CN1143989A - 用于纸张涂覆浆的粘结剂混合物 - Google Patents
用于纸张涂覆浆的粘结剂混合物 Download PDFInfo
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- CN1143989A CN1143989A CN95192138A CN95192138A CN1143989A CN 1143989 A CN1143989 A CN 1143989A CN 95192138 A CN95192138 A CN 95192138A CN 95192138 A CN95192138 A CN 95192138A CN 1143989 A CN1143989 A CN 1143989A
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 description 1
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- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
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- SXEQNYJKZGIDTG-UHFFFAOYSA-N n-methoxy-2-methylprop-2-enamide Chemical compound CONC(=O)C(C)=C SXEQNYJKZGIDTG-UHFFFAOYSA-N 0.000 description 1
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- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
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- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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Abstract
用于纸张涂覆浆的粘结剂,它使印刷能够均匀进行,含有由种子工艺制备的聚合物并包括:1-49wt%的具有玻璃化转变温度-80-+25℃和基于丙烯酸或甲基丙烯酸的酯的聚合物种子A),和51-99wt%的烯属不饱和单体B),这些单体的10-100wt%(以B为基础计)是丁二烯,在烯属不饱和单体的聚合反应之前或过程中添加聚合物种子A。
Description
本发明涉及用于纸张涂覆浆的粘结剂,它使印刷能够均匀进行,含有由种子工艺制备的聚合物并包括:
1-49wt%的具有玻璃化转变温度-80-+25℃且基于丙烯酸或甲基丙烯酸的酯的聚合物种子A),和
51-99wt%的烯属不饱和单体B),这些单体的10-100wt%(以B为基础计)是丁二烯,
在该烯属不饱和单体的聚合反应之前或过程中添加聚合物种子A。
本发明进一步涉及这些粘结剂的用途,它的含水分散体和含有该粘结剂的纸张涂覆浆以及用该浆涂覆过的纸张。
在涂层纸上胶印时,对于这一印刷方法经常遇到的问题是印刷物的不均匀性,这在技术上指成斑。这是在本技术领域中迄今一个未解决的问题并同时影响着造纸厂商和印刷商。这一现象尤其发生在多色胶印的中间色调中,并表现为色彩效应中的一种浑浊性。印刷制版中的非均匀性是十分明显的,这表现为在纸张的某些部分印刷油墨被很好地接受,而在其它部分接受不好。
不均匀的油墨接受性能的起因至今没有弄清楚。
尽管作过大量努力,但迄今还没有对这一现象有更好的理解的原因是,一方面在一定程度上在于复杂的胶印方法,和另一方面在于作为印刷材料的纸张的不太复杂的结构。
除了使纸张和印刷油墨的性能最优化以外,这些组分必须相互适应以及适合于胶印方法。
从纸张制造商的观点来看,在涂层纸的情况下,不仅在纸张涂覆方法中的方法工艺参数具有主要的影响作用,而且涂料组分的物理化学性能也起着决定性的作用。在涂覆浆中使用的粘结剂尤为重要。
除了天然产品如淀粉以外,基于苯乙烯和丁二烯或苯乙烯和丙烯酸酯的聚合物乳液也是用作纸张涂覆浆的主要粘结剂。
与丙烯酸酯(共)聚合物例如苯乙烯/丙烯酸酯共聚物相比,当基于丁二烯(共)聚合物例如苯乙烯/丁二烯共聚物的粘结剂用于涂覆胶版印涂层纸时,已知有较大的起斑趋势。
还已知基于苯乙烯/丁二烯的乳液能够与丙烯酸酯乳液混合。
日本公开的专利申请90/169 800描述了用于纸张涂覆的胶乳混合物,它包括丁二烯共聚物和丙烯酸酯共聚物,据说能得到纸张涂层的均匀的印刷油墨接受性。该胶乳混合物含有丙烯酸酯共聚物并具有最低成膜温度35-80℃,共聚物的丙烯酸烷基酯含量为20-50wt%。
日本公开的专利申请82/191 392公开了用于纸张涂覆的聚合物混合物,它由丁二烯共聚物和丙烯腈共聚物组成并赋予涂层纸高光泽。
此外,EP-A099 792公开了含有丁二烯/苯乙烯共聚物和C1-C8链烷醇丙烯酸酯的混合物的聚合物水乳液,以及它们在粘合剂中的用途。
