CN100396718C - 制备苯乙烯-丁二烯乳胶的方法 - Google Patents
制备苯乙烯-丁二烯乳胶的方法 Download PDFInfo
- Publication number
- CN100396718C CN100396718C CNB2004800129337A CN200480012933A CN100396718C CN 100396718 C CN100396718 C CN 100396718C CN B2004800129337 A CNB2004800129337 A CN B2004800129337A CN 200480012933 A CN200480012933 A CN 200480012933A CN 100396718 C CN100396718 C CN 100396718C
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- China
- Prior art keywords
- preparation
- styrene
- monomer
- butadiene
- acid
- 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.)
- Expired - Lifetime
Links
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 50
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 50
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 229920000126 latex Polymers 0.000 claims abstract description 47
- 239000004816 latex Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims description 71
- 238000002360 preparation method Methods 0.000 claims description 61
- 239000012986 chain transfer agent Substances 0.000 claims description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 18
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 18
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- 230000007704 transition Effects 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 10
- -1 Ba Dousuan Chemical compound 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 claims 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 27
- 230000001070 adhesive effect Effects 0.000 abstract description 27
- 238000001035 drying Methods 0.000 abstract description 17
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 7
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- 238000009423 ventilation Methods 0.000 description 7
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- 239000004927 clay Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BRPNNYXZQLLLSN-UHFFFAOYSA-N sodium;dodecane Chemical compound [Na+].CCCCCCCCCCC[CH2-] BRPNNYXZQLLLSN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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- 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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- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- D21H19/36—Coatings with pigments
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Abstract
本发明涉及一种制备苯乙烯-丁二烯乳胶的方法。根据本发明的苯乙烯-丁二烯乳胶的特征在于，由于通过调节最外层的凝胶含量和分子量而促进早期薄膜的形成从而具有极佳的粘附力，以及由于保持纸张薄膜的形成因而具有快的墨干燥速度和高的透气性。因为乳胶的机械稳定性和化学稳定性极佳，因而其可以被非常稳定地用于纸张涂层。
Description
技术领域
本发明涉及一种制备苯乙烯-丁二烯乳胶的方法。更具体地，本发明涉及一种制备苯乙烯-丁二烯乳胶的方法，其特点在于通过调节苯乙烯-丁二烯乳胶最外层的凝胶含量和分子量而促进在涂覆过程中初始膜的形成，因而使乳胶的粘附力极佳，并且通过维持适当的膜的形成而具有快的墨干燥速度和高透气性。由于乳胶的机械和化学稳定性极佳，因此，其可以被非常稳定地用于纸张涂层。
背景技术
通常，通过在纸张上涂覆例如粘土、碳酸钙、氢氧化铝(Al(OH)3)、氧化钛(TiO2)等的无机颜料制备纸张的涂覆层，其中由于上述无机颜料不具有粘附力，而使用如酪朊、淀粉等的天然粘合剂或如苯乙烯-丁二烯乳胶、聚乙烯醇、丙烯酸乳胶等的人工粘合剂。近来，因为相对于天然粘合剂其具有更易于调节物理性质并且更便于使用的优点，所以人工合成粘合剂被主要地使用。其中，典型使用的是不昂贵但具有极佳性能的苯乙烯-丁二烯乳胶。当制备涂层溶液时，如分散剂、增稠剂、不溶剂(insolublizer)等各种添加剂与无机颜料和粘合剂一起使用。最重要的化学物质仍然是无机颜料和粘合剂，并且应该选择无机颜料和粘合剂以获得涂料纸的均衡物理性质。
最常用的无机颜料是粘土和碳酸钙。粘土为薄片状结构，并且优点在于可以得到高纸张光泽度和打印光泽度，但缺点是低流动性、并需要大量的粘合剂。然而，若为碳酸钙，其优点在于流动性、粘附力、墨吸收性、纸张亮度、不透明性等，但问题是其需要涂层溶液对钙离子具有更强的化学稳定性。
近来，随着纸张的生产速度逐渐加快，已存在这样一种趋势，即通过提高涂覆速度以应对印刷品的生产和供应的增长。近来涂覆速度已经被提高，以加快达约1,000～1,500m/min。如此快速的涂覆速度在涂覆中会引起更大的剪切力，因而，乳胶的机械稳定性变得更重要。还需要乳胶具有高化学稳定性，因为在降低最初成本的同时碳酸钙的使用量随碳酸钙的性能的增加而增加。
如上所述，乳胶的稳定性可被分为化学、机械和热稳定性。且这三种稳定性应该被确保，以保证高度的稳定性。
随着近来在制造涂料纸中降低粘合剂含量以提高纸张质量并降低成本的强烈趋势，更热切地需要改善粘合剂的粘附力。随上述情况，由于快的印刷速度，就极大地需要改善墨水干燥速度。若仅提高这两项物理性质，就可以获得符合近来涂料纸的制造和印刷工艺的涂料纸。
当将被注入涂层溶液中的粘合剂经干燥处理且形成薄膜时，表现出涂料纸的粘附力。形成薄膜越好，粘附力变得越强。然而，尽管粘附力提高，但随涂覆层中空气泡的量减少，墨干燥速度被降低。这意味着粘附力和墨水干燥速度与物理性质略微成反比例，因此，非常难以通过单独调节乳胶的玻璃化转变温度等改善这两者。
为了同时改善苯乙烯-丁二烯乳胶的粘附力、墨干燥速度、透性和稳定性，本发明的发明人进行研究的结果发现上述目的可以通过控制多层核-壳结构中最外层壳的凝胶含量和分子量达到。换句话说，本发明的发明人发现可以通过应用控制凝胶含量和分子量的常规方法同时改善用于纸张涂覆的乳胶的粘附力、墨水干燥速度、透性和稳定性，该常规方法通过在聚合处理中与制备壳层的单体一起加入链转移剂以用壳层包裹核，并通过在加入这些单体后以适当的转化率、在确定的时间内单独引入确定量的链转移剂而调节多壳层的最外层的凝胶含量和分子量。本发明是基于上述发现完成。
发明内容
因此，本发明的一个目的是在苯乙烯-丁二烯乳胶的制备中同时提高其粘附力以及墨干燥速度和稳定性。
本发明提供了一种制备苯乙烯-丁二烯乳胶的方法，包括苯乙烯-丁二烯聚合物的核乳胶的制备步骤；涂覆多层壳层聚合物到上述核乳胶的外表面的步骤；以及通过在上述壳制备步骤后单独加入链转移剂以调节乳胶最外层凝胶含量和分子量的步骤。
