CN100523006C - Surfactant for emulsion polymerization, polymer emulsion composition obtained with the surfactant, and adhesive for fiber flocking comprising the composition - Google Patents
Surfactant for emulsion polymerization, polymer emulsion composition obtained with the surfactant, and adhesive for fiber flocking comprising the composition Download PDFInfo
- Publication number
- CN100523006C CN100523006C CNB2004800067398A CN200480006739A CN100523006C CN 100523006 C CN100523006 C CN 100523006C CN B2004800067398 A CNB2004800067398 A CN B2004800067398A CN 200480006739 A CN200480006739 A CN 200480006739A CN 100523006 C CN100523006 C CN 100523006C
- Authority
- CN
- China
- Prior art keywords
- polymerization
- active agent
- synthetic latex
- flocking
- tensio
- 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 - Fee Related
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06Q—DECORATING TEXTILES
- D06Q1/00—Decorating textiles
- D06Q1/12—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile
- D06Q1/14—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile by transferring fibres, or adhesives for fibres, to the textile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A vinyl polymer emulsion composition which is reduced in the content of coagulates generated during polymerization and is satisfactory in polymerization stability and mechanical stability; an adhesive for fiber flocking which comprises the vinyl polymer emulsion composition; and a process for producing a flocked cloth, characterized by conducting flocking with the adhesive for fiber flocking. Also provided is a surfactant for emulsion polymerization which comprises as an essential ingredient a surfactant represented by the general formula (I): R1-O-(AO)n-R2 (wherein R1 represents C1-24 branched or linear alkyl, C1-24 aryl, or aryl having C8-18 alkyl; A represents lower alkylene, and the oxyalkylene groups represented by AO may be of one or more kinds; R2 represents hydrogen or C1-3 alkyl; and n is 10 to 100 on the average) and having a hydrophilic-lipophilic balance (Griffin's HLB) of 18.5 to 19.5. The vinyl polymer emulsion composition is obtained with the surfactant for emulsion polymerization.
Description
Technical field
The letex polymerization of the present invention relates to that the coagulum growing amount is few, polymerization stability and mechanical stability are all good with tensio-active agent, contain this letex polymerization with the ethene base system synthetic latex composition of tensio-active agent, contain the fiber flocking caking agent of this ethene base system synthetic latex composition, and it is characterized in that using this fiber to carry out the manufacture method of the flocking processing cloth of flocking processing with the flocking caking agent.
Background technology
In order to reduce the Health hazard that volatile organic compounds (VOC) causes in the solvent-based compositions that the influence and the reduction of environment are seen usually, the coating that is using in the conventional organic solvents type, printing ink, seal gum and caking agent etc. are just in hydrotropisms's composition, particularly letex polymerization composition conversion.
This letex polymerization composition must meet or exceed the performance reference that solvent-based compositions is expected.As everyone knows: owing to must meet or exceed this performance reference, therefore the characteristic and the character of the employed aqueous polymeric composition of letex polymerization composition come into one's own, and performance and the rerum natura of bringing into play the surfactant composition for emulsion polymerization of rendeing a service as later dispersion stabilizer also have big influence to above-mentioned performance reference.
In the monomeric letex polymerizations of ethene base system such as acrylate or vinylbenzene, can use various letex polymerizations tensio-active agent, can select to have the tensio-active agent of the character that is fit to its application purpose.In general, anion surfactant and cats product provide the synthetic latex of the small particle size with positive and negative electric charge respectively, and nonionic surface active agent provide electric on the big particle diameter synthetic latex of neutral almost.Seldom use cats product in the practicality, anion surfactant and nonionic surface active agent can separately or merge use as a rule.Use the synthetic latex of anion surface activity, all be good aspect the polymerization stability of the polymkeric substance that generates, the mechanical stability, therefore but, in the field of not wishing especially to occur foaming, use nonionic surface active agent because its poor chemical stability, foaming are many always.Though use chemical stability, freezing plateau and the low bubble property of the synthetic latex of nonionic surface active agent all good, the polymkeric substance of talkative generation does not have sufficient stability in storage and mechanical stability, can't be met aspect all properties.
