CN1103645A - Water-thinned high molecular emulsoid with high performance - Google Patents
Water-thinned high molecular emulsoid with high performance Download PDFInfo
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- CN1103645A CN1103645A CN 93120071 CN93120071A CN1103645A CN 1103645 A CN1103645 A CN 1103645A CN 93120071 CN93120071 CN 93120071 CN 93120071 A CN93120071 A CN 93120071A CN 1103645 A CN1103645 A CN 1103645A
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Abstract
The said emulsoid is constituted with the mixture of alkyl-thioalcohol and 2-phenyl propylene dimer as chain transfering agent. Its monomer components used in synthesis are: monovinyl unsym-aromatics in 15-85 wt%, aliphatic conjugate diolefines in 20-70 wt%, unsaturated vinyl carboxylic acids or unsaturated vinyl sulphonic acids in 0.5-15 wt%, unsaturated vinyl amide 0-10 wt%, unsaturated vinyl alkyl-esters in 0-30 wt% and vinyl nitriles in 0-20 wt%.
Description
The present invention relates to a kind of blank sheet of paper (cardboard) in surface-coated add use man-hour have bonding effect with emulsion polymerization way synthetic water-thinned high molecular emulsoid with high performance.Blank sheet of paper (cardboard) adds used white pigment coating in man-hour in surface-coated, when wherein containing latex of the present invention as tackiness agent, this coating is except that having general good coating flowability, and Shang Youneng is satisfied with Ke Shi multicolour press desired printing adaptability when high speed printing.
High molecular emulsion is widely used in fine arts enamelled paper or white board and applies the tackiness agent that adds man-hour carrying out paper surface, also is applied to the tackiness agent of aspects such as carpet back-adhesive, non-textile fiber material and special paperboard processing.
High molecular emulsion is because there is high-intensity bounding force, the desired high temperature resistance whipability of good water-repellancy and drying process, and other various performances, thereby applicable to different application scenarios.And water-thinned high molecular emulsoid with high performance of the present invention mainly is applied to the tackiness agent in the employed coating of the coating course of processing of fine arts enamelled paper and white board.
As everyone knows, monomer weight in the high molecular emulsion is formed the interior bridge formation density of high molecular emulsion when, it is the gel content (Gel content) of so-called toluene, it is defined as being insoluble in the high molecular emulsion composition of toluene, the two is to the optical property and the anti-stripping property of paper desired printing in the polychrome printing process of coated paper (cardboard), and promptly doing anti-shedding phenomenon, high temperature resistance whipability, printing ink affinitys such as anti-stripping property, wet anti-stripping property has great influence.In general, the factor that influences the gel content of toluene in the latex is a lot, as monomer weight ratio of components, coincidence temperature of reaction and reaction conditions or the like, this gel content influences coated paper doing in high speed polychrome printing process and resists stripping property, the wet balancing effect that resists conflicting printing adaptability between stripping property, high temperature resistance whipability and the printing ink affinity etc.
The method of the adjusting gel content of most convenient is to utilize chain-transfer agent to make it be adjusted to optimal scope, the chain-transfer agent that generally uses is Organohalogen compounds such as chloroform, tetracol phenixin, carbon tetrabromide, utilize this type of halogenide can reach good printing adaptability as chain-transfer agent, but its shortcoming is, and is disabled because these type of Organohalogen compounds easily cause global environmental issue.
The object of the present invention is to provide a kind of water-thinned high molecular emulsoid with high performance, latex proposed by the invention is in building-up process, employed chain-transfer agent is the mixture of alkyl sulfhydryl and 2-phenyl propylene dimer, the mixing that the two is suitable and with the bridge formation density in the may command high molecular emulsion.When containing aqueous high molecular emulsion of the present invention in the coating, its coated paper (cardboard) can satisfy Ke Shi multicolour press required printing adaptability when high speed printing.
