CN103159885A - Styrene-butadiene latex for coating paper and its preparing method - Google Patents
Styrene-butadiene latex for coating paper and its preparing method Download PDFInfo
- Publication number
- CN103159885A CN103159885A CN2012105286595A CN201210528659A CN103159885A CN 103159885 A CN103159885 A CN 103159885A CN 2012105286595 A CN2012105286595 A CN 2012105286595A CN 201210528659 A CN201210528659 A CN 201210528659A CN 103159885 A CN103159885 A CN 103159885A
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- Prior art keywords
- weight
- latex
- styrene
- monomer
- paper coating
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- 239000004816 latex Substances 0.000 title claims abstract description 108
- 229920000126 latex Polymers 0.000 title claims abstract description 108
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 34
- 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 34
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 34
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims description 40
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000008360 acrylonitriles Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 3
- 230000001112 coagulating effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 7
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- -1 thiol compound Chemical class 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- PCPYTNCQOSFKGG-UHFFFAOYSA-N 1-chlorobuta-1,3-diene Chemical compound ClC=CC=C PCPYTNCQOSFKGG-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/06—Copolymers with styrene
- C09D109/08—Latex
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to styrene-butadiene latex for coating paper and its preparing method, and more specifically, relates to the following styrene-butadiene latex and its preparing method, comprising: continuously adding alkalis to a polymerization process, which improves dispersion stability of seed latex and enhances polymerization stability of a seed polymerization method, thereby reducing latex micro- coagulating articles, so the styrene-butadiene latex has advantages of excellent cohesive force, excellent mechanical stability and excellent flowability under high shear, and is very available as a paper coating material.
Description
Technical field
The present invention relates to the manufacture method for the styrene-butadiene latex of Paper Coating, in more detail, relate to styrene-butadiene latex as described below and manufacture method thereof: bases is put into polymerization process continuously, improve the dispersion stabilization of seed latex and improve the polymerization stability of seeding polymerization method, thereby reduce the little knot thing of latex, therefore bonding force and mechanical stability are outstanding, and be outstanding in the high-shear current downflow, very useful with material as Paper Coating.
Background technology
Paper Coating liquid is made of pigment, tackiness agent, additive.Pigment mainly makes up clay, calcium carbonate etc. and uses, and uses dispersion agent, water-holding agent, lubricant, insolubilizer etc. as additive.And, mainly use starch and latex as tackiness agent.Wherein, latex is that colloidal particle is dispersed in water and forms, and has by drying process to form the mechanism that film embodies bonding force.
About general Paper Coating method, have in advance to regulate by roller etc. and coating fluid is transferred to roller coating machine (roll coater) mode of body paper after the thickness of coated film and wipe knife coater (blade coater) mode that is adjusted to certain coated film thickness off after the excessive coating fluid of coating on body paper.After with the infrared rays of high temperature or hot air dryer, the paper that is coated with by mode as above being carried out drying, implement press polish (calendering) and to giving gloss on paper.
Nearest coating technique, reduce and productivity rises to purpose with effectiveness (utility), the trend of the high speed of the high density of coating fluid and surface covered is arranged, thus, flow at high speed characteristic and mechanical stability under the mobility of the coating fluid when importantly being coated with, particularly high-shear.
In addition, in order to reduce the White Board manufacturing cost, the trend that reduces the latex usage quantity is arranged, and in order to improve the bonding force of latex, the latex particle size is made littlely trend.But size of particles is less, produces more little knot things of latex in manufacturing processed.The little knot thing that produces in polymerization system easily is attached to inside reactor, is difficult to regulate polymerization temperature, and the variation of the size of particles of each production batch is serious, when mixing in hold-up vessel, and the result of bringing particle distribution to broaden.
In the time of on being applied to paper, this little knot thing can produce striped or roller pollution, can cause that in White Board bonding force descends.Moreover, the ununiformity of size of particles and wide particle diameter distribution of latex bring the result of the pore that reduces paper coating inside, cause ink setting speed slack-off, or the printing ink water-absorbent reduce.That is, for the latex small particle size as the unit that is used for raising flow at high speed and bonding force, it is highly important that and guarantee latex polymerization stability.