When using nonionic surface active agent to use tensio-active agent as letex polymerization, the HLB of nonionic surface active agent has relation closely with particle diameter, polymerization stability, mechanical stability, the stability in storage of the synthetic latex that has generated, in general, HLB increase along with nonionic surface active agent, the particle diameter of the synthetic latex that is generated reduces, but polymerization stability, mechanical stability and stability in storage have the tendency of reduction.Above-mentioned shortcoming can be eliminated by the usage quantity that increases nonionic surface active agent, if but the usage quantity of nonionic surface active agent is too much, then make synthetic latex form film, when perhaps using as caking agent, have the shortcoming that causes that water tolerance, firmness and the transparency and physical strength reduce, expectation can improve to some extent.
Therefore, conceived the present invention in order to solve the problems referred to above in the conventional art, the objective of the invention is to: a kind of dirt settling and coagulative growing amount that is attached to inside reactor that be used to obtain reducing is provided, and the polymerization stability and the mechanical stability of the stability of the synthetic latex in the letex polymerization and the synthetic latex that is generated are good, foaming is few, the letex polymerization tensio-active agent of the ethene base system synthetic latex composition that median size is little, a kind of ethene base system synthetic latex composition, a kind of fiber that uses this synthetic latex composition is with the flocking caking agent and a kind ofly it is characterized in that using this fiber to carry out the manufacture method of the flocking processing cloth of flocking processing with the flocking caking agent.
Summary of the invention
The contriver finds: by use specified letex polymerization tensio-active agent in letex polymerization, can provide a kind of be attached to the dirt settling of inside reactor and coagulative growing amount is few, in the letex polymerization stability of synthetic latex and the synthetic latex that generated polymerization stability and mechanical stability is good, foaming less, letex polymerization tensio-active agent that median size is little, thereby finished the present invention.
That is to say, the present invention relates to a kind of containing with the tensio-active agent with 18.5～19.5 hydrophilic values (HLB of Griffin) of following general formula (I) expression letex polymerization tensio-active agent as necessary composition.
R
1-O-(AO)
n-R
2 (I)
In the formula: R
1The expression carbonatoms is that 1～24 branched-chain or straight-chain alkyl, carbonatoms are 1～24 aryl and contain the aryl that carbonatoms is 8～18 alkyl, and A represents low-grade alkylidene, and the kind of the oxyalkylene group of representing with AO also can be more than a kind or 2 kinds, R
2Expression hydrogen atom or carbonatoms are 1～3 alkyl, n average out to 10～100.
Above-mentioned tensio-active agent is preferably with R
1Be R
3(R
4) CH-(R here,
3And R
4Represent independently that respectively carbonatoms is 1～22 branched-chain or straight-chain alkyl) the secondary alcohol alkoxylates of general formula (I) expression.
In addition, the present invention relates to contain the ethene base system synthetic latex composition of above-mentioned emulsion polymerization with tensio-active agent.
In addition, the present invention relates to contain the fiber flocking caking agent of above-mentioned ethene base system synthetic latex composition.
In addition, the invention still further relates to a kind of manufacture method that it is characterized in that using above-mentioned fiber to carry out the flocking processing cloth of flocking processing with the flocking caking agent.
Below describe the present invention in detail.
First aspect of the present invention relates to the letex polymerization tensio-active agent that a kind of tensio-active agent of representing with following general formula with 18.5～19.5 hydrophilic values (HLB of Griffin) contains as necessary composition.
R
1-0-(AO)
n-R
2 (I)
In the present invention, the hydrophilic value of tensio-active agent (HLB of Griffin) is preferred 18.6～19.0, and more preferably 18.8～19.0.At this moment, if HLB is less than 18.5, then letex polymerization is carried out not smoothly, the dirt settling and the coagulative growing amount that are attached to inside reactor increase, in addition, if the letex polymerization by same addition compares with tensio-active agent, then because the particle diameter of the synthetic latex that generates becomes big, in order to form roughly the same particle diameter, must volume ground use the letex polymerization tensio-active agent, and if volume ground uses the letex polymerization tensio-active agent, synthetic latex formation film then, perhaps when using, cause water tolerance as caking agent, the firmness and the transparency reduce and physical strength reduces.On the contrary, if HLB greater than 19.5, then the coagulum growing amount during letex polymerization increases, the polymerization stability of the synthetic latex that is generated, mechanical stability reduce." hydrophilic value (HLB of Grffin) (following also abbreviate as " HLB ") " is meant the value that the HLB method of calculation of the Griffin that adopts following formula (2) expression are calculated in addition, in the present invention.