未公开的欧洲专利申请93116834.8(O.Z.0050/44391)披露了一种粘结剂混合物在纸张涂覆浆中的应用,该混合物含有1-49wt%(甲基)丙烯酸酯的聚合物和51-99wt%基于丁二烯/苯乙烯的聚合物。
未公开的德国专利申请P 4325851.4(O.Z.0050/44029)披露了(甲基)丙烯酸酯(第一步)和苯乙烯/丁二烯(第二步)的多步聚合物。
本发明的目的是提供一种粘结剂,它适合用于纸张涂覆浆和具有好的性能、尤其在胶印方面,同时使得有均匀的印刷性能、即显示出极低的起斑趋势。
我们发现这一目的可通过用于纸张涂覆浆的在开头所定义的粘结剂和通过该纸张涂覆浆来实现。
合适的聚合物种子(A)是这样一种聚合物,它的计算(根据Fox)玻璃化转变温度Tg是-80℃-25℃,优选-60-0℃,尤其优选-50--15℃。
玻璃化转变温度能够根据Fox(T.G.Fox,Bull.Am.Phys.Soc.(Ser.II)1(1956)123)来计算。根据上述公开物,下面是共聚物的玻璃化转变温度的很好的近似计算方法:
其中X1、X2...Xn是单体1、2...n的质量分数,Tg1、Tg2...Tgn是单体1、2...n的玻璃化转变温度(单位“开尔文”)。
各单体的Tg已有数据,例如可参见J.Brandrup和E.H.Immergut,Polymer Handbook,第一版,J.Wiley & Sons,New York 1966。
聚合物种子(A)是基于丙烯酸或甲基丙烯酸的酯类,尤其与C4-C12链烷醇形成的酯,例如正丁醇、2-乙基己醇、异丁醇、叔丁醇、正戊醇、异戊醇、正己醇、环己醇、辛醇或月桂醇。
理想的是使用一种包括:
(a1)50-100wt%,优选50-99wt%,尤其优选80-99wt%上述的丙烯酸和/或甲基丙烯酸的C4-C12烷基酯,
(a2)0-50wt%,优选0-35wt%,尤其优选0-20wt%的不超过20个碳原子的乙烯基芳族烃,如α-甲基苯乙烯、对-甲基苯乙烯、乙烯基甲苯或尤其苯乙烯,和
(a3)0-15wt%,优选1-5wt%的其它烯属不饱和单体,的聚合物种子(A)。
优选作为(a3)的是一种或多种不饱和羧酸和/或它们的酰胺和/或酸酐,例如丙烯酸,丙烯酰胺,甲基丙烯酸,甲基丙烯酰胺或衣康酸,马来酸,富马酸,乙烯基磺酸,乙烯基膦酸或丙烯酰胺基丙烷磺酸和它们的水溶性盐。
其它合适的单体(a3)是能够进行自由基聚合反应的单体,例如:烯烃,如乙烯;乙烯基卤化物和偏二卤乙烯,如氯乙烯和偏二氯乙烯;乙烯基醇和C1-C18单羧酸的酯类,如乙酸乙烯酯、丙酸乙烯酯、正丁酸乙烯酯、月桂酸乙烯酯和硬脂酸乙烯酯;α,β-单烯属不饱和二羧酸(如马来酸,富马酸和衣康酸)与具有1-12个碳原子、优选1-9个碳原子、尤其1-4个碳原子的链烷醇的酯类,如马来酸二甲酯或马来酸正丁酯。碱性单体,如其中R1是H或CH3,R2是C1-C4亚烷基和R3和R4各自是H或C1-C4烷基,或其它含有碱性中心的能够进行自由基聚合反应单体,并也可以N-质子化或N-烷基化形式存在,例如化合物二烯丙基二甲基铵氯化物。
A)中也可以存在交联单体。这类单体的实例是共轭的C4-C8二烯,如1,3-丁二烯和异戊二烯,和能够进行自由基聚合反应的并具有至少一个环氧基、羟基、N-羟烷基、N-烷氧基、羰基或脒基或至少两个非共轭烯属不饱和双键的单体。这类单体的组合当然也可以使用。含有环氧基的单体的例子是丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和乙烯基缩水甘油醚。
优选的N-羟烷基化合物是烯属不饱和羧酸的N-羟烷基酰胺,其中烷基具有1-4个碳原子,如N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺、N-羟丙基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟乙基甲基丙烯酰胺、N-羟甲基马来酰亚胺、N-羟甲基马来酰胺和N-羟甲基-对-乙烯基苯甲酰胺。
合适的N-烷氧基甲基丙烯酰胺和N-烷氧基甲基甲基丙烯酰胺主要是烷氧基具有1-8个碳原子的化合物,如N-(甲氧基甲基)丙烯酰胺、N-(丁氧基甲基)丙烯酰胺、N-(甲氧基甲基)甲基丙烯酰胺和N-(丁氧基甲基)甲基丙烯酰胺,以及羟甲基烯丙基氨基甲酸酯(其中羟甲基被C1-C8烷基所醚化)。优选的含羰基化合物是丙烯醛、双丙酮丙烯酰胺、甲酰基苯乙烯、乙烯基烷基酮类和(甲基)丙烯酰氧基烷基丙醛(根据EP专利0,003,516)、双丙酮丙烯酸酯、丙烯酸丙酮基酯、双丙酮甲基丙烯酸酯、2-羟丙基丙烯酸酯乙酰乙酸酯和1,4-丁二醇丙烯酸酯乙酰乙酸酯。
含丫丙啶基的单体的例子是2-(1-丫丙啶基)乙基甲基丙烯酸酯。
