中性松香施胶剂的制备、应用及作用机理
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摘要
松香胶目前仍是造纸用主要施胶剂，且已从皂化胶、强化胶、
阴离子乳液松香胶发展到阳离子乳液松香胶—第四代产品。同时施
胶正从酸性向中性工艺转变。我国目前仍以非木材纤维造纸为主，
以速生丰产的桉木为原料造纸进行中性造纸是今后发展方向。本课
题主要研究开发高效中性松香施胶剂，主要工作如下：
（1）制备出XQ-CR阳离子松香胶、XQ-AR阴离子中性松香胶，使
之用于桉木化机浆及其他浆料配抄优质印刷纸的中性施胶。XQ-CR
阳离子松香胶的制备关键是阳离子松香的制备及乳化，采用的是高
分子乳化剂。XQ-AR阴离子中性松香胶的制备关键是特效乳化剂的
制备，其主要成分是烷基酚聚氧乙烯醚马来酸酯磺酸盐。
（2）中性乳液松香胶必须配加相同离子性的聚丙烯酸树脂增效
剂，这种增效剂同时具有分散和增强作用，本身亦可用于对施胶度
要求不高的纸种的施胶处理。本课题分别研究了阴离子和阳离子聚
丙烯酸树脂增效剂的制备条件，重点解决了松香改性及乳化、乳液
贮存和应用工艺等问题。
（3）制备出中性施胶用的专用留着剂。分别研究了阳离子淀粉、
阳离子聚丙烯酰胺和阳离子聚酰胺多胺环氧氯丙烷等的应用条件，它
们的共同特点是，具有较高的相对分子质量和较强的阳离子性，可
在中性或弱碱性条件下显示正电性，与纤维有较强的结合作用，能
够通过化学和物理作用产生一定的增强、留着效果。但作为中性施
胶松香留着剂，效果以聚酰胺多胺环氧氯丙烷最佳，其在碱性条件下
可发生自交联作用，本身亦可用于对施胶要求并不很高的纸种的施
胶。
大 连理 工 大 学 埔 土 学 位诠 文
W分别确定了上述产品的制备和应用工艺。XQ－CR阳离子松香
胶的最佳应用邯是：硫酸铝 4o／b，胶料 0．5‘yo－1．OO／O，PAE 0．25。X；－
0．5％，碳酸钙25O／O左右。采用逆向施胶工艺，硫酸铝加入稠浆处，
胶料加入稀浆处。夏季施胶应提高硫酸铝及胶料用量，同时加入阳
离子留着剂可消除高温和高 pH值对施胶的不利影响。XQ－AR阴离
子松香胶的最佳应用条件：胶料0．5O－l．OO／O，硫酸铝4o／o，PAE
0．25％－0．5％，碳酸钙25％左右。采用正向施胶工艺。
间进行了上述产品的结构表征和性能检测，研究了相应的湿部
化学作用衅。对中性施胶腴断了研究。
上述研究是国家jit攻关 捡木化机浆配用系列助剂－XQ－
CR中性施胶剂、XQ－助留助滤剂及 XQ－增强剂一的部分内容。研究
自1997年6月始，目前已胁结束，XQ－CR阳离子中陇胶剂及
XQ－AR阴离子中性贿胶均可填补国内空白，达到国夕中胜施胶剂水
平；对草浆淋浆均具有明显的施胶效果，可使纸的质量提高，生
产咸本降低，对于提高咸纸强度、抄造性能、印刷性能和邯性能，
降低能耗和浆耗，减轻设备腐蚀和废水污染等；具有重大意义。且
贮存稳定性好，如在全国推广，则纶得巨大的经济赃。
The rosin sizes are still the mainl~ sizing agents for paperrnaking by now. The
cationic rosin sizing agents are called to be the fourth generation production from the
soaped sizes. the fortified sizes and the anionic rosin sizes of emulsion. Simultaneously.
the papermaking technology have been conversing from acidic to weekly acidic or
neutral sizing. Also the non-wood fiber are still the mainly materials for papermaking
in china, but using the eucalyptus wood as the new raw material for papemiaking at
neutral conditions will be the direction of development. The present investigation relates
to sizes for a papermaking. more specifically to an internal size which works very well
in papermaking under weakly acidic to neutral conditions. Series emulsions of rosin
sizes have been gotten based on lots of the literatures of at home and abroad.