HLB＝20×(1-W
0/W) (2)
W in following formula (2)
0Be the molecular weight of hydrophobic group in the tensio-active agent, and W is the molecular weight of tensio-active agent integral body.
As mentioned above, the letex polymerization of using among the present invention contains compound with general formula (I) expression as necessary composition with tensio-active agent, and R in the general formula (I)
1Expression: carbonatoms is 1～24, and is preferred 8～18, more preferably 10～14 branched-chain or straight-chain alkyl; Carbonatoms is 1～24, and is preferred 8～18, more preferably 10～14 aryl; Contain carbonatoms and be 8～18, the aryl of preferred 10～14, more preferably 12～14 alkyl.At this moment, if sub stituent R
1Carbonatoms not in suitable scope, then produce following problem: letex polymerization is carried out not smoothly, being attached to the dirt settling of inside reactor and coagulative growing amount increases, the polymerization stability of the synthetic latex that obtains and mechanical stability reduce.And by making sub stituent R
1Carbonatoms in above-mentioned scope, can carry out letex polymerization expeditiously, can reduce, prevent to be attached to the dirt settling and the coagulative generation of inside reactor, can also guarantee the polymerization stability and the mechanical stability of resulting synthetic latex.
As above-mentioned R
1Middle carbonatoms is 1～24 branched-chain or straight-chain alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, neo-pentyl, hexyl, isohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, 2-ethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.In addition, be 1～24 aryl as carbonatoms, can enumerate phenyl, benzyl, styroyl, neighbour, or p-methylphenyl, 2,3-or 2,4-xylyl, Lai Ji, naphthyl, anthryl, phenanthryl, xenyl, diphenyl-methyl, trityl, pyrenyl etc.In addition,, can enumerate the neighbour as containing the aryl that carbonatoms is 8～18 alkyl,, right-tolyl, neighbour,, right-phenylethyl, styroyl, xylyl, neighbour,, right-cumyl, neighbour,, p-cymene base, neighbour,, right-
Alkyl,
Base, diphenyl methyl etc.
Preferred R wherein
1Have side chain, the more preferably alkyl of side chain is most preferably with formula: R
3(R
4) the secondary alkyl represented of CH-.At this moment, tensio-active agent of the present invention becomes with R in general formula (I)
1Be R
3(R
4) secondary alcohol alkoxylates of general formula (I) expression of CH-.Like this, if by being used for the letex polymerization tensio-active agent as necessary surfactant composition with secondary alcohol alkoxylates, compare with tensio-active agent with other letex polymerization, because can be with few addition dispersed monomer fully, therefore compare by same addition, then when letex polymerization, can further suppress to be attached to the dirt settling and the coagulative growing amount of inside reactor, can generate the synthetic latex of small particle size, can improve simultaneously this synthetic latex and process the water tolerance that the fiber that uses with adhesive composite is used the flocking processed goods as flocking, the firmness and the transparency, and improve feel.R in following formula
3And R
4Represent independently that respectively carbonatoms is 1～22 branched-chain or straight-chain alkyl, preferred straight chained alkyl.R
3Carbonatoms and R
4Carbonatoms add up to 1～23, preferred 7～17, more preferably 9～13.Specifically, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, neo-pentyl, hexyl, isohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, 2-ethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.
Above-mentioned R
1Be with formula: R
3(R
4) the secondary alkyl represented of CH-, that is to say, at tensio-active agent of the present invention is in the particularly preferred mode of secondary alcohol alkoxylates, the addition position of oxyalkylene group in the secondary alcohol alkoxylates (in the general formula (I)-(AO)-) is represented with the addition position of the oxyalkylene group that the carbon from the alkyl end begins to calculate, for example, if carbonatoms is 12 secondary alcohol alkoxylates, then 2,3,4,5,6 position exists.As the addition position distribution of preferred oxyalkylene group, the maximum of single addition set of locations compound is below 25% weight, more preferably below 20% weight.The addition position of oxyalkylene group is approximate equality ground addition in this expression secondary alcohol alkoxylates, by making the addition position equalization of this oxyalkylene group, the polymerization stability of monomeric dispersiveness and monomer particle in the time of can improving letex polymerization, and can suppress to be attached to the dirt settling and the coagulative growing amount of inside reactor, and at the fiber that improve to use this synthetic latex with the feel of flocking processed goods etc. and improve as letex polymerization aspect the availability of Surfactant the useful prerequisite of can saying so.