具有至少两个丙烯酸酯基、甲基丙烯酸酯基、烷基或乙烯基的交联组分或相应的组合的例子是二(甲基)丙烯酸亚烷基二醇酯类,如二丙烯酸乙二醇酯、二丙烯酸1,3-丁二醇酯、二丙烯酸丙二醇酯、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸1,3-甘油酯、二甲基丙烯酸(1,1,1-三羟甲基丙烷)酯、二丙烯酸(1,1,1-三羟甲基乙烷)酯、三甲基丙烯酸季戊四醇酯、五甲基丙烯酸脱水山梨糖醇酯、亚甲基双丙烯酰胺、甲基丙烯酸烯丙基酯、二乙烯基苯、甲基丙烯酸乙烯酯、丁烯酸乙烯基酯、丙烯酸乙烯基酯和己二酸二乙烯基酯、邻苯二甲酸二烯丙基酯、甲基丙烯酸烯丙基酯、丙烯酸烯丙基酯、马来酸二烯丙基酯、衣康酸二烯丙基酯、丙二酸二烯丙基酯、碳酸二烯丙基酯、柠檬酸三烯丙基酯、二乙烯基醚、乙二醇二乙烯基醚和环戊二烯基丙烯酸酯和甲基丙烯酸酯。
其它合适的单体是具有SiR1R2R3基团的那些单体,其中R1、R1和R3相互独立地是C1-C4烷基或烷氧基,如甲基,乙基,甲氧基或乙氧基,例如乙烯基三烷氧基硅烷,丙烯酰氧基硅烷,例如γ-甲基丙烯酰氧基丙基三甲氧基硅烷和甲基丙烯酰氧基乙基三甲基硅烷。
除了使用此类交联单体外,在聚合反应结束后,通过添加金属盐(例如Ca,Mg或Zn盐)在某些情况下能够提高聚合物膜的粘合性能,只要聚合物含有能够结合这些盐的基团,例如羰基;此外,在聚合反应结束后可以添加肼衍生物类,氨基氧基链烷和基于甲醛、蜜胺、酚和/或脲的缩合物。
如果存在,丙烯腈或甲基丙烯腈在聚合物种子(A)中的含量优选低于5wt%,更优选低于2wt%。
在一优选实施方案中,使用在分子量调节剂存在下制备的聚合物A),例如叔十二烷基硫醇,四氯化碳,四溴化碳,三氯一溴甲烷,丁基硫醇,烯丙基醇,聚四氢呋喃双硫醇,巯基乙醇,乙酰丙酮,巯基乙酸或巯基乙酸盐。这些物质最好以与所要聚合的单体的混合物形式加入到反应混合物中。
聚合物种子优选通过乳液聚合反应制备。得到被分散聚合物颗粒的含水分散体。粒度可通过简单的措施调节到所需要的范围内,如改变乳化剂的量或搅拌速度。
合适的乳液一般具有数均粒度10-1000nm,尤其20-500nm,尤其优选50-200nm,非常优选70-150nm。双峰型和多峰型粒度分布也是理想的。可以使用合适的、更细微地分散的种子乳液制备种子乳液。
烯属不饱和单体B)含有10-100wt%,尤其20-80wt%,尤其优选20-50wt%的丁二烯和0-90wt%,尤其20-80wt%,尤其优选50-80wt%的苯乙烯或上述乙烯基芳族烃和0-10wt%的单-或多-不饱和羧酸和/或其酰胺和/或其酸酐,例如丙烯酸、甲基丙烯酸乙酯、衣康酸或(甲基)丙烯酰胺。
此外,组分(B)可含有0-10wt%的其它共聚单体,优选丙烯腈和/或甲基丙烯腈和/或(甲基)丙烯酸与C1-C12链烷醇的酯类。
为了制备聚合物(B),可以使用占单体用量的0-5wt%的分子量调节剂。合适的物质是在制备组分(A)时提到的那些。
单体(B)的聚合反应能够由使用普通自由基聚合引发剂的乳液聚合反应来进行。
合适的自由基聚合引发剂是能够引发含水的自由基乳液聚合反应的所有那些引发剂。它可以是过氧化物类,例如过二硫酸碱金属盐、过氧化二苯甲酰、γ-丁基过新戊酸酯、过-2-乙基己酸叔丁基酯、2,5-二甲基-2,5-二(叔丁基过氧)己烷或氢过氧化枯烯,和偶氮化物,如偶氮二异丁腈或2,2’-偶氮双(2-脒基丙烷)二盐酸化物。
由至少一种有机还原剂和至少一种过氧化物和/或氢过氧化物,例如叔丁基氢过氧化物和羟基甲烷亚硫酸的钠盐或过氧化氢和抗坏血酸,组成的组合体系也是合适的。其它合适的结合体系是另外还含有少量金属化合物的那些体系,该金属化合物可溶于聚合介质和该化合物的金属组分能够以几种价态存在,例如抗坏血酸/硫酸铁(II)/过氧化氢,羟基甲烷亚硫酸的钠盐、亚硫酸钠、亚硫酸氢钠或偏亚硫酸氢钠通常代替抗坏血酸使用,以及叔丁基氢过氧化物或过二硫酸碱金属盐和/或过二硫酸铵盐通常代替过氧化氢使用。一般,自由基引发剂体系的用量为0.1-3wt%,以所要聚合的单体的总量为基础计。过二硫酸铵盐和/或碱金属盐本身或作为结合体系的一部分,特别优选用作引发剂。
在该新型含水乳液自由基聚合反应的过程中将自由基引发剂体系加入到聚合反应器中的方式与本技术领域中的熟练人员已知的方式类似。该引发剂可以首先全部装入聚合反应器中,或者以一定的速度连续或分阶段加入,在该速度下使得引发剂在含水乳液自由基聚合反应的全过程中消耗完。具体地说,按本技术领域中的熟练人员已知的方式,这即取决于引发剂体系的化学性质又取决于聚合反应温度。优选地,首先加入一些(引发剂)和剩余部分以相当于消耗速度的速度添加到聚合反应区。
在乳液聚合的情况下,通常能够使用已知的离子和/或非离子乳化剂和/或保护性胶体或稳定剂。