通过乳液聚合包括苯乙烯、1，3-丁二烯、烯基不饱和酸单体、氰乙烯基单体、可与上述物质共聚合的单体以及链转移剂的核组合物而制备上述核乳胶。上述核组合物由35～90重量份的苯乙烯、10～55重量份的1，3-丁二烯、1～18重量份的烯基不饱和酸单体、0.5～15重量份的氰乙烯基单体、1～25重量份的可共聚合的单体以及0.1～1.0重量份的链转移剂构成。
通过乳液聚合包括苯乙烯、1，3-丁二烯、烯基不饱和酸单体、氰乙烯基单体、可与上述物质共聚合的单体以及链转移剂的壳组合物而制备上述壳乳胶。特别是，上述壳组合物包括30～80重量份的苯乙烯、10～70重量份的1，3-丁二烯、0.5～18重量份的烯基不饱和酸单体、1.0～20重量份的氰乙烯基单体、1.0～20重量份的可共聚合的单体以及0.1～5.0重量份的链转移剂。
上述链转移剂可以为具有7～16个碳原子的硫醇，其用量可以为0.05～5.0重量份。
上述烯基不饱和酸单体可以为选自包括甲基丙烯酸、丙烯酸、衣康酸、巴豆酸、反丁烯二酸、和顺丁烯二酸的组的一种或多种不饱和羧酸；或者选自包括衣康酸单乙基酯、反丁烯二酸单丁基酯、和顺丁烯二酸单丁基酯的组的具有一个或多个羧基的一种或多种不饱和羧酸烷基酯。
上述氰乙烯基单体可以为丙烯腈或甲基丙烯腈。
可以共聚合的上述单体可以为选自包括可以为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、或甲基丙烯酸丁酯的不饱和羧酸烷基酯；可以为丙烯酸β-羟乙酯、丙烯酸β-羟丙酯、或甲基丙烯酸β-羟乙酯的不饱和羧酸羟烷基酯；可以为丙烯酰胺、甲基丙烯酰胺、衣康酸酰胺或顺丁烯二酸单酸酰、或其衍生物的不饱和羧酸酰胺；以及可以为α-甲基苯乙烯、乙烯基甲苯、或p-甲基苯乙烯的芳香族乙烯基单体的组的一种或多种化合物。
本发明还提供了苯乙烯-丁二烯乳胶的制备方法，其特点是上述最终苯乙烯-丁二烯乳胶的凝胶含量为30～90％。上述核乳胶的玻璃化转变温度为-10～50℃，并且上述壳聚合物的玻璃化转变温度为-20～40℃。上述核乳胶的平均颗粒直径为40～90nm，并且以上制备的最终苯乙烯-丁二烯乳胶的平均颗粒直径为130～260nm。
进一步，本发明中提供了根据上述制备苯乙烯-丁二烯乳胶的方法制备的苯乙烯-丁二烯乳胶。
再进一步，本发明中还提供了包含在制备苯乙烯-丁二烯乳胶的上述方法中制备的苯乙烯-丁二烯乳胶的纸张涂层溶液组合物。
本发明还提供了涂覆了涂层溶液组合物的纸张，其中涂层溶液组合物包括根据上述制备苯乙烯-丁二烯乳胶的方法制备的苯乙烯-丁二烯乳胶，以及本发明还提供了一种具有苯乙烯-丁二烯聚合物作为苯乙烯-丁二烯乳胶中的壳聚合物而被多层地涂覆在上述苯乙烯-丁二烯聚合物的核乳胶的外层上的结构的苯乙烯-丁二烯乳胶。
具体实施方式
本发明的苯乙烯-丁二烯乳胶包括多核-壳聚合步骤。更具体地，本发明包括制备核的第一步骤和形成核-壳的第二步骤，在第二步骤中具有不同组成的多层壳被涂覆在核上，其中各个步骤通过乳液聚合完成。可以有一层或多层壳，优选为2～4层壳，并且考虑到玻璃化转变温度、凝胶含量、分子量等，设计每层壳应具有适当的核-壳结构。第三个步骤是在多壳层聚合完成后、当转化率达到60～95％时，在确定时间内单独加入定量的链转移剂的步骤。该步骤调节乳胶颗粒最外层的凝胶含量和分子量是一个必需步骤。优选地，基于100重量份加入的总单体重量，链转移剂的加入量为0.05～5.0重量份。
相对于最终的乳胶，通过上述第一步骤制备的核的特点在于具有适当的亲水性和适当的凝胶含量。在第二步聚合中，其特点在于具有适当的玻璃化转变温度以及若被用于薄片胶印时的高凝胶含量或者若被用于卷筒纸胶印时的低凝胶含量。
根据本发明的苯乙烯-丁二烯乳胶的制备方法如下更详细地描述：
第一步骤是用于核初始聚合的步骤，其中的核包括35～90重量份的苯乙烯、10～55重量份的1，3-丁二烯、1～18重量份的烯基不饱和酸单体、0.5～15重量份的氰乙烯基单体、1～25重量份的可共聚合的单体以及0.1～1.0重量份的链转移剂。
上述苯乙烯为赋予共聚物适当硬度和防水性的物质。如果单体中含有少于35重量份的苯乙烯，则不能得到足够硬度和防水性；并且如果苯乙烯的量超过90重量份，则其粘附力和形成薄膜的能力均被降低。
上述1，3-丁二烯赋予共聚物可塑性。如果1，3-丁二烯的量小于10重量份，则共聚物可能变得太硬；并且如果1，3-丁二烯的量超过55重量份，则硬度可能会降低。
适当地使用上述烯基不饱和酸单体以提高共聚物的粘附力和乳胶颗粒的稳定性。其组分比例优选为1～18重量份。如果烯基不饱和酸单体的量小于1重量份，则不能得到上述效果；并且如果烯基不饱和酸单体的量超过18重量份，则可能发生聚合稳定性的问题等。并且优选该烯基不饱和酸单体为具有一个或多个羧基的不饱和羧酸或不饱和羧酸烷基酯。
