烘缸的光滑度并在纸上留下痕迹的任何坚硬的、易碎的并且稳固地粘合的涂层。该涂层应该是柔韧的，应该基本上与纸分离，并且应该经常被替换。为了能够掌握这一平衡作用，造纸工使用粘合剂和粘合剂混合物作为起皱助剂，这些粘合剂和粘合剂混合物常常还与脱膜剂配合使用。
被施用于烘缸上或施用于纸幅上并且合适的话，还包含其它粘合剂、增粘剂或脱模剂的已知粘合剂的实例是聚乙烯醇，乙烯与乙酸乙烯酯的共聚物，聚乙酸乙烯酯，聚丙烯酸酯和可热固化的阳离子性聚酰氨基胺树脂。最后提及的树脂是聚酰氨基胺和表氯醇的可热固化缩合物，它们仍旧包含例如当加热至较高温度时会交联的反应性基团。这类树脂例如在生产薄页纸的过程中用作所谓的湿强度剂。然而，由于它们的反应性，它们作为起皱助剂不能容易地处理，因为在起皱烘缸上的聚合物涂层常常变得不规则、坚硬且易碎，从而在生产过程中产生生产和质量问题。由于湿强度树脂具有较高浓度的氯离子，当所述树脂用作起皱助剂时，起皱烘缸可能发生明显的腐蚀。通常情况下，还将水溶性无机磷酸盐用作额外的增粘剂。
在EP-A 0 856 083中公开的用于将纸起皱的方法中，将呈水溶液形式的用表氯醇交联的水溶性聚酰氨基胺和非热固化的或改性聚酰氨基胺作为粘合剂直接施用于起皱鼓的表面。
在US-A-5,602,209中公开的用于将纸起皱的粘合剂包含1-25重量％的聚
唑啉和聚酰氨基胺/表氯醇树脂。然而，聚
唑啉还可以与其它聚合物配合使用，例如与聚乙烯基酰胺、聚乙烯醇、乙醛酸化的聚乙烯酰胺、聚氧化乙烯、聚乙烯亚胺、聚乙烯基吡咯烷酮和Carbowax
聚乙二醇配合使用。如由这些实例可见，与聚
唑啉和另外聚合物的配合使用的效力高于单独聚合物的效力。
现有的德国专利申请DE 102004025861.9描述了在生产皱纹纸的方法中使用如下物质作为粘合剂：(i)聚乙烯亚胺，(ii)聚乙烯亚胺与烷基二烯酮、一元羧酸或其酯或酰氯的反应产物，以及(iii)聚烷基多胺与至少一种双氯醇醚或聚亚烷基二醇的双甘油基醚的反应产物。
因此，本发明的目的是提供用于将纸起皱的另外的粘合剂。
根据本发明，上述目的通过一种生产皱纹纸的方法得以实现，该方法通过借助有机合成聚合物或包含所述聚合物的混合物将纸幅粘结到起皱烘缸上，压缩并从起皱烘缸上移走起皱纸来进行，其中所用有机合成聚合物是至少一种包含乙烯基胺单元的聚合物。
包含乙烯基胺单元的聚合物是已知的，参见US-A-4,421,602、US-A-5,334,287、EP-A-0216387、US-A-5,981,689、WO-A-00/63295、US-A-6,121,409和US-A-6,132,558。它们通过水解包含N-乙烯基羧酰胺单元的开链聚合物来制备。这些聚合物可例如通过聚合如下单体而获得：N-乙烯基甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺和N-乙烯基丙酰胺。所述单体可以单独聚合，或者与其它单体一起聚合。优选N-乙烯基甲酰胺。
与N-乙烯基羧酰胺共聚的合适单烯属不饱和单体是所有可与之共聚的化合物。这些化合物的实例是具有1-6个碳原子的饱和羧酸的乙烯基酯，如甲酸乙烯酯、乙酸乙烯酯、N-乙烯基吡咯烷酮、丙酸乙烯酯和丁酸乙烯酯，以及乙烯基醚，如C1-C6烷基.乙烯基醚，例如甲基.乙烯基醚或乙基.乙烯基醚。其它合适的共聚单体是烯属不饱和C3-C6羧酸的具有例如1-6个碳原子的醇的酯，所述羧酸的酰胺和腈类，例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯和马来酸二甲酯，丙烯酰胺和甲基丙烯酰胺，以及丙烯腈和甲基丙烯腈。