这一类型的合适表面活性剂主要是保护性胶体和通常用作分散剂的乳化剂。合适的保护性胶体的详细描述见Houben-Weyl,Methoden derorganischen Chemie,XIV/1卷,Makromole-kulare Stoffe,Georg-Thieme-Verlag,Stuttgart,1961,411-420页。合适的辅助乳化剂是阴离子、阳离子和非离子乳化剂。只有相对分子量通常低于2000的(与保护性胶体相反)乳化剂优选用作辅助表面活性剂。当使用表面活性剂的混合物时,当然,各组分必须相互相容,这可借助于几个初级实验就疑问点加以检验即可。阴离子和非离子乳化剂优选用作辅助表面活性剂。常规的辅助乳化剂例如是乙氧基化脂肪醇(乙氧基化度:3-50,烷基:C8-C36),乙氧基化的单-、二-和三-烷基酚类(乙氧基化度:3-50,烷基:C4-C9),磺基琥珀酸二烷基酯的碱金属盐以及烷基硫酸(烷基:C8-C12)、乙氧基化链烷醇(乙氧基化度:4-30,烷基:C12-C18)、乙氧基化烷基酚类(乙氧基化度:3-50,烷基:C4-C9)、烷基磺酸(烷基:C12-C18)和烷基芳基磺酸(烷基:C9-C18)的碱金属盐和铵盐。
其它合适的分散剂是以下通式II的化合物:其中R5和R6各自是氢或C4-C14烷基且不同时是氢,及X和Y是碱金属离子和/或铵离子。R5和R6各自优选是具有6-18个碳原子的,尤其6、12或16个碳原子的直链或支化烷基,或是氢,而且不同时是氢。X和Y各自优选是钠、钾或铵离子,钠是特别优选的。其中X和Y各自是钠、R5是具有12个碳原子的支化烷基和R6是氢或是R5的化合物II是特别理想的。通常使用含有50-90wt%单烷基化产品的工业混合物,例如DowfaxR2A1(Dow Chemical Company的商标)。
其它合适的乳化剂被描述在Houben-Weyl,Methoden derorganischen Chemie,XIV/1卷,Makromolekulare Stoffe,GeorgThieme Verlag,Stuttgart,1961,192-208页。
除了所存在的乳化剂以外还能够使用保护性胶体,或者在没有乳化剂存在下,制备分散体,保护性胶体的量是至多100wt%,优选0.5-30wt%,以所使用的单体的量为基础计。
在本方法中,这一保护性胶体可以全部或部分地与单体同时或不同时加入或者单独加入;有利的是首先在水溶液中加入至多30wt%,优选至多10wt%的保护性胶体,以单体为基础计。
天然保护性胶体的例子是淀粉,酪蛋白,明胶和藻酸盐,改性天然产品的例子是羟乙基纤维素,甲基纤维素和羧甲基纤维素以及阳离子改性淀粉。合适的合成保护性胶体包括聚丙烯酸和其盐,聚丙烯酰胺,水溶性丙烯酸共聚物,水溶性丙烯酰胺共聚物,聚乙烯基吡咯烷酮,聚乙烯醇和部分水解的聚乙烯醇。
如果一部分保护性胶体被接枝到聚合物上则是有利的。
乳液聚合反应一般是在30-95℃,优选75-90℃下进行。聚合介质可由水单独或由水和水溶性液体如甲醇的混合物组成。水单独使用是优选的。乳液聚合反应可以作为间歇方法和以进料(feed)工艺的形式(包括分步或梯度工艺)进行。优选使用进料方法:其中聚合批料的一部分最初被取出,加热至聚合反应温度并进行聚合,以及聚合批料的剩余部分-连续地、逐渐地或在保持聚合反应的同时有浓度梯度的加入,通常借助于几个单独的进料流,它们中的一个或多个含有纯净形式或乳化形式的单体-被加入到聚合反应区中。
该新型的乳液自由基聚合反应当然也可在超常压或减压下进行。
聚合物A),优选以其含水分散体的形式,可在单体B)的乳液聚合反应的开始使用(最初取出的物质)以制备限定数目的分散体颗粒或随后在乳液聚合反应过程中添加(添加的量)。在最初取出的物质中,聚合物种子A)可以单独使用或与任何其它聚合物种子结合使用。如果随后添加种子,可以在B)的聚合反应中的生长颗粒已达到聚合物种子颗粒的平均粒径时添加。所得到的乳液的单峰粒度分布是聚合反应结束时的结果。然而,也可在任何其它时间添加。那么将形成双峰粒度分布。聚合物种子乳液也可以在几次不同的时间添加。具有不同平均粒度的聚合物种子乳液可以在不同的加料时间加入。结果得到不同的粒度分布。
所得到的粘结剂含有1-49wt%,优选1-19wt%,特别优选3-15wt%的聚合物种子,以固体含量为基础计。单体B)的存在量为51-99wt%,优选81-99wt%,特别优选85-97wt%,以固体含量为基础计,A)和B)的总和是100wt%。
包括A)和B)的粘结剂优选以含水乳液形式在纸张涂覆浆中使用。
所制得的新型的粘结剂的含水聚合反应乳液一般具有总固含量15-75wt%,优选40-60wt%。
乳液可含有常规的助剂,如作为中和剂的氢氧化钾、氨或乙醇胺,作为消泡剂的硅氧烷化合物,农药和硅油或用于减少粘性的蜡。
可以使用粘结剂或它们的含水乳液,用于涂料中或作为涂料,例如表面涂料,粘合剂如接触粘合剂或纸张涂覆浆。
该新型的纸张涂覆浆含有基于A)和B)的粘结剂,含量优选为1-20wt%,尤其5-15wt%,以纸张涂覆浆中的颜料含量为基础计。
颜料通常是纸张涂覆浆的主要组分。通常使用的颜料例如是硫酸钡,碳酸钙,硫铝酸钙,高岭土,滑石,二氧化钛,氧化锌,石灰石或含泥粘土。
纸张涂覆浆也可含有常规分散剂。合适的分散剂例如是聚磷酸或聚丙烯酸的聚合阴离子(聚合盐类),通常它们的含量是0.1-3wt%,以颜料的量为基础计。
纸张涂覆浆也可含有助粘结剂。天然助粘结剂的例子是淀粉、酪蛋白、明胶和藻酸盐,和改性天然产品的例子是羟乙基纤维素、甲基纤维素和羧甲基纤维素以及阳离子改性淀粉。然而,也可以使用常规的合成助粘结剂,例如基于乙酸乙烯酯的那些。
这些助粘结剂的存在量为0.1-10wt%,以颜料的量为基础计。