上述不饱和羧酸优选为选自甲基丙烯酸、丙烯酸、衣康酸、巴豆酸、反丁烯二酸、和顺丁烯二酸的组的一种或多种酸。并且上述不饱和羧酸烷基酯为选自衣康酸单乙基酯、反丁烯二酸单丁基酯、和顺丁烯二酸单丁基酯的组的一种或多种酯。
上述氰乙烯基单体是为了提高印刷光泽度。其含量优选为3～10重量份。因为氰乙烯基单体与烯基不饱和酸单体具有高亲水性，因此优选根据聚合的各个步骤将氰乙烯基单体的亲水性调节到需要的范围内。上述氰乙烯基单体进一步优选为丙烯腈或甲基丙烯腈。
其次，可以共聚合的上述单体优选为选自包括例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯等的不饱和羧酸烷基酯；例如丙烯酸β-羟乙酯、丙烯酸β-羟丙酯、甲基丙烯酸β-羟乙酯等的不饱和羧酸羟烷基酯；例如丙烯酰胺、甲基丙烯酰胺、衣康酸酰胺、顺丁烯二酸单酸酰等的不饱和羧酸酰胺及其衍生物；以及例如α-甲基苯乙烯、乙烯基甲苯、p-甲基苯乙烯等的芳香族乙烯基单体的组的一种或多种化合物。上述不饱和羧酸烷基酯使共聚物具有适当的硬度，并且改善膜形成能力。因为如果其含量超过25重量份则可能导致对其防水性的反作用，因而其含量优选为3～15重量份。另外，上述不饱和羧酸酰胺及其衍生物对提高共聚物乳胶的化学稳定性、机械稳定性、和防水性有作用。其含量更优选为1～10重份。
用于本发明的链转移剂优选地选自具有7～16个碳原子的硫醇的组，更优选地选自正十二烷基硫醇和叔十二烷基硫醇。
本发明的核通过加入例如一般的聚合引发剂、乳化剂、电解质等的添加剂到上述核组合物中的普通乳液聚合反应而制备。本发明的乳胶核的凝胶含量优选为80重量％或更小，特别是40～70重量％。如果核的凝胶含量超过80重量％，在第二步骤和进一步在制备核的步骤之后的聚合中可能变得难以控制其结构、并且难以形成多层核-壳结构。
制备本发明的乳胶的步骤中的第二步骤是将壳包裹在上述第一步骤中制备的核乳胶上的步骤。壳组合物包括30～80重量份的苯乙烯、10～70重量份的1，3-丁二烯、0.5～18重量份的烯基不饱和酸单体、以及0.1～5.0重量份的链转移剂。还可以进一步包括1.0～20重量份的氰乙烯基单体和1.0～20重量份的可与其它单体聚合的另外的单体。
在本发明的第二步骤中制备的多层壳的凝胶含量优选为30～90重量％，更优选地，若被用于薄片胶印时为60～85重量％，或者若被用于卷筒纸胶印时为40～60重量％。若被用于薄片胶印时，如果在第二步骤中制备的壳的凝胶含量小于60重量％，则粘附力、墨干燥速度和乳胶稳定性可能会降低；并且如果其大于85重量％，则可能难以保证粘附力。若用于卷筒纸胶印时，如果在第二步骤中制备的壳的凝胶含量小于20重量％，则粘附力和乳胶稳定性可能会降低；并且如果其超过70重量％，则抗起泡特性降低。
在本发明的乳胶制备步骤的第二步骤中的核-多层壳的制备是通过当在先前步骤中单体到聚合物的转化率为55～95％时，加入新单体混合物而聚合完成的。如果在先前步骤中向聚合物的转化率小于55％，则因为在先前步骤中的单体和在下面步骤中壳的单体被混合、并不能明确地分离，而难以获得有效的多核-壳结构。可以在上述第二步骤中使用的各种单体可以与在第一步骤中制备核的步骤中使用的原料相同。
制备本发明的乳胶的第一步骤包括加入用于最终壳聚合的单体并完成多壳聚合步骤后，在确定时间内单独加入确定量的链转移剂的步骤。该步骤对于调节最终乳胶的凝胶含量和分子量是非常重要的步骤。在完成加入用于最终壳聚合的单体后，适当的转化率为60～95％。如果转化率低于60％或高于95％，则难以表现出通过加入的链转移剂控制最外层凝胶含量和分子量的效果。优选地，，加入的时间段为在完成加入用于最终壳聚合的单体后的立即的2小时，更优选为在加入完成后的立即的1小时。优选地，上述链转移剂的加入量为0.05～5.0重量份，更优选为0.1～1.0重量份。
在本发明的乳胶的制备中，重要的是具有在多层壳聚合的第二步骤中适当的各个壳层的厚度和玻璃化转变温度。各个壳层的厚度可以通过调节核和单体的含量而被控制。如果其没有被适当地控制，则不能得到具有预期结构的乳胶。可以通过在各个步骤中适当地控制玻璃化转变温度、凝胶含量和分子量而控制例如粘附力、墨干燥速度、乳胶稳定性等的物理性质。
对于在本发明的乳胶的制备中适当的厚度，优选地，在第一步骤中的核聚合后的平均颗粒直径为40～90nm，并且最终壳聚合后的平均颗粒直径为110～260nm。
另外，在本发明的乳胶的制备中，优选地，第一步骤种子的适当的玻璃化转变温度为-10～50℃，并且多层壳的玻璃化转变温度为-20～40℃。对于温度超出上述给出的范围的情况，如果玻璃化转变温度为-20℃或更低，则不能具有理想的如光泽度等的物理性质，并且如果玻璃化转变温度超过40℃，则不能具有理想的如粘附力等的物理性质。只有在所给出的温度范围内才能得到这些物理性质。