(1) The XQ-CR cationic rosin sizes and the XQ-AR anionic rosin sizes have been
developed. Conventional rosin emulsion sizes consists mainly of so-called fortified
rosins, i.e., rosins modified with ctj~-unsaturated dibasic acids, and an anionic surfactant.
Among a few of anionic surfactants. the sulfate ester of the maleic anhydride and
polyoxyethylene nonylphenyl ether has shown to be the effective emulsifying agent.
The anionic and cationic rosin sizes are both used in a dispersion in the present of the
alkyl acrylate resin emulsions which can be used as the size synergist.
(2) Comprising a rosin sizing agent fortified by adding the same ionic copolymer
emulsion of alkyl actylate with stvrene wherein the rosin and modified rosin are
dispersed in water with the aid of an emulsifying agent and the size synergist, and paper
sized therewith. The rosin emulsion sizing agent of the present invention have exhibited
an distinguished sizing effect in neutral papermaking systems even when content of the
calcium carbonate is high therein and been excellent in mechanical and storage stability
while decreasing the production cost in addition the sizing agent presents no significant
difficulties in its production.
(3) To increase the size degree of above rosin emulsion, the polyaminoamide
epichlorohydrin (PAE) has been used. Comprising the copolymer of cationic acrylamide
with other hydrophilic monomer and the cationic starch, it serves very well as both a
retention aid and a sizing agent for neutral paper because its sizing quality around the
neuthel pH is low The high molecular weight ard the Stronger cationic ctwes are
necesSary for attributing the excellent proPerties of retention and sizing. Not only as the
sPecial retention agent for rosin sizes, but also the PAE can be used as the wet
reinfOrcing agent by crossing of itself at the neutrai or basic condition.
(4) The best conditions of preparaion and aPpiicaion of above products have been
detendned, the sizing technology of catiohic size XQ-CR is as mis: sulfate altalniurn
4%. XQ-CR 0.5W1 .0%,PAE 0.259M.5%. calciurn carbomate 25% with the reverse
sining. in the summer, the disadvantaged infiuences of high temperatUr and high pH
value tO sdrig are reduced by adding more sulfate aIurnndum and sizing agent and PAE.
The selected technology ofedonic sizing agen XQ-AR is as this: XQ-AR 0.5Wl.0%.
sulfate aiwtum 4%, PAE 0.259ed.5%. talcium carbomate 25% with the bet
seq.
(5) The measure ofsimCtUr and Properties for above ProduCts are cAned out. lt is
helpful for studying on the chdrical interachon mechasm betwen aids and the Paper
fiber and neutral sthe mecbosm in wet processing.