该新型的纸张涂覆浆能够通过常规的方法涂覆在待涂覆纸张上(参见Ullmann’s Encyklopadie der Technischen Chemie,第4版,17卷,Page603 et seq.)。
在随后的印刷方法中,以这种方式涂覆的纸张具有良好的均匀印刷性,即极少的起斑趋势。
实施例1
使用在最初取出的物质中的聚合物种子A)制备乳液
聚合物种子的制备
最初取出的物质:280.0g 去离子水63.0g 十二烷基硫酸钠,在水中,浓度为10%10.0g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%86.0g 进给料16.3g 进给料2
进给料1:445.0g 去离子水144.0g 十二烷基硫酸钠,在水中,浓度为10wt%100.0g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%31.0g 丙烯酸900.0g 丙烯酸正丁酯100.0g 苯乙烯
进给料2:120.0g 去离子水5.0g 过硫酸钠
最初取出的物质在一搅拌烧瓶中被加热至85℃,并聚合15分钟。之后,剩余量的进给料1在85℃下经2小时计量加入,并且,与进给料1同时开始,进给料2经2.5小时计量加入。反应混合物然后在85℃下进一步搅拌1小时。获得固体含量49.5wt%的乳液,数均粒度(Malvern Autosizer)是71nm和LD值97%。
粘结剂的制备
最初取出的物质:6000.0g 去离子水16.7g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%3030.0g 如上获得的聚合物种子的乳液1107.0g 进给料1212g.0g 进给料2
进给料1:5124.0g 去离子水5100.0g 丁二烯9375.0g 苯乙烯541.0g 丙烯酸120.0g 叔十二烷基硫醇133.3g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%250.0g 十二烷基硫酸钠,在水中,浓度为15wt%
进给料2:120.0g 过硫酸钠2000.0g 去离子水
最初取出的物质在一搅拌耐压釜中被加热至85℃,并聚合15分钟。之后,剩余量的进给料1在85℃下经4.5小时计量加入,并且,与进给料1同时开始,进给料2经4.5小时计量加入。反应混合物然后在85℃下进一步搅拌1小时。获得固体含量50.6%的乳液,粒度(Malvern Autosizer)是156nm和LD值54%。玻璃化转变温度是25℃,根据Fox的计算值。
实施例2
通过使用随后添加的聚合物种子制备乳液
聚合物种子的制备
最初取出的物质:210.0g 去离子水10.5g 十二烷基硫酸钠,在水中,浓度为10wt%1.7g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%61.1g 进给料15.2g 进给料2
进给料1:430.0g 去离子水12.0g 十二烷基硫酸钠,在水中,浓度为10wt%5.0g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%23.0g 丙烯酸675.0g 丙烯酸正丁酯75.0g 苯乙烯
进给料2:100.0g 去离子水3.75g 过硫酸钠
最初取出的物质在一搅拌烧瓶中被加热至85℃,并聚合15分钟。之后,剩余量的进给料1在85℃下经2小时计量加入,并且,与进给料1同时开始,进给料2经2.5小时计量加入。反应混合物然后在85℃下进一步搅拌1小时。获得固体含量49.4%的乳液,粒度(Malvern Autosizer)是120nm和LD值88%。
粘结剂的制备
最初取出的物质:5820.0g 去离子水98.0g 十二烷基硫酸钠,在水中,浓度为10wt%1164.0g 进给料1315.0g 进给料2
进给料1:5124.0g 去离子水5100.0g 丁二烯9375.0g 苯乙烯541.0g 丙烯酸120.0g 叔十二烷基硫醇133.3g C12-烷基二苯基醚二磺酸钠,在水中,浓度为45%250.0g 十二烷基硫酸钠,在水中,浓度为15%
进给料2:120.0g 过硫酸钠2000.0g 去离子水
进给料3:2884.0g 如上获得的聚合物种子的乳液
最初取出的物质在一搅拌耐压釜中被加热至85℃,并聚合15分钟。之后,剩余量的进给料1在85℃下经4.5小时计量加入,并且,与进给料1同时开始,进给料2经4.5小时计量加入。在剩余量的进给料1和进给料2计量加入开始后的1.5小时,进给料3在3分钟内全部一次加入。在进给料1和进给料2的加完后,反应混合物在85℃下进一步搅拌1小时。获得固体含量50.3%的乳液,粒度(Malvern Autosizer)是50%。玻璃化转变温度是24℃。
实施例3
不使用聚合物种子制备基于丁二烯的聚合物乳液
最初取出的物质:19.4g 去离子水0.25g 十二烷基硫酸钠,在水中,浓度为10%3.88g 进给料11.05kg 进给料2