本发明的苯乙烯-丁二烯乳胶可以与有机或无机颜料、增稠剂或其它添加剂混合以制备水性涂层溶液，只要将该水性涂层溶液涂覆在纸张上，其可以用于涂料纸的制备。上述无机颜料可以包括普通颜料和填充剂，例如氧化钛、碳酸钙、粘土等。基于100重量份的水性涂层溶液的固体，乳胶含量优选为5～20重量份。
上述和其它目的、技术方案、和优点可以从下面对本发明的优选实施例详细的描述被更好的理解，但应该清楚地理解本发明并不限于此：
[实施例1～9]
在以下面三个步骤中制备本发明的苯乙烯-丁二烯乳胶：
步骤1：核的制备步骤
在安装有搅拌器、温度计、冷却器和氮气进口并装有单体、乳化剂和连续加入的聚合引发剂的10L加压反应器用氮气取代，之后，加入33重量份的丁二烯、49重量份的苯乙烯、8重量份的甲基丙烯酸甲酯、5重量份的丙烯腈、5重量份的衣康酸、6重量份的十二烷基二苯磺酸钠、0.3重量份的叔十二烷基硫醇、0.4重量份的碳酸氢钠、和420重量份的离子，并加热到60℃。向该混合物中加入0.8重量份的聚合引发剂过硫酸钾并混合约300分钟以完成种子的聚合。
用激光散射分析仪(Nicomp)测量上述核的结果表明平均颗粒直径为68nm，凝胶含量为53％，且转化率为97％。
步骤2：多层壳的制备步骤
为了用壳包裹在上述步骤1中得到的核，再向反应器中加入8重量份的核乳胶和30重量份的离子交换水并加热到80℃。此后，加入具有适当组成的壳组合物以进行乳液聚合，其中的壳组合物包括50重量份的苯乙烯、30重量份的1，3-丁二烯、10重量份的烯基不饱和酸单体、3重量份的链转移剂、11重量份的氰乙烯基单体和100重量份的可与其它单体聚合的另外单体。在优选实施例1和2中，壳的数量为2；且在优选实施例3～9中，壳数量为3。此时加入的壳组合物的单体总量为100，且所有组分被加入后的转化率为70～90％。
表1
步骤3：最外层的凝胶含量和分子量的调节步骤
为了通过向步骤2中得到的乳胶中单独地加入链转移剂以调节最外层的凝胶含量和分子量，装有步骤2中的组分的反应器的温度要保持在80℃，并且连续地加入以上表1的步骤3中的组分并聚合30分钟。
在优选实施例6～9中，在步骤2中制备第二壳层后，单独地加入以上表1中的组分，并且制备第三壳层。此后，进行步骤3。
在所有上述组分被加入后，通过将温度提高至90℃以加速反应的同时再混合100分钟而完成聚合。完全聚合的乳胶的转化率为98～100％，且平均颗粒直径经测量为180nm。
[对比实施例1]
以与优选实施例1和2中步骤1和2的相同方法制备具有2层壳的核-壳乳胶。并且当在步骤2中制备壳层时调节链转移剂的量，而不是没有步骤3，以控制最终的凝胶含量与优选实施例中的最终凝胶含量几乎相同。
[对比实施例2]
以与优选实施例3～5中步骤1和2的相同方法制备具有3层壳的核-壳乳胶。如对比实施例1中，当在步骤2中制备壳层时，调节链转移剂的量以控制最终的凝胶含量与优选实施例中的最终凝胶含量几乎相同。
[对比实施例3～6]
以与优选实施例6～9中步骤1和2的相同方法制备具有3层壳的核-壳乳胶。如优选实施例6～9中，在制备第二壳层后，在30分钟内加入如下表2所示的链转移剂后，制备第三壳层。同时，当在步骤2中制备壳层时调节链转移剂的量以控制最终的凝胶含量与优选实施例中的最终凝胶含量几乎相同。
表2
[测试实施例1]
为了测量乳胶的机械稳定性，通过使用Maron检测器单独测量乳胶。并且为了同时测量其化学和机械稳定性，制备了其中混合乳胶和人工颜料的涂层颜料(参考下面测试实施例2)，并用Maron检测器测量。对于稳定性的测量结果，Maron测试完成后，用325目过滤器过滤乳胶和涂层颜料，并且以ppm为单位测量聚集体。
表3
通过进行乳胶的Maron测试，可以测量乳胶自身的机械稳定性。如果由外部强力破坏乳胶的稳定性，则乳胶被固化并表现为聚集体。因而，聚集体的含量越小，其机械稳定性更佳。并且如上表3中可以看出，相对于对比实施例，优选实施例具有更佳的机械稳定性。同时，在用Maron测试仪测量涂层颜料中，根据钙离子在涂层颜料中的作用不仅机械稳定性而且化学稳定性也起作用，并因此，优选实施例具有比对比实施例更佳的稳定性。
[测试实施例2]
为了对比和评估优选实施例和对比实施例中的乳胶，制备包括30重量份的粘土(初级的)和70重量份的碳酸钙的固体、12重量份的乳胶、0.8重量份的增稠剂和1.2重量份的其它添加剂的具有64重量份的固体的纸张涂层溶液。通过用15g/m2的纸张涂层溶液按照被动双面棒涂覆(棒涂覆，第7号)而涂覆纸张的两面以制备涂料纸，然后在105℃干燥30秒，并在80℃、40kg/cm下通过强度砑光机两次(通过速度为4m/min)。