Water-thinned high molecular emulsoid with high performance of the present invention is to utilize well-known emulsion polymerization way synthetic, and its employed monomer has:
(a) the inclined to one side aromatics monomer of single ethene (monovinylidene aromatic monomers), for example: vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, neighbour, to dimethyl styrene, neighbour, right-diethylbenzene ethene, dichlorostyrene, Vinylstyrene, t-butyl styrene, monochloro vinylbenzene and Vinyl toluene etc.Consider factors such as these monomer sources, price, usability, more preferably use vinylbenzene and Vinyl toluene, especially preferably use vinylbenzene, its consumption is preferably and accounts for the percentile 15%-85% of whole monomer weights, especially is preferably 25%-75%(weight).If consumption surpasses 85%(weight) time, the latex rigidity is forced very much to such an extent that the bond strength of latex dies down, if consumption is lower than 15%(weight) time, then the rigidity of latex is not enough;
(b) aliphatics conjugated diene monomer (aliphatic conjugated diene monomers), these monomers contain 4-9 carbon atom, for example: 1, the 3-divinyl, the 2-methyl isophthalic acid, the 3-divinyl, 2,3-dimethyl-1, the 3-divinyl, pentadiene, 2-neo-pentyl-1,3-divinyl and other analogues, as: 2-chloro-1,3-butadiene and 2-cyano group-1,3-divinyl etc., more than various monomers its property is respectively arranged, but owing to consider factor such as these monomer sources, wherein, more preferably 1,3-divinyl, its consumption are preferably and account for the percentile 20%-70% of whole monomer weights, especially are preferably 30%-60%(weight).If consumption is lower than 20%(weight) time, the bounding force of latex is not enough, if consumption surpasses 70%(weight) time, then the water-resistant capacity of latex is poor, and bounding force is not good yet simultaneously;
(c) unsaturated ethylene carboxylic-acid monomer (ethylenically unsaturated carboxylic acid monomers), the organic acid that can overlap altogether with other monomers, for example: vinylformic acid, methacrylic acid, butylene-[1]-acid, 3-phenylallene-[2]-acid, suitable-butene dioic acid, methyne Succinic Acid, anti--butene dioic acid etc.; Perhaps unsaturated ethylene sulfonic acid class monomer (ethylencally unsaturated sulfonic acid monomers), for example: vinylformic acid-2-sulfonic group ethyl ester, methacrylic acid-2-sulfonic group propyl ester, 2-methyl isophthalic acid-propene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, styrene sulfonic acid, methacrylic sulfonic acid etc., the alkaline metal salt of above-mentioned acid or ammonium salt also can use.Whole consumptions of unsaturated ethylene olefinic carboxylic acid and unsaturated ethylene sulfonic acid account for the percentile 0.5%-15% of whole monomer weights.If consumption is lower than 0.5%(weight) time, the mechanical stability of latex is not good, and the mixed stability of pigment is also poor, if consumption surpasses 15%(weight) time, then the viscosity of latex is too high, and is not suitable for actually operating, and its optimal consumption is preferably 1%-12%(weight);
(d) unsaturated ethylene acrylamide monomer (ethylenically unsaturated amide monomers), for example: acrylamide, Methacrylamide, N-hydroxymethyl acrylamide and butoxymethyl acrylamide etc., its whole consumptions account for the percentile 0%-10% of whole monomer weights, add this monomeric purpose and be for the mechanical stability that improves latex and the mixed stability of pigment, its more preferably usage quantity be 0.25%-8%(weight);
(e) unsaturated ethylene alkyl esters monomer (ethylenically unsaturated alkylester monomers), these monomeric usage quantitys account for the percentile 0%-30% of whole monomer weights, especially be preferably 0%-20%(weight), can use the propylene carboxylic hydroxy alkyl ester that contains 2 to 4 carbon atoms, vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxypropyl acrylate, methacrylic acid-4-hydroxy butyl ester, and alkyl acrylic (methacrylic acid) alkyl ester that contains 1 to 18 carbon, for example: methyl acrylate, ethyl propenoate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, isopropyl methacrylate, phenyl methacrylate, methacrylic acid chloroethene ester, the methacrylic cyclohexyl, the acrylic acid epoxy propyl ester, glytidyl methacrylate etc.;
(f) ethene nitrile monomer (ethyleni nitrile monomers), for example: vinyl cyanide, methacrylonitrile, propylene dichloride nitrile etc., these monomeric consumptions account for the percentile 0%-20% of whole monomer weights, especially are preferably 0%-15%(weight).