其它合适的羧酸酯衍生自二醇或聚亚烷基二醇，在每种情况下前述二醇只有一个OH基团被酯化，例如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯以及摩尔质量为500-10000的聚亚烷基二醇的丙烯酸单酯。其它合适的共聚单体是烯属不饱和羧酸与氨基醇的酯，如例如丙烯酸二甲基氨基乙基酯、甲基丙烯酸二甲基氨基乙基酯、丙烯酸二乙基氨基乙基酯、甲基丙烯酸二乙基氨基乙基酯、丙烯酸二甲基氨基丙基酯、甲基丙烯酸二甲基氨基丙基酯、丙烯酸二乙基氨基丙基酯、丙烯酸二甲基氨基丁基酯和丙烯酸二乙基氨基丁基酯。碱性丙烯酸酯可以以游离碱形式，以与无机酸如盐酸、硫酸或硝酸的盐形式，以与有机酸如甲酸、乙酸、丙酸或磺酸的盐形式，或者以季化形式使用。合适的季化剂例如是硫酸二甲酯、硫酸二乙酯、氯甲烷、氯乙烷或苄基氯。
其它合适的共聚单体是烯属不饱和羧酸的酰胺，如丙烯酰胺、甲基丙烯酰胺，其具有的烷基含有1-6个碳原子的烯属不饱和羧酸的N-烷基单酰胺和二酰胺，如N-甲基丙烯酰胺、N，N-二甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺和叔丁基丙烯酰胺，以及碱性(甲基)丙烯酰胺，如例如二甲基氨基乙基丙烯酰胺、二甲基氨基乙基甲基丙烯酰胺、二乙基氨基乙基丙烯酰胺、二乙基氨基乙基甲基丙烯酰胺、二甲基氨基丙基丙烯酰胺、二乙基氨基丙基丙烯酰胺、二甲基氨基丙基甲基丙烯酰胺和二乙基氨基丙基甲基丙烯酰胺。
其它合适的共聚单体是N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、丙烯腈、甲基丙烯腈、N-乙烯基咪唑和取代的N-乙烯基咪唑，如例如N-乙烯基-2-甲基咪唑、N-乙烯基-4-甲基咪唑、N-乙烯基-5-甲基咪唑和N-乙烯基-2-乙基咪唑，以及N-乙烯基咪唑啉，如N-乙烯基咪唑啉、N-乙烯基-2-甲基咪唑啉和N-乙烯基-2-乙基咪唑啉。除了以游离碱形式使用以外，N-乙烯基咪唑和N-乙烯基咪唑啉还以用无机酸或有机酸中和的形式或者以季化形式使用，其中季化优选使用硫酸二甲酯、硫酸二乙酯、氯甲烷或苄基氯进行。还合适的是二烯丙基二烷基铵二卤化物，如例如二烯丙基二甲基氯化铵。
共聚物包含以共聚单元形式引入的例如：
-95-5摩尔％、优选90-10摩尔％的至少一种N-乙烯基羧酰胺，优选N-乙烯基甲酰胺，和
-5-95摩尔％、优选10-90摩尔％的单烯属不饱和单体。所述共聚单体优选不含酸基团。
单体的聚合经常在自由基聚合引发剂存在下进行。可以通过所有已知方法来获得均聚物和共聚物；例如，它们通过在水、醇、醚或二甲基甲酰胺或在多种溶剂的混合物中的溶液聚合，通过沉淀聚合，反相悬浮聚合(含单体的水相在油相中的乳液的聚合)以及水包水乳液的聚合(例如，其中将单体水溶液溶解或乳化在水相中，聚合形成水溶性聚合物的水悬浮体，如例如WO 00/27893中所述)来获得。聚合之后，将包含聚合的N-乙烯基羧酰胺单元的均聚物和共聚物按照如下所述部分或全部水解。
为了制备包含乙烯基胺单元的聚合物，优选从N-乙烯基甲酰胺的均聚物开始，或者从可通过如下单体的共聚获得的共聚物开始：
-N-乙烯基甲酰胺与
-甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丙烯腈、丙烯酸甲酯、丙烯酸乙酯和/或甲基丙烯酸甲酯，
然后水解所述均聚物或所述共聚物，由聚合的N-乙烯基甲酰胺单元形成乙烯基胺单元，其中水解度例如为1-100摩尔％，优选5-100摩尔％，特别优选50-100摩尔％，尤其70-100摩尔％。水解度对应于聚合物中乙烯基胺基团的百分摩尔含量。上述聚合物的水解以已知方法通过酸(例如无机酸，如硫酸、盐酸或磷酸，羧酸，如甲酸或乙酸，或者磺酸或膦酸)、碱或酶的作用来进行，例如如DE-A 31 28 478和US-A-6,132,558中所述。当酸用作水解剂时，聚合物的乙烯基胺单元以铵盐存在，然而，在用碱水解的情况下形成游离氨基。