对于上面制备的涂料纸的物理性质，测量其粘附力、墨干燥速度和透性。测量方法如下所示，且结果列于表4中：
通过用RI印刷机印刷涂料纸几次、并用裸眼测定撕裂程度，以5点法测量粘附力。高分数表示良好的粘附力，并且通过使用技术值(tech-value)12、14、和16的墨测量粘附力以得到平均值。
对于墨干燥速度，在用RI印刷机印刷涂料纸后根据5点法测量按时间的墨的拖尾效应的程度。高分数表示更快的墨干燥速度。
通过用OKEN孔隙率计测量涂料纸的多个部分以得到透气性的平均值，其中，该数值表示单位体积的气体通过涂料纸的时间。越小的数值表示空气更快的透过，其进一步表明涂覆层的透气性极佳。该单位以秒表示。
表4
如上表4中所示，涂层溶液和涂料纸的物理性质测量结果和印刷的结果表明相对于没有在制备双层壳后加入链转移剂的对比实施例1的乳胶的性质，优选实施例1和2中双核-壳结构的乳胶具有更优的粘附力以及墨干燥速度和透气性；同样，相比于对比实施例2中三核-壳结构的乳胶的性质，在通过在制备壳层后单独加入链转移剂以调节最外层的凝胶含量和分子量的优选实施例3～5中的三核-壳结构的乳胶具有更佳的粘附力以及非常良好的墨干燥速度和透气性。
进一步，其表明，在壳的制备中，通过在包裹三层壳的制备中在包裹第二壳层后单独地加入链转移剂以调节凝胶含量和分子量的对比实施例3～6中，相比于对比实施例2，墨干燥速度和透气性仅略微提高，但并未得到极佳的物理性质。并且如优选实施例6～9的情况，其中通过在制备最后和第三层壳后单独加入链转移剂以调节最外层的凝胶含量和分子量，从而得到极佳的粘附力以及墨干燥速度和透气性。
工业实用性
根据本发明的苯乙烯-丁二烯乳胶的特征在于由于通过调节最外层的凝胶含量和分子量而促进早期薄膜的形成因此具有极佳的粘附力，以及由于保持纸张薄膜的形成而具有快的墨干燥速度和高的透气性。因为乳胶的机械稳定性和化学稳定性极佳，因而其可以被非常稳定地用于纸张涂层。
尽管本发明的某些优选实施例已被展示和说明，但可以清楚地理解本发明并不限制于此，另外在随后的权利要求的范围内的多种体现和实践都是可以的。
Claims (16)
1.一种苯乙烯-丁二烯乳胶的制备方法，包括步骤：
苯乙烯-丁二烯聚合物的核乳胶的制备；
在所述核乳胶的外面多重涂覆壳聚合物；和
在制备所述壳聚合物的所述步骤后通过单独地加入链转移剂以调节乳胶的最外层的凝胶含量和分子量，
其中核乳胶的凝胶含量为80重量％或更小并且在制备壳聚合物的步骤中转化率在60～95％之间。
2.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于通过乳液聚合包括苯乙烯、1，3-丁二烯、烯基不饱和酸单体、氰乙烯基单体、可与所述单体共聚合的单体、和链转移剂的核组合物而制备所述核乳胶。
3.根据权利要求2的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述核组合物包括35～90重量份的苯乙烯、10～55重量份的1，3-丁二烯、1～18重量份的烯基不饱和酸单体、0.5～15重量份的氰乙烯基单体、1～25重量份的可与所述单体共聚合的单体、以及0.1～1.0重量份的链转移剂。
4.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于通过乳液聚合包括苯乙烯、1，3-丁二烯、烯基不饱和酸单体、氰乙烯基单体、可与所述单体共聚合的单体、以及链转移剂的壳组合物而制备所述壳聚合物。
5.根据权利要求4的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述壳组合物包括30～80重量份的苯乙烯、10～70重量份的1，3-丁二烯、0.5～18重量份的烯基不饱和酸单体、1.0～20重量份的氰乙烯基单体、1.0～20重量份的可与所述单体共聚合的单体、以及0.1～5.0重量份的链转移剂。
6.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述链转移剂为具有7～16个碳原子的硫醇。
7.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述链转移剂的用量为0.05～5.0重量份。
8.根据权利要求2或4的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述烯基不饱和酸单体为：
选自由甲基丙烯酸、丙烯酸、衣康酸、巴豆酸、反丁烯二酸、和顺丁烯二酸组成的组的一种或多种不饱和羧酸；或
一种或多种选自由衣康酸单乙基酯、反丁烯二酸单丁基酯、和顺丁烯二酸单丁基酯组成的组的具有一个或多个羧基的不饱和羧酸烷基酯。