阴离子乳液松香胶发展到阳离子乳液松香胶—第四代产品。同时施
胶正从酸性向中性工艺转变。我国目前仍以非木材纤维造纸为主，
以速生丰产的桉木为原料造纸进行中性造纸是今后发展方向。本课
题主要研究开发高效中性松香施胶剂，主要工作如下：
（1）制备出XQ-CR阳离子松香胶、XQ-AR阴离子中性松香胶，使
之用于桉木化机浆及其他浆料配抄优质印刷纸的中性施胶。XQ-CR
阳离子松香胶的制备关键是阳离子松香的制备及乳化，采用的是高
分子乳化剂。XQ-AR阴离子中性松香胶的制备关键是特效乳化剂的
制备，其主要成分是烷基酚聚氧乙烯醚马来酸酯磺酸盐。
（2）中性乳液松香胶必须配加相同离子性的聚丙烯酸树脂增效
剂，这种增效剂同时具有分散和增强作用，本身亦可用于对施胶度
要求不高的纸种的施胶处理。本课题分别研究了阴离子和阳离子聚
丙烯酸树脂增效剂的制备条件，重点解决了松香改性及乳化、乳液
贮存和应用工艺等问题。
（3）制备出中性施胶用的专用留着剂。分别研究了阳离子淀粉、
阳离子聚丙烯酰胺和阳离子聚酰胺多胺环氧氯丙烷等的应用条件，它
们的共同特点是，具有较高的相对分子质量和较强的阳离子性，可
在中性或弱碱性条件下显示正电性，与纤维有较强的结合作用，能
够通过化学和物理作用产生一定的增强、留着效果。但作为中性施
胶松香留着剂，效果以聚酰胺多胺环氧氯丙烷最佳，其在碱性条件下
可发生自交联作用，本身亦可用于对施胶要求并不很高的纸种的施
胶。
大 连理 工 大 学 埔 土 学 位诠 文
W分别确定了上述产品的制备和应用工艺。XQ－CR阳离子松香
胶的最佳应用邯是：硫酸铝 4o／b，胶料 0．5‘yo－1．OO／O，PAE 0．25。X；－
0．5％，碳酸钙25O／O左右。采用逆向施胶工艺，硫酸铝加入稠浆处，
胶料加入稀浆处。夏季施胶应提高硫酸铝及胶料用量，同时加入阳
离子留着剂可消除高温和高 pH值对施胶的不利影响。XQ－AR阴离
子松香胶的最佳应用条件：胶料0．5O－l．OO／O，硫酸铝4o／o，PAE
0．25％－0．5％，碳酸钙25％左右。采用正向施胶工艺。
间进行了上述产品的结构表征和性能检测，研究了相应的湿部
化学作用衅。对中性施胶腴断了研究。
上述研究是国家jit攻关 捡木化机浆配用系列助剂－XQ－
CR中性施胶剂、XQ－助留助滤剂及 XQ－增强剂一的部分内容。研究
自1997年6月始，目前已胁结束，XQ－CR阳离子中陇胶剂及
XQ－AR阴离子中性贿胶均可填补国内空白，达到国夕中胜施胶剂水
平；对草浆淋浆均具有明显的施胶效果，可使纸的质量提高，生
产咸本降低，对于提高咸纸强度、抄造性能、印刷性能和邯性能，
降低能耗和浆耗，减轻设备腐蚀和废水污染等；具有重大意义。且
贮存稳定性好，如在全国推广，则纶得巨大的经济赃。
The rosin sizes are still the mainl~ sizing agents for paperrnaking by now. The
cationic rosin sizing agents are called to be the fourth generation production from the
soaped sizes. the fortified sizes and the anionic rosin sizes of emulsion. Simultaneously.
the papermaking technology have been conversing from acidic to weekly acidic or
neutral sizing. Also the non-wood fiber are still the mainly materials for papermaking
in china, but using the eucalyptus wood as the new raw material for papemiaking at
neutral conditions will be the direction of development. The present investigation relates
to sizes for a papermaking. more specifically to an internal size which works very well
in papermaking under weakly acidic to neutral conditions. Series emulsions of rosin
sizes have been gotten based on lots of the literatures of at home and abroad.
(1) The XQ-CR cationic rosin sizes and the XQ-AR anionic rosin sizes have been
developed. Conventional rosin emulsion sizes consists mainly of so-called fortified
rosins, i.e., rosins modified with ctj~-unsaturated dibasic acids, and an anionic surfactant.
Among a few of anionic surfactants. the sulfate ester of the maleic anhydride and
polyoxyethylene nonylphenyl ether has shown to be the effective emulsifying agent.
The anionic and cationic rosin sizes are both used in a dispersion in the present of the
alkyl acrylate resin emulsions which can be used as the size synergist.
(2) Comprising a rosin sizing agent fortified by adding the same ionic copolymer
emulsion of alkyl actylate with stvrene wherein the rosin and modified rosin are
dispersed in water with the aid of an emulsifying agent and the size synergist, and paper
sized therewith. The rosin emulsion sizing agent of the present invention have exhibited
an distinguished sizing effect in neutral papermaking systems even when content of the
calcium carbonate is high therein and been excellent in mechanical and storage stability
while decreasing the production cost in addition the sizing agent presents no significant
difficulties in its production.