在多数情况下，所用均聚物和共聚物的水解度为85-95摩尔％。均聚物的水解度等于聚合物中乙烯基胺单元的含量。对于包含以聚合单元形式引入的乙烯基酯的共聚物，除了N-乙烯基甲酰胺单元的水解之外，还可能发生酯基的水解，形成乙烯基醇单元。当共聚物的水解在氢氧化钠溶液存在下进行时，尤其如此。以聚合单元形式引入的丙烯腈还在水解过程中被化学改性。这里，例如形成酰氨基或羧基。包含乙烯基胺单元的均聚物和共聚物合适的话，还可包含至多20摩尔％脒单元，这些脒单元例如通过甲酸与两个相邻氨基的反应或者通过氨基与相邻酰氨基的分子内反应而形成，例如通过呈聚合单元形式引入的N-乙烯基甲酰胺的分子内反应而形成。
包含乙烯基胺单元的聚合物的平均摩尔质量Mw例如为500至10百万，优选750至5百万，特别优选1000至2百万克/摩尔(由光散射法测定)。该摩尔质量对应于例如K值为30-150，优选60-100(根据H.Fikentscher，在5％强度的氯化钠水溶液中，于25℃和pH7下，在0.5重量％的聚合物浓度下测定)。特别优选使用的是包含乙烯基胺单元且K值为85-95的聚合物。
包含乙烯基胺单元的聚合物具有例如0-18meq/g、优选5-18meq/g、尤其是10-16meq/g的电荷密度(于pH7下测定)。
包含乙烯基胺单元的聚合物优选以无盐形式使用。包含乙烯基胺单元的聚合物的无盐水溶液可以例如由上述含盐的聚合物溶液，用1000-500000道尔顿、优选10000-300000道尔顿的切取级份借助在合适膜上的超滤而制备。
包含乙烯基胺单元的聚合物的衍生物还可以用作起皱助剂。因此，例如可以由包含乙烯基胺单元的聚合物通过聚合物的氨基的酰胺化、烷基化、形成磺酰胺、形成脲、形成硫脲、形成氨基甲酸酯、酰基化、羧甲基化、膦酰甲基化或Michael加成而制备各种合适的衍生物。此处特别感兴趣的是，未交联的聚乙烯基胍，该聚合物可以通过使包含乙烯基胺单元的聚合物、优选聚乙烯基胺与氰基氨化物(R1R2N-CN，其中R1和R2是H、C1-C4烷基、C3-C6环烷基、苯基、苄基、烷基取代的苯基或萘基)反应而获得，参见US-A-6,087,448，第3栏第64行至第5栏第14行。
包含乙烯基胺单元的聚合物还包括：例如N-乙烯基甲酰胺在聚亚烷基二醇、聚乙酸乙烯酯、聚乙烯醇、聚乙烯基甲酰胺、聚糖(如淀粉)、低聚糖或单糖上的接枝聚合物的水解接枝聚合物。这些水解接枝聚合物可通过使例如N-乙烯基甲酰胺在水性介质中在至少一种所述接枝基质存在下，合适的话与其它可共聚单体一起进行自由基聚合，然后以已知方式将接枝上的乙烯基甲酰胺单元水解成乙烯基胺单元而获得。
包含乙烯基胺单元的优选聚合物是K值为30-150、尤其为60-100的如下聚合物：N-乙烯基甲酰胺的水解度为1-100摩尔％、优选25-100摩尔％的乙烯基胺均聚物，以及N-乙烯基甲酰胺与甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丙烯腈、丙烯酸甲酯、丙烯酸乙酯和/或甲基丙烯酸甲酯的水解度为1-100摩尔％、优选25-100摩尔％的共聚物。上述N-乙烯基甲酰胺的均聚物特别优选用于本发明方法中。
这些包含乙烯基胺单元的聚合物在本发明方法中用作粘合剂。