9.根据权利要求2或4的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述氰乙烯基单体为丙烯腈或甲基丙烯腈。
10.根据权利要求2或4的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述可共聚合单体为选自以下组的一种或多种化合物：
选自由丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸丁酯组成的组的不饱和羧酸烷基酯；
选自由丙烯酸β-羟乙酯、丙烯酸β-羟丙酯和甲基丙烯酸β-羟乙酯组成的组的不饱和羧酸羟烷基酯；
选自由丙烯酰胺、甲基丙烯酰胺、甲叉丁二酰胺和顺丁烯二酸单酰胺组成的组的不饱和羧酸酰胺；和
选自由α-甲基苯乙烯、乙烯基甲苯和p-甲基苯乙烯组成的组的芳香族乙烯基单体。
11.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述最终制备的苯乙烯-丁二烯乳胶的凝胶含量为30～90％。
12.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述核乳胶的玻璃化转变温度为-10～50℃，并且所述壳聚合物的玻璃化转变温度为-20～40℃。
13.根据权利要求1的苯乙烯-丁二烯乳胶的制备方法，其特征在于所述核乳胶的平均颗粒直径为40～90nm，并且所述最终制备的苯乙烯-丁二烯乳胶的平均颗粒直径为130～260nm。
14.一种根据权利要求1至13任意一项的制备方法制备的苯乙烯-丁二烯乳胶。
15.一种包含根据权利要求1至13任意一项的制备方法制备的苯乙烯-丁二烯乳胶的纸张涂层溶液。
16.一种用包含根据权利要求1至13任意一项的制备方法制备的苯乙烯-丁二烯乳胶的纸张涂层溶液涂覆的涂料纸。
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| KR20100083064A (ko) | 2009-01-12 | 2010-07-21 | (주) 아이티비엠지 | 디지털 케이블 방송환경에서 양방향 서비스를 제공하기 위한 시스템 |
| CN102020749B (zh) * | 2009-09-15 | 2013-09-04 | Lg化学株式会社 | 具有优异的耐白化性的多层橡胶共聚物及其制备方法 |
| US20150361208A1 (en) * | 2013-02-06 | 2015-12-17 | Basf Se | Hybrid latex comprising polymeric particles having core-shell structure and its preparation method |
| KR101442412B1 (ko) * | 2013-05-03 | 2014-09-17 | 주식회사 엘지화학 | 고무 강화 그라프트 공중합체용 고무질 중합체 및 그 제조방법 |
| KR101666273B1 (ko) * | 2014-06-13 | 2016-10-24 | 주식회사 엘지화학 | 스티렌-부타디엔계 라텍스 및 그 제조방법 |
| WO2016048997A1 (en) * | 2014-09-23 | 2016-03-31 | Bridgestone Bandag, Llc | Carbon black pellets bound by styrene-butadiene latex polymer |
| CN105820284B (zh) * | 2016-04-28 | 2018-01-30 | 浙江天晨胶业股份有限公司 | 一种草坪用聚合胶乳的制备方法 |
| CN108841334A (zh) * | 2018-07-12 | 2018-11-20 | 江苏金大包装材料科技有限公司 | 一种导热不干胶及其制备方法 |
| KR102155685B1 (ko) * | 2018-12-20 | 2020-09-14 | 금호석유화학 주식회사 | 시드 중합 조성물, 공액 디엔계 공중합체, 성형체 및 이의 제조방법 |
| CN110483676B (zh) * | 2019-07-18 | 2022-04-15 | 广东腾龙化工科技有限公司 | 一种多相结构的丁二烯-苯乙烯共聚物胶乳及其制备方法和应用 |
| CN110483673B (zh) * | 2019-07-18 | 2022-04-15 | 广东腾龙化工科技有限公司 | 一种纸张涂布用多相结构的丁苯胶乳及其制备方法和应用 |