The adjusting of molecular weight in the aqueous high molecular emulsion of the present invention and latex intramolecularly interlinkage degree, be to adopt alkyl sulfhydryl and 2-phenyl propylene dimer and be used as chain-transfer agent, wherein alkyl sulfhydryl contains 5 to 14 carbon atoms, especially be preferably the alkyl sulfhydryl that contains 12 carbon atoms, for example: lauryl mercaptan, just-dodecyl-1-mercaptan, 4-normal-butyl-n-octylcyclam-mercaptan, dodecyl-6-mercaptan, two-2-normal-butyl propyl group thiomethyl alcohol, the 2-methyl-just-nonyl-thiomethyl alcohol, 1,1-dimethyl-n-decane base-1-mercaptan and uncle-dodecyl-1-mercaptan, its consumption accounts for the percentile 0.1%-5% of whole monomer weights, especially is preferably 0.2%-3.5%(weight).2-phenyl propylene dimer can be 2,4-phenylbenzene-4-methyl-1-pentene, 2, and 4-phenylbenzene-4-methyl-2-amylene, these monomeric consumptions account for the percentile 0.05%-5% of whole monomer weights, especially are preferably 0.1%-4%(weight).The gel content of aqueous high molecular emulsion of the present invention is controlled in the scope of 35%-90%, and poor if gel content is lower than 35% dried peel strength, the printing ink affinity is poor, and is poor if gel content surpasses 90% wet peel strength.
High-performance water-based latex of the present invention adopts emulsion polymerization, monomer under agitation is emulsified in aqueous phase uniformly, wherein and contain the free radical and the emulsifying agent of reaction initiator, the kind of reaction initiator is not restricted, and commonly used have an organo-peroxide, as: tertbutyl peroxide, propyloxy phenyl base hydrogen peroxide, or azo-compound, as: 2,2 '-Diisopropyl azodicarboxylate, or inorganic oversulfated thing, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate all can.The also available oxidation-reduction mode of above-mentioned reaction initiator, with reductive agent, as: S-WAT, ferrous sulfate etc. are also used.The consumption of initiator accounts for the percentile 0.05%-3% of whole monomer weights, especially is preferably 0.1%-2%(weight).
Emulsifying agent can be according to desired scope of the particle diameter of latex particle and the suitable emulsification degree that can reach, on consumption and kind and be allowed a choice, usually letex polymerization can be selected anionic, non-ionic type, amphoteric and cationic emulsifier for use, generally uses also using of one or more emulsifying agents at least.The average particle size range of latex is at the 0.08-0.5 micron.
Typical anionic emulsifier is derivative, the fatty acid soaps of alkylsulfonate, alkylbenzene sulfonate, sulfonic group succsinic acid alkyl diester, the poly-ethanol alkyl of sulfonation or alkyl aryl ether etc.Commonly used have Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sulfonic group succsinic acid-just-octadecyl ester disodium, a sulfonic group-dodecylphenyl ether disodium etc.
Typical non-ionic interfacial agent is polyethylene glycol alkyl ether, polyalkylene glycol alkyl phenolic ether, lipid acid sorb ester, polyethylene glycol fatty acid sorb ester etc.
Typical both sexes interfacial agent is: N-trialkyl glycine derivative, amino acid derivative.Derivative, N-lauryl-two (amino-ethyl) glycine, octadecyl-two (amino-ethyl) glycine that lauryl glycine, octadecyl glycine etc. are arranged commonly used.
Typical cationic interfacial agent is the derivative of fatty acid alkyl ammonium salt and quaternary ammonium salt, and commonly used have dodecyl-QAE muriate, an octadecyl-QAE muriate.
Preferred solvent is a Sodium dodecylbenzene sulfonate, and the consumption of emulsifying agent accounts for the 0.05%-4% of whole monomer weight ratios, especially is preferably 0.1%-3%(weight).If consumption is lower than 0.05%(weight) time, the poor stability during polyreaction then, and since the particle of latex can cause applying (cardboard) printing very little the time anti-stripping property relatively poor.If consumption surpasses 4%(weight) time, the poor water resistance of macromolecule latex glued membrane then, and have bubble problem in coating preparation or circulation time.
Can when letex polymerization, add and use alkali, sequestrant, chain-transfer agent, solvent and ionogen etc. according to specific purpose in addition.
Carry out the monomer of emulsion polymerization, can be in the presence of emulsifying agent and initiator, be heated owing to heating and induce reaction, begin to form latex particle, temperature of reaction can be chosen in 50 ℃-100 ℃, be preferably 55 ℃-95 ℃, the addition manner of monomer and raw material also has many kinds, can adopt: continous way additive process, monomer component additive process, full dose are mixed single additive process etc., polyreaction can be performed until productive rate and reach set objective according to selected temperature, add alkaline purification, deodorization processing then and be concentrated into needed scope.