(3) To increase the size degree of above rosin emulsion, the polyaminoamide
epichlorohydrin (PAE) has been used. Comprising the copolymer of cationic acrylamide
with other hydrophilic monomer and the cationic starch, it serves very well as both a
retention aid and a sizing agent for neutral paper because its sizing quality around the
neuthel pH is low The high molecular weight ard the Stronger cationic ctwes are
necesSary for attributing the excellent proPerties of retention and sizing. Not only as the
sPecial retention agent for rosin sizes, but also the PAE can be used as the wet
reinfOrcing agent by crossing of itself at the neutrai or basic condition.
(4) The best conditions of preparaion and aPpiicaion of above products have been
detendned, the sizing technology of catiohic size XQ-CR is as mis: sulfate altalniurn
4%. XQ-CR 0.5W1 .0%,PAE 0.259M.5%. calciurn carbomate 25% with the reverse
sining. in the summer, the disadvantaged infiuences of high temperatUr and high pH
value tO sdrig are reduced by adding more sulfate aIurnndum and sizing agent and PAE.
The selected technology ofedonic sizing agen XQ-AR is as this: XQ-AR 0.5Wl.0%.
sulfate aiwtum 4%, PAE 0.259ed.5%. talcium carbomate 25% with the bet
seq.
(5) The measure ofsimCtUr and Properties for above ProduCts are cAned out. lt is
helpful for studying on the chdrical interachon mechasm betwen aids and the Paper
fiber and neutral sthe mecbosm in wet processing.
引文
[1] Enos H I, Harris G C and Hedrick G W.Encyclopedia of Chernical Technoiogy.2nd Ed. Vol. 17.Wiley. New York. 1968
[2] Smith K E. Pulp Pap.Jan. 1983:P142
[3] Davison R W. Marton T. Tappi. 1964.47(10):609
[4] 徐忠恺、李春芳．上海造纸．1992．23(1)：14
[5] 徐忠恺、李春芳．国外造纸．1992．11 (2)：15
[6] Casey J P. Pulp and Paper. Chemistry and Chemical Techmology.3rd Ed. Vol.3.Wiley-Interscience.New York.1981
[7] 约翰逊 R W，弗里兹 E 编．工业脂肪酸及其尖用．陆用海、胡征宇译．中国轻工业出版社．1991：611～642
[8] Strazdins E.Tappi. 1965.48:157
[9] 牛华．纸和造纸．1997．增刊：37
[10] Strazdins E.Tappi. 1977.60:102
[11] Strazdins E.Tappi. 1981.64:31
[12] Strazdins E.Tappi.1984.67:110
[13] 中华．造纸化学品．1997．2：19
[14] 邓亚君．造纸化学品．1997．2：25
[15] 特开昭 55-129450
[16] 特开昭 5-33291
[17] Marton E.Tappi. 1980.63: 121
[18] Arnson T R.Tappi. 1982.65:125
[19] Arnson T R and Stration R A.Tappi. 1983.66:72
[20] Porter R B.in Internal Sizing of Paperand Paperboard.Tappi Monograph 33.T W Swanson.ed.Tappi Press. New York.1971:146
[21] Liu J.Paper Technology. 1993.34 (8): 20
[22] Anson T. Notes of 1987 TAPPI Sizing Short Course: 31
[23] Strazding E.Tappi. 1963.46 (7): 432