进给料1:24.25kg 去离子水17.5kg 丁二烯31.0kg 苯乙烯1.5kg 丙烯酸0.5kg 叔十二烷基硫醇2.75kg 十二烷基硫酸钠,在水中,浓度为15%
进给料2:0.4kg 过硫酸钠4.85kg 去离子水
最初取出的物质被加热至85℃,并聚合15分钟。之后,剩余量的进给料1经5小时加入,并且,与进给料1同时开始,进给料2经5.5小时加入。然后,聚合反应在85℃下继续进行2小时。获得粒度(MalvernAutosizer)是170nm和固体含量50%的乳液。玻璃化转变温度是17℃。
应用实施例
在实施例中描述的乳液用作具有以下组成的纸张涂覆浆中的粘结剂(份数是重量份数):60份 细微分散的石灰石40份 细微分散的粘土1份 羧甲基纤维素0.6份 分子量为4000的聚丙烯酸的钠盐(BASF聚盐)12份 粘结剂乳液(固含量:66wt%,PH8.5-9,用NaOH调节)
所使用的纸张是具有基重70g/m2的道林涂布原纸。将涂覆浆涂在两面,每面的涂覆量均为13g/m2,在实验用涂覆机(涂覆方法:辊涂,计量方法:刮刀)上,以1000m/min的速度涂覆。借助于IR干燥装置和空气干燥,将卷筒纸调节至纸温汽含量5.5%。
最高卷筒温度100℃。
卷筒纸经过简单地通过高度砑光机而被砑光。轧点压力250kN/m,卷筒速度300m/min和温度80℃。
为了评价印刷性能,用Tobias试验机测定起斑扫描值。(测量方法描述在:Philipp E.Tobias等,Tappi Journal,72卷,No.5,1989年5月)。在着色区域测定起斑扫描值,该区域在4-色彩胶印机上由单张纸胶印方法印刷后,油墨覆盖度为青色的最大油墨覆盖度的50%。
粘结剂 | 起斑扫描值 |
实施例1 | 425 |
实施例2 | 358 |
实施例3 | 623 |
低的起斑扫描值是指良好的印刷性能,即少的起斑现象。
Claims (9)
1、包括由种子工艺制备的聚合物的粘结剂,它包括:
1-49wt%的具有玻璃化转变温度-80-+25℃、基于丙烯酸或甲基丙烯酸的酯的聚合物种子A),和
51-99wt%的烯属不饱和单体B),以B为基础计,这些单体的10-100wt%是丁二烯,
在烯属不饱和单体的聚合反应之前或过程中添加聚合物种子A。
2、根据权利要求1所要求的粘结剂,含有作为聚合物种子A)的聚合物,这一聚合物包括:
(a1)50-100wt%丙烯酸或甲基丙烯酸的C4-C12烷基酯,或这类酯的混合物,
(a2)0-50wt%乙烯基芳族烃,和
(a3)0-15wt%的其它烯属不饱和单体。
3、根据权利要求1或2所要求的粘结剂,含有作为聚合物种子的聚合物,该聚合物包括:
(a1)80-99wt%丙烯酸或甲基丙烯酸的C4-C12烷基酯,或这类酯的混合物,
(a2)0-20wt%苯乙烯或苯乙烯衍生物或其混合物,和
(a3)1-5wt%的丙烯酸或甲基丙烯酸或其混合物。
4、根据权利要求1-3中任何一项所要求的粘结剂作为纸张涂覆浆中的粘结剂以获得均匀的印刷性能的用途。
5、含有根据权利要求1-3中任何一项所要求的粘结剂的水乳液。
6、根据权利要求5所要求的水乳液在纸张涂覆浆中的用途。
7、用于胶印的纸张涂覆浆,它含有颜料和1-20wt%(以颜料含量为基础计)的根据权利要求1-3中任何一项所要求的粘结剂。
8.使用权利要求7所要求的纸张涂覆浆可获得的涂层纸。
9、根据权利要求5所要求的水乳液作为粘合剂,尤其作为接触粘合剂的用途。
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DE4403480A DE4403480A1 (de) | 1994-02-04 | 1994-02-04 | Bindemittelmischungen für Papierstreichmassen |
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US (1) | US5759347A (zh) |
EP (1) | EP0742857B1 (zh) |
KR (1) | KR970700802A (zh) |
CN (1) | CN1143989A (zh) |
AT (1) | ATE168425T1 (zh) |
AU (1) | AU679836B2 (zh) |
CA (1) | CA2182405A1 (zh) |
DE (2) | DE4403480A1 (zh) |
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CN103547735A (zh) * | 2011-05-30 | 2014-01-29 | 巴斯夫欧洲公司 | 具有阻隔涂层的纸和卡纸板包装 |
CN103975107A (zh) * | 2011-12-06 | 2014-08-06 | 巴斯夫欧洲公司 | 具有阻挡涂层的纸和纸板包装 |
CN109535324A (zh) * | 2018-09-30 | 2019-03-29 | 浙江佳润新材料有限公司 | 一种耐水耐油脂造纸浆料及其制备方法 |