Generally when making, latex produces little knot thing in order to suppress, although as method utilize when the polymerization or polymerization after increase emulsifier, but might produce the latex of a lot of forms, can produce operational problem or reduce the White Board water tolerance, therefore can not say sufficient solution countermeasure.As another method, improve acid monomer content and can improve stability when latex is made.But viscosity of latex rose and had problems on the workability such as transmission, storage due to a large amount of carboxyl that exists on latex particle surface or water layer this moment.
in addition, as Paper Coating latex, the manufacture method that discloses styrene-butadiene latex in 2002-50007 is disclosed in Korean Patent, it comprises for the vinylbenzene of 100 weight parts and the monomer composition of divinyl, the weight with 1:0.1 to 1:10 of adding 0.1 to 10 weight part recently contain the simple function thiol compound and have two above sulfydryls multi-functional thiol compound chain-transfer agent and carry out the step of emulsion polymerization, in disclosing No. 2005-4949, Korean Patent also discloses the technology of using chain-transfer agent as described below: after outside coating 2～4 floor shell polymeric of core latex, add separately chain-transfer agent, thereby regulate the outermost gel content of latex and molecular weight.
But, this Paper Coating styrene-butadiene latex in the past, bonding force improves and the improvement of mechanical properties although emphasis lays particular emphasis on, and polymerization stability is also bad, can not effectively control the generation of little knot thing.
in addition, in disclosing No. 1997-61924, Korean Patent discloses the compound styrene-butadiene latex of particle of macroparticle and the compound formation of small-particle, it is characterized in that, the above-mentioned seed latex of input of the macroparticle of 130～250nm size of being made by the seed latex sensitization that makes 30～40nm size of 65～90 % by weight and 10～35 % by weight and the small-particle of 40～100nm size of making consist of, although improve the physical property such as workability in the high-shear field and mechanical stability, but can not solve the problem that White Board physical property and printing ink water-absorbent reduce owing to differing from one another interparticle heterogeneous sense.
In addition, disclose the Paper Coating styrene-butadiene latex in Korean Patent discloses No. 2003-41575, it is characterized in that, latex contains: the 1,3-butadiene of 5～55 % by weight; The vinylbenzene of 40～94 % by weight; The ethylenic unsaturated acid monomer of 1～15 % by weight; The acrylonitrile base monomer of 0～10 % by weight; Other of 0～30 % by weight can carry out the vinyl monomer of copolymerization; And the sodium methallyl sulfonate of 0.01～10 % by weight (sodium methallyl sulfonate), it contains the molecular weight regulator of 0.2～10 % by weight, it is the ion monomer that can carry out copolymerization with the monomer of formation composition latex, particularly disclose the use sodium methallyl sulfonate and improve aggregation phenomenon or a lot of physical property, but in this case, still can't resolve latex polymerization improved stability effect little, water-fast strength decreased gets greatly, the problem that speed of response postpones.
Summary of the invention
In order to improve above-mentioned problem in the past, in forming with latex, suppresses Paper Coating the generation of little knot thing, make the outstanding latex of physical property, and through the long-time result of studying, in order to make styrene-butadiene latex when using bases in polymerization process, can improve the dispersion stabilization of seed latex and improve greatly the polymerization stability of seeding polymerization method, thereby suppressing greatly the generation of little knot thing, having completed the present invention based on these.
Therefore, the object of the invention is to, provide latex particle knot thing few, the Paper Coating styrene-butadiene latex that the mobility under mechanical stability and high-shear is outstanding.
In addition, other purposes of the present invention are, are provided at the outstanding Paper Coating styrene-butadiene latex of bonding force in the White Board typography, ink setting and printing ink water-absorbent.
In addition, another purpose of the present invention is, the dispersion stabilization that improves seed latex is provided and improves greatly the Paper Coating of polymerization stability with the manufacture method of styrene-butadiene latex.
in order to solve the above problems, the invention provides the Paper Coating styrene-butadiene latex, it is by 1 of 10～60 % by weight, the 3-divinyl, the vinylbenzene of 10～70 % by weight, the vinyl cyanide class monomer of 1～10 % by weight, the polymerization single polymerization monomer of 100 weight parts that the vinyl unsaturated alkyl ester of the vinyl unsaturated acid monomer of 1～10 % by weight and 1～20 % by weight consists of, with the styrene monomer by 60～99 % by weight, the divinyl of 0～39 % by weight, the seed latex of 0.5～10 weight part that the vinyl unsaturated acid monomer emulsion polymerization of 1～10 % by weight forms, under the existence of the bases of the reaction initiator of 0.1～10 weight part and 0.01～10 weight part, form by emulsion polymerization.