Water-thinned high molecular emulsoid with high performance of the present invention is applicable to as paper and cardboard and applies with the tackiness agent in the coating that the general composition that applies with white pigment coating contains tackiness agent, white pigment and other chemical assistants.
Coating of the present invention is for when white pigment dry weight 100%, the relative dry weight of tackiness agent is 5%-30%, and the relative dry weight of chemical assistant is 0.1-5%, and tackiness agent can use single type latex or latex and help glue to use type with, generally speaking, latex is 40%-100% with the dry weight ratio that helps glue.
White pigment can be used kaolin, lime carbonate, aluminium hydroxide, titanium white, barium sulfate, Sha Dingbai, mica powder and pigment dyestuff, as: polystyrene, resol.
To help glue can be natural or the synthetic tackiness agent as lactic casein, soybean protein, starch, methylcellulose gum, sodiun alginate, SRB latex, MBR latex, polyvinyl alcohol, PVAc latex and acrylate copolymer latex.Auxiliary agent comprises dispersion agent, viscosity modifier, dyestuff, whitening agent, lubricant, interfacial agent, water-resisting agent, pH regulator agent, defoamer and sanitas etc.
Coating of the present invention is used for blank sheet of paper (cardboard) surface-coated and adds and use man-hour, and is applicable to various coating machines, as: scraper type coating machine, roll rumble formula coating machine, rod coater and air-blade type coating machine etc.
The comparative descriptions of embodiments of the invention and comparative example is as follows, but the present invention is not subjected to the restriction of following example.
Embodiment 1 (synthesizing of high-performance water-based latex)
With 100 parts of deionized waters, 0.15 part of Sodium dodecylbenzene sulfonate, 0.15 part of Potassium Persulphate is stretched 0.01 part of diethyl triamine five acetic acid sodium salt as sequestrant, instead-2 parts of butene dioic acids, add in the reactor and, be warming up to 60 ℃ then, after 3/4 hour, be fed in the still with nitrogen replacement, reinforced 6 parts of the vinylbenzene that include, 5 parts of methyl methacrylates, 0.3 part of 7 parts of divinyl and uncle's dodecyl-1-mercaptan and 2,0.08 part of 4-phenylbenzene-4-methyl-1-pentene is also used.This section charging reaction one hour, again add other monomer thereafter, these monomers comprise: 30 parts of vinylbenzene, 4.5 parts of vinyl cyanide, 15 parts of methyl methacrylates, 28 parts of divinyl, 1 part in vinylformic acid, 0.5 part of methacrylic acid, 1 part of acrylamide, 0.6 part of uncle's dodecyl-1-mercaptan and 2,0.6 part of 4-phenylbenzene-4-methyl-1-pentene is also used, in 3.5 hours, add continuously with constant speed, add continuously with 6 hours constant speed in addition simultaneously and contain 40 parts of deionized waters, 1 part of Sodium dodecylbenzene sulfonate, the water-based liquid that 0.15 part in sodium hydroxide and Potassium Persulphate are 0.8 part, total overall reaction finished after 16 hours, this moment, transformation efficiency reached 98%, after the cooling, and with sodium hydroxide adjusting pH value to 8, thereafter residual monomer is removed in deodorization, and to be concentrated into solids content be 48%, and the particle diameter of latex is about 0.18 micron.
Embodiment 2-18 reaches comparative example a-h shown in table-2 shown in table-1, its synthetic method and embodiment 1 described method are similar.
The polymeric membrane for preparing 0.3 mm thick with the synthetic latex, accurately take by weighing the film of 0.4g, be placed in the airtight bottle that includes 100 milliliters of toluene, vibration is 6 hours in 30 ℃ of homothermic water-baths, thereafter filter with 100 mesh filter screens, oven dry filtrate calculates the filtrate per-cent heavy with respect to film, this is the solvable composition of toluene, and gel content then is 100% to deduct the amount of the solvable composition of toluene.
Application examples
Embodiments of the invention 1 are to embodiment 18 and comparative example a-h institute synthetic latex, according to the proportioning of table-3, are modulated into 62% solids content and pH value about 9 coating, and its range of viscosities is at 1000-2500cps.
Its prescription is as follows:
Wherein:
(* 1) UW-90 is Engelhard mining industry and (the Engelhard Mineral ﹠amp of chemical company; Chemicals) product.