A represents low-grade alkylidene in the above-mentioned general formula (I), represents that preferred carbonatoms is 2～8, and more preferably carbonatoms is 2～4 low-grade alkylidene.At this moment, if A is the alkylidene group of carbonatoms more than 9, then manufacturing cost increases, because of hydrophobicity strong excessively, letex polymerization is carried out smoothly, the dirt settling and the coagulative growing amount that are attached to reactor section are increased, perhaps become the polymerization stability of the synthetic latex that is generated and the essential factor that mechanical stability reduces, so not preferred.Therefore, as the oxyalkylene group of representing with AO, for example be oxyethylene group, oxypropylene group, oxybutylene base, oxidation pentenyl, oxidation hexenyl, oxidation heptenyl, octylene oxide base and oxidation phenyl vinyl etc., preferred oxyethylene group, oxypropylene group and oxybutylene base, more preferably oxyethylene group and oxypropylene group.In addition, there are a plurality of AO in the above-mentioned general formula (I).That is to say that if n is 2 when above in the general formula (I), then the oxyalkylene group that defines with AO can also be by constituting more than 2 kinds except also can only constituting by a kind.If by constituting oxyalkylene group more than 2 kinds, then the oxyalkylene group more than 2 kinds both can irregularly dispose, also can press the block configuration respectively.For example, also can be the structure that the part of oxyethylene group long-chain is taken as oxypropylene group.
N represents to be present in the mean number of the oxyalkylene group in the tensio-active agent of general formula (I), average out to 10～100, preferred 60～90 in the above-mentioned general formula (I).At this moment, if n greater than 100, then coagulative growing amount increases during letex polymerization, the polymerization stability of the synthetic latex that is generated and mechanical stability might reduce etc., so not preferred.On the contrary, if n is less than 10, then letex polymerization can not be carried out smoothly, the dirt settling and the coagulative growing amount that might be attached to inside reactor increase, if perhaps compare by adding same tensio-active agent, then because the increase of the particle of the synthetic latex that is generated, in order to form roughly the same median size, must use the letex polymerization tensio-active agent in large quantities, and if use the letex polymerization tensio-active agent in large quantities, then might make synthetic latex form film, perhaps when using as caking agent, water tolerance and firmness and also have transparency to reduce physical strength reduction etc. perhaps occurs, so still not preferred.In addition, change, can control desired monomeric dispersiveness, hydrophobicity etc.,, suitably determine the scope of n therefore more preferably according to desired characteristic and purposes by the addition mole number n that makes AO.In addition, if n is more than 2, then the kind of the oxyalkylene group of representing with AO also can be more than a kind or 2 kinds, if this oxyalkylene group is more than 2 kinds, then various oxyalkylene groups all is made as average n.
R in above-mentioned general formula (I)
2Expression hydrogen atom or carbonatoms are 1～3 alkyl (methyl, ethyl, propyl group or sec.-propyl).Preferable methyl or ethyl.
The tensio-active agent manufacture method of general formula of the present invention (I) is not particularly limited, and well-known method can be used either alone or in combination.Below describe the manufacture method of the secondary alcohol alkoxylates of best mode of the present invention in detail.For example alkylene oxide can be added to C
12～14(Japanese catalyzer (strain) company produces secondary alcohol, trade(brand)name: in ソ Off ノ-Le-A).As the addition method of this alkylene oxide, be that 50 ℃～200 ℃, reaction pressure are normal pressure～20kg/cm in temperature of reaction for example by making above-mentioned secondary alcohol
2Under the condition of scope,, thereby can access secondary alcohol alkoxylates as target with alkylene oxide reaction.If above-mentioned temperature of reaction is lower than 50 ℃, then can suppress to decompose and the increase of secondary resultant, but speed of response is slack-off.In addition, if greater than 200 ℃,, can cause decomposition and secondary resultant increase etc., so not preferred though then speed of response is accelerated.In addition, in above-mentioned secondary alcohol, during the addition alkylene oxide, also can use alkaline catalystss such as acid catalysts such as BF3 and sodium hydroxide, potassium hydroxide.No matter this acid catalyst and alkaline catalysts are that powder or particulate state can be added, and also can be used as the aqueous solution in addition and add.