In addition, the present invention provides the manufacture method of Paper Coating with styrene-butadiene latex in the process of the styrene-butadiene latex of making above-mentioned composition, it is characterized in that, when carrying out emulsion polymerization, drops into continuously reaction initiator and bases.
Styrene-butadiene latex of the present invention is to use bases in polymerization process, thereby improve the dispersion stabilization of seed latex and improve greatly the polymerization stability of seeding polymerization method, latex particle knot thing is few, mobility under mechanical stability and high-shear is outstanding, therefore as Paper Coating with and very suitable.
In addition, latex of the present invention has bonding force, ink setting and the outstanding effect of printing ink water-absorbent in the White Board typography.
Embodiment
Below, further describe the present invention by embodiment.
Styrene-butadiene latex of the present invention comprises: seed latex, butadiene type monomer, styrene monomer, vinyl cyanide class monomer, the unsaturated class monomer of vinyl and unsaturated carboxylic acid alkyl ester comprise reaction initiator and bases together with these monomers.
Acting as of above-mentioned butadiene type monomer given bonding force to latex, can use general aliphatics conjugated diene.Specifically, can use 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, chlorbutadiene etc. use with 10～60 % by weight in whole polymerization single polymerization monomer.Bonding force reduces if exist its usage quantity to cross at least, if cross the problem that causes when Paper Coating due to cementability that at most back flow roll pollutes.
Acting as of above-mentioned styrene monomer given hardness to latex, can use general styrene monomer.Specifically, can use vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene, 4-chloro-styrene etc., use with 10～70 % by weight in whole polymerization single polymerization monomer.If exist its usage quantity to cross lower hardness at least, if problem excessive that bonding force reduces.
Acting as of above-mentioned vinyl cyanide class monomer given chemical resistant properties to latex, can use general vinyl cyanide class monomer.Specifically, can use vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc., use with 1～10 % by weight in whole polymerization single polymerization monomer.Print gloss reduces if exist its content to cross at least, if cross the problem of printing ink set-off (ink set off) reduction at most.
The unsaturated acids monomer of above-mentioned vinyl act as stability and the bonding force of giving latex, can use general unsaturated carboxylic acid or have the unsaturated carboxylic acid alkyl ester of more than one carboxyl.Specifically, about the vinyl unsaturated acid monomer, can be with the vinyl unsaturated carboxylic acid of 1～10 % by weight use as methylene-succinic acid, vinylformic acid, methacrylic acid, fumaric acid, toxilic acid etc., if exist its usage quantity to cross at least the problem that stability and bonding force reduce, and if cross viscosity of latex raising at most and deposit in the use problem.And, as vinyl unsaturated alkyl ester, can be with the unsaturated carboxylic acid alkyl ester of 1～20 % by weight use as methyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate etc., if stability reduces to exist its usage quantity to cross at least, print gloss reduces if cross at most, the problem that the latex manufacturing cost rises.
As the reaction initiator that uses in latex of the present invention is made, can use the water soluble starter such as the persulphates such as ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide or with the redox class initiator of the reductive agent combinations such as they and S-WAT, amine, use 0.1～10 weight part take whole polymerization single polymerization monomer 100 weight parts as benchmark.If exist its usage quantity to cross the too low problem of polymerization velocity at least, if cross the too fast and problem that exists reaction heat to control of speed of response at most.
In the present invention, the bases as being mixed together with reaction initiator can use one or more that select from potassium hydroxide, sodium hydroxide and ammonium hydroxide, uses 0.01～10 weight part take whole polymerization single polymerization monomer 100 weight parts as benchmark.If it is general to exist its usage quantity to cross the dispersion stabilization effect of seed latex at least, if cross the problem of viscosity of latex rising when latex is made at most.