(* 2) Ultracote-90 is the product of Engelhard mining industry and chemical company.
(* 3) Omyalite-90 is the product of Pluess-Staufer AG.
(* 4) Aron T-40 is East Asia Synesis Company (Toa Gosei Co, product Ltd.).
(* 5) Surirez 636 is Sumitomo Chemical Co. Ltd.'s (Sumitomo Chemical Co, product Ltd.).
(* 6) Nylgum A-85 is the product of Avebe Veendam-Holland.
More than each coating all be used in basic weight 100mg/m
2Vellum, apply with soft knife coater, coated weight is 15 ± 0.5g/m
2, with 150 ℃, oven dry in 30 seconds places 23 ℃, following 24 hours of 50% humidity, and this coated paper is passed through secondary with the superpressure ray machine of 60 ℃ of temperature, line pressure 100kg/cm, and with following method test, test result is shown in table-4 and table-5 then.
Dried peel strength (dry pick)
(Akira Seisakusho) repeatedly prints paper with the RI trier, and uses the printing ink of high viscosity, takes place until having shelled phenomenon, shelled degree with the visual method evaluation then, is divided into 5 points, and the 5th is best, and the 1st for the poorest.
Wet peel strength (wet pick)
Use the RI trier, coated paper is wetting by wet rumble earlier, and with the printing ink of different viscosity, printing takes place up to having shelled phenomenon, has shelled degree with the visual method evaluation then, is divided into 5 points then, and the 5th is best, and the 1st for the poorest.
Printing ink affinity (ink affinity)
Use the RI trier, rumble is rotated in mixing even back of the printing ink of printing rumble and the water that adds 1cc, make ink emulsification, be printed in then on the coated paper, represent the more that by last China ink its printing ink affinity is better, judge that with visual 5 methods be the best at the 5th, the 1st for the poorest.
Glossiness (Gloss)
With 75 °/75 ° reflection angle tests of model ZRM 102 Reflectometer minute surfaces.Print gloss is then first with (quantity of ink is the 0.4g/ rumble) behind the RI press printing with pattern, again test in the same manner.
Example described in the present invention is not to be used for limiting claim scope of the present invention as describing the present invention with reference to use.
Claims (8)
1, a kind of with emulsion polymerization way synthetic water-thinned high molecular emulsoid with high performance, monomer weight ratio used when it is synthetic is composed as follows:
(a) the inclined to one side aromatics monomer of single ethene, this monomer accounts for the percentile 15%-85% of all wts;
(b) aliphatics conjugated diene monomer, this monomer account for the percentile 20%-70% of all wts;
(c) unsaturated ethylene carboxylic-acid monomer and unsaturated ethylene sulfonic acid class monomer, the two usage quantity accounts for the percentile 0.5%-15% of all wts;
(d) unsaturated ethylene acrylamide monomer, this monomer account for the percentile 0%-10% of all wts;
(e) unsaturated ethylene alkyl esters monomer, this monomer account for the percentile 0%-30% of all wts;
(f) ethene nitrile monomer, this monomer account for the percentile 0%-20% of all wts.
2, water-thinned high molecular emulsoid with high performance as claimed in claim 1, monomer wherein:
(a) be vinylbenzene, alpha-methyl styrene, Vinyl toluene, monochloro vinylbenzene;
(b) be 1,3-butadiene, halogenated butadienes;
(c) be vinylformic acid, methacrylic acid, butylene-[1]-acid, 3-phenylallene-[2]-acid, methyne Succinic Acid, anti--butene dioic acid, suitable-butene dioic acid, styrene sulfonic acid, 2-methyl isophthalic acid-propene sulfonic acid, 2-acrylamide-2-methyl-propene sulfonic acid;
(d) be acrylamide, Methacrylamide, N hydroxymethyl acrylamide;
(e) be methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl acrylate, vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-3-hydroxypropyl acrylate, vinylformic acid-4-hydroxy butyl ester, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxypropyl acrylate, acrylic acid epoxy propyl ester, glytidyl methacrylate;
(f) be vinyl cyanide, methacrylonitrile, propylene dichloride nitrile.
3, water-thinned high molecular emulsoid with high performance as claimed in claim 1, wherein, the average particle size range of this latex is at the 0.08-0.5 micron.