[24] 朱勇强等．中国造纸．1997．5：39
[25] 郑博文等．中国造纸．1989．8 (5)：22
[26] 朱勇强等．中国造纸．1993．12 (3)：42
[27] 朱勇强等．中国造纸．1994．13 (6)：30
[28] 朱勇强等．中国造纸．1997．5：39
[29] 朱勇强等．广东造纸．1997．No．5～6：60；No．5～6：86
[30] 朱勇强等．华南理工大学学报．1994．13 (6)：40
[31] Get. Pat.2 031 293
[32] 叶晓春等．林产化学与工业．1996．24 (12)：79
[33] 日本特许公开-250 297 (1987)
[34] 日本特许公开-36 629 (1990)
[35] JP 120 197
[36] US 4 199 369
[37] US 4 437 894
[38] JP163 811
[39] 汪曾祁．造纸化学品．1997．3：2
[40] 徐仲恺等．纸和造纸．1997．增刊：32
[41] US 4 743 303
[42] US 4 404 034
[43] US 4 203 776
[44] US 3 044 890
[45] GP Appl.3 856 858
[46] JP 147 211
[47] BP 859 789
[48] 张本智．天津造纸，1987．1：38
[49] EP 74 544
[50] 陈均志等．西北轻工业学院学报．1996，3：23
[51] 姚光裕．国际造纸，1994．13 (6)：38
[52] 林民等．天津造纸．1994．4：19
[55] 林民等．中国造纸．1996．3：15
[54] 李丰年．中国造纸．1990．5：63
[55] 周大斌等．中国造纸．1988．5：28
[2] Smith K E. Pulp Pap.Jan. 1983:P142
[3] Davison R W. Marton T. Tappi. 1964.47(10):609
[4] 徐忠恺、李春芳．上海造纸．1992．23(1)：14
[5] 徐忠恺、李春芳．国外造纸．1992．11 (2)：15
[6] Casey J P. Pulp and Paper. Chemistry and Chemical Techmology.3rd Ed. Vol.3.Wiley-Interscience.New York.1981
[7] 约翰逊 R W，弗里兹 E 编．工业脂肪酸及其尖用．陆用海、胡征宇译．中国轻工业出版社．1991：611～642
[8] Strazdins E.Tappi. 1965.48:157
[9] 牛华．纸和造纸．1997．增刊：37
[10] Strazdins E.Tappi. 1977.60:102
[11] Strazdins E.Tappi. 1981.64:31
[12] Strazdins E.Tappi.1984.67:110
[13] 中华．造纸化学品．1997．2：19
[14] 邓亚君．造纸化学品．1997．2：25
[15] 特开昭 55-129450
[16] 特开昭 5-33291
[17] Marton E.Tappi. 1980.63: 121
[18] Arnson T R.Tappi. 1982.65:125
[19] Arnson T R and Stration R A.Tappi. 1983.66:72
[20] Porter R B.in Internal Sizing of Paperand Paperboard.Tappi Monograph 33.T W Swanson.ed.Tappi Press. New York.1971:146
[21] Liu J.Paper Technology. 1993.34 (8): 20
[22] Anson T. Notes of 1987 TAPPI Sizing Short Course: 31
[23] Strazding E.Tappi. 1963.46 (7): 432
[24] 朱勇强等．中国造纸．1997．5：39
[25] 郑博文等．中国造纸．1989．8 (5)：22
[26] 朱勇强等．中国造纸．1993．12 (3)：42
[27] 朱勇强等．中国造纸．1994．13 (6)：30
[28] 朱勇强等．中国造纸．1997．5：39
[29] 朱勇强等．广东造纸．1997．No．5～6：60；No．5～6：86
[30] 朱勇强等．华南理工大学学报．1994．13 (6)：40
[31] Get. Pat.2 031 293
[32] 叶晓春等．林产化学与工业．1996．24 (12)：79
[33] 日本特许公开-250 297 (1987)
[34] 日本特许公开-36 629 (1990)
[35] JP 120 197
[36] US 4 199 369
[37] US 4 437 894
[38] JP163 811
[39] 汪曾祁．造纸化学品．1997．3：2
[40] 徐仲恺等．纸和造纸．1997．增刊：32
[41] US 4 743 303
[42] US 4 404 034
[43] US 4 203 776
[44] US 3 044 890
[45] GP Appl.3 856 858
[46] JP 147 211
[47] BP 859 789
[48] 张本智．天津造纸，1987．1：38
[49] EP 74 544
[50] 陈均志等．西北轻工业学院学报．1996，3：23
[51] 姚光裕．国际造纸，1994．13 (6)：38
[52] 林民等．天津造纸．1994．4：19
[55] 林民等．中国造纸．1996．3：15
[54] 李丰年．中国造纸．1990．5：63
[55] 周大斌等．中国造纸．1988．5：28