On the other hand, use seed latex in order to make above-mentioned latex in the present invention, and the seed latex about using, for example use the styrene monomer of 60～100 % by weight, the divinyl of 0～40 % by weight, the vinylformic acid of 0～10 % by weight, make and use by general emulsion polymerization method.This seed latex is to use 0.5～10 weight part take whole polymerization single polymerization monomer 100 weight parts as benchmark.Latex particle size is too small at most if its usage quantity is crossed, thereby exists viscosity and print sexual incompatibility to be used for the problem of Paper Coating.
the most typical method of making latex of the present invention is as follows: to the styrene monomer by 60～99 % by weight of 0.5～10 weight part, the divinyl of 0～40 % by weight, the seed latex that the vinyl unsaturated acid monomer emulsion polymerization of 1～10 % by weight forms, ratio with 100 weight parts is added 1 of 10～60 % by weight, the 3-divinyl, the vinylbenzene of 10～70 % by weight, the vinyl cyanide class monomer of 1～10 % by weight, the polymerization single polymerization monomer of the vinyl unsaturated alkyl ester of the vinyl unsaturated acid monomer of 1～10 % by weight and 1～20 % by weight, the reaction initiator of continuous input 0.1～10 weight part and the bases of 0.01～10 weight part also carry out emulsion polymerization.
In addition, in order to make latex of the present invention, can additionally use general emulsifying agent, chain-transfer agent, ionogen, dispersion agent etc.
As mentioned above, the present invention uses in the latex manufacturing processed did not have used bases in the past, had improved the dispersion stabilization of seed latex and had improved greatly polymerization stability.
Its result, show characteristic as described below: the particle knot thing that has suppressed latex, when being applied to Paper Coating, mechanical stability and the mobility under high-shear of coating fluid are outstanding, and bonding force, ink setting and printing ink water-absorbent are outstanding in the White Board typography.
Latex constructed in accordance, its polymerisation conversion shows more than 99%, and median size is 80～170nm, and gel content is 70～95%.This means, show preferred physical property on the bonding force of the required physical property that is used for Paper Coating and printing physical property side.
According to the present invention, can make well above-mentioned styrene-butadiene latex is used Paper Coating liquid as tackiness agent.
In addition, use this Paper Coating liquid and the paper made shows very outstanding characteristic.
On the other hand, above-mentioned styrene-butadiene latex of the present invention is except using as Paper Coating with latex, in the latex manufacture method that can use with, foam backing in carpet use, non-woven fabrics use, pouncing paper use, building water-proof agent, concrete modifying agent, water-soluble binder, gloves impregnation etc., use as the manufacture method that improves polymerization stability.
Below, describe the present invention in detail according to embodiment, but the present invention is not limited to embodiment.
[embodiment 1]
After the reaction under high pressure gas displacement with 5L was nitrogen, the seed latex of the vinylformic acid of the ion exchanged water of input 30 weight parts, the methylene-succinic acid of 1.0 weight parts, 1.0 weight parts and the independent manufacturing of 2 weight parts was warmed up to 75 ℃ with temperature.The tert-dodecyl mercaptan of the chain-transfer agent of the methyl methacrylate of the divinyl of continuous 6 hours afterwards, input 40.0 weight parts, the vinylbenzene of 44.8 weight parts, 9 weight parts, the vinyl cyanide of 2 weight parts, 1.4 weight parts.Meanwhile, drop into continuously the solution that the dialkyl group phenylbenzene oxidation sodium disulfonate of the vinylformic acid of methylene-succinic acid, 1.5 weight parts of ion exchanged water with 28 weight parts, 2.0 weight parts and 0.5 weight part mixes.In addition, the solution of sodium hydroxide that drops into continuously Potassium Persulphate, 0.1 weight part of ion exchanged water, 1.1 weight parts of 23 weight parts with same time has been implemented polymerization.
After all the components input is completed, stir outside supplements under the state of holding temperature and completed polymerization in 2 hours.The polymerisation conversion of the latex that so obtains is 99%, and median size is 120nm, and gel content is 80%.
[embodiment 2～4]
Except using as the sodium hydroxide that drops into of the amount table 1, made styrene-butadiene latex by the method identical with above-described embodiment 1 together with the Potassium Persulphate that uses as initiator.Shown in its table 1 composed as follows.
[embodiment 5]
As Korean Patent disclose No. 2003-41575 disclosed, import as having made latex with the sodium methallyl sulfonate (sodium methallyl sulfonate) of the ion monomer of polymerization single polymerization monomer copolymerization.As shown in the following Table 1, except the sodium methallyl sulfonate that drops into 5 weight parts, made styrene-butadiene latex with the method identical with embodiment 1.
[comparative example 1]
As shown in the following Table 1, except not dropping into sodium hydroxide, made styrene-butadiene latex with the method identical with above-described embodiment 1.
[comparative example 2]
As shown in the following Table 1, do not drop into sodium hydroxide, drop into the sodium methallyl sulfonate of 5 weight parts, and made styrene-butadiene latex with the method identical with above-described embodiment 1.