| CN115044331B (zh) * | 2021-03-09 | 2023-05-09 | 南京工业大学 | 一种锂离子电池用水分散型聚合物微粒子乳液粘结剂及其制备方法 |
| CN113831439A (zh) * | 2021-11-02 | 2021-12-24 | 上海昶法新材料有限公司 | 一种造纸用羧基丁腈胶乳及其制备方法 |
| CN118562207A (zh) * | 2024-08-01 | 2024-08-30 | 潍坊蓝励新材料有限公司 | 一种增粘环保型丁苯胶乳及其制备方法 |
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- 2003-06-27 KR KR10-2003-0042582A patent/KR100512366B1/ko active IP Right Grant
-
2004
- 2004-02-12 US US10/553,586 patent/US9040118B2/en active Active
- 2004-02-12 CA CA 2530691 patent/CA2530691C/en not_active Expired - Lifetime
- 2004-02-12 EP EP20040821822 patent/EP1639031B1/en not_active Expired - Lifetime
- 2004-02-12 JP JP2006508517A patent/JP2006526681A/ja active Pending
- 2004-02-12 WO PCT/KR2004/000279 patent/WO2005105898A1/en active Search and Examination
- 2004-02-12 CN CNB2004800129337A patent/CN100396718C/zh not_active Expired - Lifetime
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|---|---|---|---|---|
| US4331738A (en) * | 1980-12-04 | 1982-05-25 | The General Tire & Rubber Company | Blend of a carboxylated copolymer latex and of an acrylate copolymer latex for coating rubber and product |
| US5703157A (en) * | 1992-01-10 | 1997-12-30 | Sumitomo Dow Limited | Process of preparing copolymer latex and use thereof |
| US5770303A (en) * | 1994-07-06 | 1998-06-23 | Gencorp Inc. | Occluded composite-particle latex |
| CN1401033A (zh) * | 2000-12-18 | 2003-03-05 | Lg化学株式会社 | 人造颜料及其制备方法 |
| CN1404489A (zh) * | 2000-12-20 | 2003-03-19 | Lg化学株式会 | 一种用于铜版纸的乳胶的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US9040118B2 (en) | 2015-05-26 |
| EP1639031A4 (en) | 2006-07-12 |
| EP1639031B1 (en) | 2012-05-23 |
| KR100512366B1 (ko) | 2005-09-02 |
| JP2006526681A (ja) | 2006-11-24 |
| CA2530691A1 (en) | 2005-11-10 |
| EP1639031A1 (en) | 2006-03-29 |
| WO2005105898A1 (en) | 2005-11-10 |
| CA2530691C (en) | 2010-08-03 |
| KR20050004949A (ko) | 2005-01-13 |
| CN1788039A (zh) | 2006-06-14 |
| US20060263602A1 (en) | 2006-11-23 |
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