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JP3093965B2 (ja) * | 1994-12-28 | 2000-10-03 | 日本製紙株式会社 | 吸水性を改良した印刷用紙及び新聞印刷用紙 |
DE19522400A1 (de) * | 1995-06-21 | 1997-01-02 | Basf Ag | Verwendung von Papierstreichmassen mit hohem Butadiengehalt im Tiefdruck |
US20020025430A1 (en) * | 1996-12-23 | 2002-02-28 | Rudolf Weissgerber | Compsite paper material with a pressure-sensitive adhesive coating finished to be resistant to repulping |
US5861209A (en) * | 1997-05-16 | 1999-01-19 | Minerals Technologies Inc. | Aragonitic precipitated calcium carbonate pigment for coating rotogravure printing papers |
JP4577914B2 (ja) * | 1997-10-13 | 2010-11-10 | 株式会社中戸研究所 | 防曇性コーティング材料および防曇性物品 |
DE10008276A1 (de) * | 2000-02-23 | 2001-08-30 | Basf Ag | Papierstreichmassen auf Basis von gering vernetzten Bindemitteln |
JP5112291B2 (ja) * | 2005-04-08 | 2013-01-09 | ナルコ カンパニー | 紙材製造のための改良された組成物及びプロセス |
EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
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US2791571A (en) * | 1954-12-01 | 1957-05-07 | Goodrich Co B F | Aqueous interpolymer dispersions and non-blocking films therefrom |
US3875097A (en) * | 1971-12-23 | 1975-04-01 | John Andrew Sedlak | Ionic vinylamide polymer latex and manufacture of paper therewith |
US4064304A (en) * | 1973-06-18 | 1977-12-20 | Kanzaki Paper Manufacturing Company, Ltd. | Coated synthetic paper adapted for offset printing and method for production thereof |
US4173596A (en) * | 1977-12-23 | 1979-11-06 | The B. F. Goodrich Company | Soft-seeded tougheners for polyvinyl chloride |
DE2926631A1 (de) * | 1979-07-02 | 1981-01-29 | Wacker Chemie Gmbh | Waessrige dispersion auf grundlage von (meth-)acrylsaeurederivaten, ihre herstellung und verwendung |
JPS57191392A (en) * | 1981-05-11 | 1982-11-25 | Mitsui Toatsu Chemicals | Paper coating resin composition |
FR2529899A1 (fr) * | 1982-07-09 | 1984-01-13 | Rhone Poulenc Spec Chim | Dispersions aqueuses de resines synthetiques, leur utilisation comme liants dans les compositions adhesives et compositions adhesives obtenues |
US5093405A (en) * | 1984-12-20 | 1992-03-03 | Rohm And Haas Company | Modified latex polymer compositions |