[table 1]
| Content (weight part) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Divinyl | 40 | 40 | 40 | 40 | ? | 40 | ? |
| Vinylbenzene | 43.5 | 43.5 | 43.5 | 43.5 | 38.5 | 43.5 | 38.5 |
| Methyl methacrylate | 9 | 9 | 9 | 9 | 9 | 9 | 9 |
| Vinyl cyanide | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Methylene-succinic acid | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Vinylformic acid | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| Methylpropene sodium sulfonate | - | - | - | - | 5 | - | 5 |
| Emulsifying agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Chain-transfer agent | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 | 1.4 |
| Potassium Persulphate | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| Sodium hydroxide | 0.3 | 0.5 | 1.0 | 1.5 | 0.3 | 0 | 0 |
| Ion exchanged water | 81 | 81 | 81 | 81 | 81 | 81 | 31 |
In above-mentioned table 1, weight part is all as 100 weight part benchmark with polymerization single polymerization monomer, use dodecylated diphenyl ether disulfonate as emulsifying agent, use tert-dodecyl mercaptan as chain-transfer agent, use redistilled water by the RiOs device fabrication of Millipore company as ion exchanged water.
[experimental example 1]
As the metering of the polymerization stability of estimating latex, latex coagulum (coagulum) after polymerization is sieved with 300 orders, and measured its solids component with ppm unit.And, in order to estimate the only mechanical stability of latex self, use Ma Langshi trier (Marontester) and complete the stirring of 10 minutes with the power of 98N after, the coagulum that produces is sieved with 300 orders, and measure with ppm unit, its result is illustrated in table 2.
[table 2]
As confirmation in above-mentioned table 2, in the situation that embodiment 1-5,1-2 compares with comparative example, confirms the latex coagulum and significantly reduces, and the later coagulative generation of certain condition also significantly reduces, thereby it is very outstanding to confirm mechanical stability.In the situation that embodiment, due to the outstanding property of this physical property, the generation of roller pollution or striped significantly reduces when being applied to Paper Coating, improves greatly the coating workability, and the bonding force of White Board and printing ink water-absorbent become outstanding.
[experimental example 2]
Use physical property for the coating of measuring the latex of making in above-described embodiment and comparative example, made coating fluid with method as described below.For the latex of making in above-described embodiment and comparative example, after mixing with the ratio of the thickening material of the insolubilizer of the dispersion agent of the styrene-butadiene latex of the water-ground limestone of the clay of 20 weight parts, 80 weight parts, 11 weight parts, 0.5 weight part, 0.5 weight part, 0.1 weight part, add ion exchanged water and make solids component account for 69% to have made coating fluid.
Utilize the MLC coating machine with the coating fluid of manufacturing with 18g/m
2Weight coated to paper.Made the paper warm air drying that is coated with 30 seconds under 120 ℃.Afterwards, implemented twice press polish with under 60 ℃, the condition of 73KN in supercalender.
The physical property of the White Board by manufacturing has been measured bonding force, water-fast intensity, printing ink set-off, ink trapping.Evaluation method the results are shown in following table 3 as shown below.
About bonding force, utilize the RI printing press, after repeatedly White Board being printed, with the naked eye estimated it take five point-scores as benchmark and torn degree.At this moment, the higher expression bonding force of mark is more outstanding.
About water-fast intensity, add moisture retention water with the Moulton roller in the RI printing press, with the method identical with above-mentioned bonding force, with the naked eye estimated it take five point-scores as benchmark and torn degree.The water-fast intensity of the higher expression of mark is more outstanding.
About the printing ink set-off, utilizing after the RI printing press prints White Board, with the naked eye estimated the degree of gluing printing ink along with the time take five point-scores as benchmark.At this moment, the higher expression ink setting of mark speed is faster.
About ink trapping, utilize the RI printing press at first to White Board process yellow printing ink after, at the printing green ink, with the naked eye estimated the printing degree of green ink take five point-scores as benchmark how.
[table 3]
Follow above-mentioned table 2, can be confirmed by above-mentioned table 3, in the situation that drop into continuously the embodiment 1～5 that the bases of appropriate amount comes polymerization, compare with the comparative example 1～2 of method manufacturing by in the past, not only the mechanical stability of latex polymerization stability and the coating fluid that is made of latex and additive is outstanding, and in being applied to Paper Coating the time, the mechanical stability of coating fluid, bonding force, water-fast intensity, printing ink set-off, ink trapping show outstanding result.