4, water-thinned high molecular emulsoid with high performance as claimed in claim 1, wherein, the used chain-transfer agent of this latex is to contain the alkyl sulfhydryl of 5-14 carbon atom and the mixture of 2-phenyl propylene dimer, its consumption is as follows:
(a) consumption of alkyl sulfhydryl accounts for the percentile 0.1%-5% of all wts;
(b) consumption of 2-phenyl propylene dimer accounts for the percentile 0.05%-5% of all wts.
5, water-thinned high molecular emulsoid with high performance as claimed in claim 4, wherein, chain-transfer agent:
(a) alkyl sulfhydryl is: just-dodecyl-1-mercaptan, 4-normal-butyl-n-octylcyclam-mercaptan, 1,1-dimethyl-n-decane base-1-mercaptan and uncle's dodecyl-1-mercaptan;
(b) 2-phenyl propylene dimer is: 2, and 4-phenylbenzene-4-methyl-1-pentene, 2,4-phenylbenzene-4-methyl-2-amylene.
6, water-thinned high molecular emulsoid with high performance as claimed in claim 1, wherein, the scope of the toluene gel content of this latex is at 35%-90%.
7, water-thinned high molecular emulsoid with high performance as claimed in claim 1, wherein, this latex can be used as tackiness agent, cooperates pigment and auxiliary agent in addition, is used as the white pigment water-borne coatings that the white board surface-coated adds man-hour, and therefore, this water-borne coatings contains:
(a) pigment and auxiliary agent;
(b) with the described water-thinned high molecular emulsoid with high performance of claim 1 as tackiness agent.
8, water-thinned high molecular emulsoid with high performance as claimed in claim 1, wherein, tackiness agent gross weight used in the water-borne coatings composition is 5 parts to 30 parts for the dry weight with respect to the white pigment that uses 100 parts of dry weights, and latex accounts for the 40%-100% of whole tackiness agent gross weights.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120071A CN1050856C (en) | 1993-12-10 | 1993-12-10 | Water-thinned high molecular emulsoid with high performance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93120071A CN1050856C (en) | 1993-12-10 | 1993-12-10 | Water-thinned high molecular emulsoid with high performance |
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| Publication Number | Publication Date |
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| CN1103645A true CN1103645A (en) | 1995-06-14 |
| CN1050856C CN1050856C (en) | 2000-03-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93120071A Expired - Fee Related CN1050856C (en) | 1993-12-10 | 1993-12-10 | Water-thinned high molecular emulsoid with high performance |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109211A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109210A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN105639756A (en) * | 2016-02-23 | 2016-06-08 | 浙江聚丰时装有限公司 | Manufacturing method of fur garment |
| CN109135445A (en) * | 2018-08-09 | 2019-01-04 | 深圳市前海奇迹新材料有限公司 | A kind of styrene-acrylic emulsion priming paint |
| CN118185525A (en) * | 2024-05-16 | 2024-06-14 | 江苏斯瑞达材料技术股份有限公司 | High-shear-strength thermosetting pressure-sensitive adhesive and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5590697A (en) * | 1978-12-28 | 1980-07-09 | Sumitomo Naugatuck | Production of paper coat composition |
| DE2939657A1 (en) * | 1979-09-29 | 1981-04-16 | Basf Ag, 6700 Ludwigshafen | BINDERS FOR PAPER COATING |
| JPS6038415A (en) * | 1983-08-12 | 1985-02-28 | Nippon Zeon Co Ltd | Production of copolymer latex |
-
1993
- 1993-12-10 CN CN93120071A patent/CN1050856C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109211A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109210A (en) * | 2013-04-19 | 2014-10-22 | 中国石油化工股份有限公司 | Chain transferring agent, and preparation method and application thereof |
| CN104109211B (en) * | 2013-04-19 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of chain-transfer agent and its preparation method and application |
| CN104109210B (en) * | 2013-04-19 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of chain-transfer agent and its preparation method and application |
| CN105639756A (en) * | 2016-02-23 | 2016-06-08 | 浙江聚丰时装有限公司 | Manufacturing method of fur garment |
| CN109135445A (en) * | 2018-08-09 | 2019-01-04 | 深圳市前海奇迹新材料有限公司 | A kind of styrene-acrylic emulsion priming paint |
| CN118185525A (en) * | 2024-05-16 | 2024-06-14 | 江苏斯瑞达材料技术股份有限公司 | High-shear-strength thermosetting pressure-sensitive adhesive and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1050856C (en) | 2000-03-29 |
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