包含乙烯基胺单元的聚合物在湿纸页和起皱烘缸上的粘合力通常随着包含乙烯基胺单元的聚合物的分子量的增加而增加。如果某种烘缸材料的表面由于之前刚使用的包含乙烯基胺单元的聚合物的结果而太粘的话，那么该粘性可通过使用具有较低分子量的包含乙烯基胺单元的聚合物来降低。如果一方面纸在烘缸上的粘合太弱，则它可以通过使用具有较高分子量的包含乙烯基胺单元的聚合物来增加。在起皱方法中对于纸在烘缸上的粘合的其它控制变量是包含乙烯基胺单元的聚合物的水解度，高水解度也意味着强的粘合，这可以通过较低的水解度来降低。两种可能的控制当然还可以一起使用，其中用于调节的可能方式的多样性非常大。此外，使用如上所述的共聚单体影响包含乙烯基胺单元的聚合物在湿纸页和起皱烘缸上的粘合力。
根据本发明用作起皱助剂的上述粘合剂经常以0.05-15重量％、优选0.1-10重量％强度的水溶液或混合物使用。这种其聚合物浓度为例如10-30重量％的市购产品在用作起皱助剂之前通过添加水或掺入到混合物中而稀释。起皱助剂的即用聚合物水溶液的pH例如为4-12，优选6-10。
本发明还涉及至少一种包含乙烯基胺单元的聚合物作为起皱助剂的用途。
根据本发明用作起皱助剂的聚合物可以例如在造纸过程中喷雾到湿纸幅上，或者直接施用于起皱烘缸。然而，也可以将干燥后的纸后来进行起皱工艺。为此，将干纸或者首先用水润湿(例如润湿至约5-20重量％的湿含量)或者用粘合剂的水溶液直接喷雾，该溶液将根据本发明使用。优选的是，例如在现代TAD机器中，将纸以干态送入烘缸，继而用粘合剂喷雾。粘合剂的用量可以根据需要进行选择：例如，它可以为每平方米纸用1mg-250mg，优选2mg-50mg。起皱烘缸的温度例如为100-150℃，通常为125-145℃。
根据本发明使用的粘合剂可以单独使用，或者以相互的混合物使用。根据本发明的粘合剂的混合物及它们与脱模剂的混合物对于更好地控制在起皱烘缸上的粘合也是可行的，如在其中混入另外的粘合促进剂那样。
然而，还可以将根据本发明使用的粘合剂以与已知起皱助剂的混合物使用。这类混合物可以包含例如10-90、优选20-70重量％的至少一种下列有机合成聚合物：聚乙烯醇，乙烯与乙酸乙烯酯的共聚物，聚乙酸乙烯酯，聚酰氨基胺，聚丙烯酸酯和聚甲基丙烯酸酯，聚丙烯酸和聚甲基丙烯酸，聚乙烯亚胺和聚烷基多胺。所述聚合物以及合适的话，其它添加剂如脱模剂和增粘剂在制备混合物之前应该测试它们与将根据本发明使用的粘合剂的相容性，使得混合物的各组分不相互聚结。合适的脱模剂例如是对纸额外具有软化效果的矿物油和表面活性化合物。增粘剂例如是水溶性的无机磷酸盐。
下列实施例用于解释本发明，而不限制本发明。
除非另有说明，否则实施例中给出的百分数都是重量百分数。K值根据H.Fikentscher，Cellulose-Chemie，第13卷，58-64和71-74(1932)，在5％氯化钠水溶液中，于25℃的温度和pH7下，在0.5重量％的聚合物浓度下测定。
实施例1
在造纸机上生产基重为约20g/m2且基于脱墨废纸的厕所用皱纹纸。借助喷雾棒向起皱烘缸以每平方米纸连续喷雾包含乙烯基胺单元的聚合物(通过水解聚-N-乙烯基甲酰胺而制备，水解度为90摩尔％，K值为90)的10％强度水溶液0.4g作为粘合剂。进行纸的起皱，没有问题发生。在试验工序过程中以及甚至在后续工序中，在起皱烘缸上没有发现麻烦的沉积物和根本没有发生蚀损斑迹象。在造纸机的废水中，基本上没有发现任何可测量得到的痕量来源于所用废纸的有机氯化合物。
对比例1
重复实施例1，唯一的不同点在于，现在借助喷雾棒向起皱烘缸喷雾已知为强度剂的聚酰氨基胺/表氯醇树脂(Luresin
KNU，来自BASF Aktiengesellschaft)的10％强度水溶液0.35g作为粘合剂。在仅仅短时间之后，在起皱烘缸上形成麻烦的沉积物，使得必需停止造纸生产，并且反复打磨起皱烘缸。此外，作为再循环生产废物的结果，切边和其它加工残余物、氯化合物进入造纸机的水循环中。