Claims (7)
1. a Paper Coating styrene-butadiene latex, is characterized in that,
this Paper Coating styrene-butadiene latex is made in the following way: under the existence of the bases of the reaction initiator of 0.1～10 weight part and 0.01～10 weight part, to by 1 of 10～60 % by weight, the 3-divinyl, the vinylbenzene of 10～70 % by weight, the vinyl cyanide class monomer of 1～10 % by weight, the polymerization single polymerization monomer of 100 weight parts that the vinyl unsaturated alkyl ester of the vinyl unsaturated acid monomer of 1～10 % by weight and 1～20 % by weight consists of and by the styrene monomer of 60～99 % by weight, the divinyl of 0～39 % by weight, the seed latex of 0.5～10 weight part that the vinyl unsaturated acid monomer emulsion polymerization of 1～10 % by weight forms is carried out emulsion polymerization.
2. Paper Coating styrene-butadiene latex according to claim 1, is characterized in that,
Bases is one or more that select from the group that is made of potassium hydroxide, sodium hydroxide and ammonium hydroxide.
3. Paper Coating styrene-butadiene latex according to claim 1, is characterized in that,
This Paper Coating is 80nm～170nm with the median size of styrene-butadiene latex, and gel content is 70%～95%.
4. the manufacture method of a Paper Coating use styrene-butadiene latex, is characterized in that,
styrene monomer to 60～100 % by weight, the seed latex of 0.5～10 weight part that the vinylformic acid of the divinyl of 0～40 % by weight and 0～10 % by weight forms by emulsion polymerization, ratio with 100 weight parts adds 1 of 10～60 % by weight, the 3-divinyl, the vinylbenzene of 10～70 % by weight, the vinyl cyanide class monomer of 1～10 % by weight, the polymerization single polymerization monomer of the vinyl unsaturated alkyl ester of the vinyl unsaturated acid monomer of 1～10 % by weight and 1～20 % by weight, the reaction initiator of continuous input 0.1～10 weight part and the bases of 0.01～10 weight part also carry out emulsion polymerization.
5. Paper Coating according to claim 4 with the manufacture method of styrene-butadiene latex, is characterized in that,
Bases is one or more that select from the group that is made of potassium hydroxide, sodium hydroxide and ammonium hydroxide.
6. a Paper Coating liquid, is characterized in that, this Paper Coating liquid comprises any one latex of selecting in Accessory Right requirement 1 to 3, as tackiness agent.
7. a paper, is characterized in that, is coated with Paper Coating liquid claimed in claim 6 on this paper.
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| CN107936166A (en) * | 2017-12-12 | 2018-04-20 | 杭州龙驹合成材料有限公司 | Styrene-butadiene latex and preparation method thereof |
| CN113279286A (en) * | 2021-04-06 | 2021-08-20 | 金东纸业（江苏）股份有限公司 | Coated paper and preparation method thereof |
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| KR101726266B1 (en) | 2014-06-13 | 2017-04-12 | 주식회사 엘지화학 | Manufacture apparatus of polybutadiene latex particles and Manufacturing of polybutadiene latex particles by continuous process using the same |
| CN113929804B (en) * | 2021-10-21 | 2024-12-06 | 海南必凯水性新材料有限公司 | Styrene-butadiene rubber latex for cellophane, preparation method thereof and cellophane coating |
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| KR100212973B1 (en) | 1996-12-26 | 1999-08-02 | 차동천 | The process for manufacturing styrene butadiene latex with good paper coating properties |
| KR101817356B1 (en) * | 2010-02-26 | 2018-01-10 | 니폰 에이 엔 엘 가부시키가이샤 | Copolymer latex, method for manufacturing the same, and paper coating composition |
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| US6660814B1 (en) * | 1996-10-02 | 2003-12-09 | Basf Aktiengesellschaft | Preparation of emulsion homo- and copolymers and device therefore |
| CN1537143A (en) * | 2001-08-02 | 2004-10-13 | Poiymer compositions having improved property constancy | |
| CN101191003A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | High transparence MBS resin composition with excellent impact property |
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| CN113279286A (en) * | 2021-04-06 | 2021-08-20 | 金东纸业（江苏）股份有限公司 | Coated paper and preparation method thereof |
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