US5093449A (en) * | 1988-07-18 | 1992-03-03 | Reichhold Chemicals, Inc. | Styrene-butadiene latex compositions |
JPH02169800A (ja) * | 1988-12-16 | 1990-06-29 | Asahi Chem Ind Co Ltd | 紙塗工用ラテックス |
US5444118A (en) * | 1989-06-30 | 1995-08-22 | Japan Synthetic Rubber Co., Ltd. | Process for producing copolymer latex and paper coating composition, carpet backing composition or adhesive composition comprising said latex |
US5246981A (en) * | 1989-07-10 | 1993-09-21 | Mitsui Toatsu Chemicals, Inc. | Aqueous emulsion |
DE4236316A1 (en) * | 1991-10-31 | 1993-05-06 | Takeda Chemical Industries Ltd | Copolymer lattices, useful as binders in paper coating compsns. - by two=stage emulsion polymerisation of monomer mixt., with hydrophilic chain transfer agent and hydrophobic agent in second stage |
DE4315881A1 (de) * | 1993-05-12 | 1994-11-17 | Basf Ag | Zweistufig aufgebautes Copolymerisat |
US5356683A (en) * | 1993-10-28 | 1994-10-18 | Rohm And Haas Company | Expandable coating composition |
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- 1995-01-23 EP EP95907581A patent/EP0742857B1/de not_active Expired - Lifetime
- 1995-01-23 WO PCT/EP1995/000224 patent/WO1995021294A1/de active IP Right Grant
- 1995-01-23 CN CN95192138A patent/CN1143989A/zh active Pending
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103547735A (zh) * | 2011-05-30 | 2014-01-29 | 巴斯夫欧洲公司 | 具有阻隔涂层的纸和卡纸板包装 |
CN103975107A (zh) * | 2011-12-06 | 2014-08-06 | 巴斯夫欧洲公司 | 具有阻挡涂层的纸和纸板包装 |
CN103975107B (zh) * | 2011-12-06 | 2016-09-14 | 巴斯夫欧洲公司 | 具有阻挡涂层的纸和纸板包装 |
CN109535324A (zh) * | 2018-09-30 | 2019-03-29 | 浙江佳润新材料有限公司 | 一种耐水耐油脂造纸浆料及其制备方法 |
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EP0742857B1 (de) | 1998-07-15 |
ATE168425T1 (de) | 1998-08-15 |
EP0742857A1 (de) | 1996-11-20 |
DE59502829D1 (de) | 1998-08-20 |
KR970700802A (ko) | 1997-02-12 |
AU1575595A (en) | 1995-08-21 |
WO1995021294A1 (de) | 1995-08-10 |
US5759347A (en) | 1998-06-02 |
CA2182405A1 (en) | 1995-08-10 |
DE4403480A1 (de) | 1995-08-10 |
AU679836B2 (en) | 1997-07-10 |
FI963069A (fi) | 1996-08-02 |
FI963069A0 (fi) | 1996-08-02 |
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