Claims (6)
1.一种通过借助有机合成聚合物或包含所述聚合物的混合物作为粘合剂将纸幅粘结到起皱烘缸上、压缩并从起皱烘缸上移走起皱纸而生产皱纹纸的方法，其中所用有机合成聚合物是至少一种包含乙烯基胺单元的聚合物，该聚合物是水解度为1-100摩尔％的N-乙烯基甲酰胺的均聚物，其中包含乙烯基胺单元的聚合物的平均分子量为1000至2百万克/摩尔。
2.根据权利要求1的方法，其中包含乙烯基胺单元的聚合物与至少一种选自如下聚合物组成的组中的有机合成聚合物混合用作粘合剂：聚乙烯醇，乙烯与乙酸乙烯酯的共聚物，聚乙酸乙烯酯，聚酰氨基胺，聚丙烯酸酯和聚甲基丙烯酸酯，聚丙烯酸和聚甲基丙烯酸，聚乙烯亚胺和聚烷基多胺。
3.根据权利要求1或2的方法，其中粘合剂包含脱模剂。
4.根据权利要求1或2的方法，其中每平方米纸使用1-250mg粘合剂。
5.根据权利要求3的方法，其中每平方米纸使用1-250mg粘合剂。
6.至少一种包含乙烯基胺单元的聚合物在根据权利要求1-5中任一项的方法中作为起皱助剂的用途，该聚合物是水解度为1-100摩尔％的N-乙烯基甲酰胺的均聚物，其中包含乙烯基胺单元的聚合物的平均分子量为1000至2百万克/摩尔。
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| PCT/EP2005/011278 WO2006048131A1 (de) | 2004-10-29 | 2005-10-20 | Verfahren zur herstellung von gekrepptem papier |
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| US7718035B2 (en) * | 2005-03-15 | 2010-05-18 | Georgia-Pacific Consumer Products Lp | Phosphoric acid quenched creping adhesive |
| US8293073B2 (en) * | 2005-06-30 | 2012-10-23 | Nalco Company | Modified vinylamine/vinylformamide polymers for use as creping adhesives |
| US9266301B2 (en) * | 2005-06-30 | 2016-02-23 | Nalco Company | Method to adhere and dislodge crepe paper |
| CN103243611B (zh) * | 2013-05-09 | 2016-06-08 | 杭州特种纸业有限公司 | 皱纹滤纸及其制作工艺 |
| CN106283864A (zh) * | 2016-08-23 | 2017-01-04 | 山东太阳生活用纸有限公司 | 一种改性聚乙烯亚胺粘缸剂 |
| WO2023212501A1 (en) * | 2022-04-29 | 2023-11-02 | Ecolab Usa Inc. | Creping adhesives comprising polyelectrolyte complex |
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| US20090145565A1 (en) | 2009-06-11 |
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