The tensio-active agent of above-mentioned general formula (I) is except can be only by constituting more than a kind or 2 kinds, the letex polymerization combinations-of surfactants of it and other can also be constituted letex polymerization tensio-active agent of the present invention.For example, also secondary alcohol alkoxylates more than the HLB18.5 and the nonionic surface active agent below the HLB18.5 can be made up, can also be with secondary alcohol alkoxylates more than the HLB18.5 and anion surfactant combination.Be not particularly limited with tensio-active agent for the letex polymerization of using, for example, can enumerate polyethylene oxide alkyl ethers such as polyoxyethylene bay ether, polyoxyethylene n-Hexadecane ether, polyoxyethylene octadecane ether, polyoxyethylene n-Hexadecane ether as nonionogenic tenside; Polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylplenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether; Fatty acid esters such as polyoxyethylene Span-20, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene propylene oxide stearate, polyoxyethylene glycerin fatty acid ester also can use the reactive surfactant that has functional group in surfactant structure in addition.Polyethylene oxide alkyl ethers such as wherein preferred especially polyoxyethylene bay ether, polyoxyethylene n-Hexadecane ether, polyoxyethylene octadecane ether, polyoxyethylene n-Hexadecane ether.
As anion surfactant, for example can enumerate straight chained alkyl sulfuric acid, linear alkylbenzene sulfonate, polyethylene oxide alkyl ethers sulfuric acid, polyoxyethylene alkyl phenyl ether sulfuric acid etc.Other above-mentioned tensio-active agent (nonionic surface active agent and/or anion surfactant) also can use individually or use in the mode of mixture more than 2 kinds, in addition, ratio when making up more than 2 kinds is not particularly limited, and can substantially not have combination in the scope of influence.Special in letex polymerization can not be carried out smoothly, therefore at aspect of performances such as the polymerization stability that suppresses to be attached to the dirt settling of inside reactor and the synthetic latex that coagulum growing amount and raising generated, mechanical stabilities, preferably concoct the present invention's other letex polymerization tensio-active agent in addition.At this moment, more than preferred 70% weight ratio of the content of tensio-active agent in surfactant composition for emulsion polymerization of general formula of the present invention (I), more preferably the scope more than 80% weight ratio is suitable.
Second aspect of the present invention is to contain the ethene base system synthetic latex composition of letex polymerization of the present invention with tensio-active agent.
With respect to the synthetic latex total composition, letex polymerization uses the addition of tensio-active agent preferably in the scope of 0.1～10.0% weight, more preferably in the scope of 1.0～5.0% weight in the synthetic latex composition of the present invention.If this letex polymerization uses the addition of tensio-active agent not in suitable scope, the dirt settling and the coagulum growing amount that then are attached to inside reactor increase, the grain diameter of the synthetic latex that is generated increases, and polymerization stability, mechanical stability and monomer productive rate have the tendency of reduction.
Be not particularly limited for the ethene base system monomer that constitutes synthetic latex composition of the present invention, can use well-known ethene base system monomer.For example: aromatic vinyl monomers such as vinylbenzene, alpha-methyl styrene, chloro-styrene, dimethylamino vinylbenzene, nitrostyrolene, Vinylstyrene; Vinyl halides and meta-halo ethylene monomers such as bromine ethene, vinylchlorid, vinylidene chloride; Vinyl acetate monomer such as vinyl acetate, propionate; Ethylene series monomers such as ethene, propylene, 1-butylene, 1-hexene, 1-octene; Divinyl, isoprene equiconjugate diene; (methyl) acrylate such as (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid methyl ethyl ester, EHA, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxyl ethyl ester; Acrylamide, 2-acrylamide; Vinyl cyanide, (methyl) vinyl cyanide, diethyl fumarate etc.Wherein, preferred (methyl) butyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester, 2-acrylamide, the vinylbenzene of using especially preferably uses (methyl) acrylate.
As the polymerization starter that is used for letex polymerization of the present invention, so long as promote the polymeric catalyzer, can both use, be not particularly limited, can use general superoxide, azo series initiators and oxygenant and reductive agent are merged the reducto oxydative system polymerization starter that uses, it is suitable using the reducto oxydative system polymerization starter.The oxygenant that uses as the reducto oxydative system polymerization starter can be enumerated Potassium Persulphate, Sodium Persulfate, ammonium persulphate, benzoyl peroxide, Diisopropyl azodicarboxylate, hydrogen peroxide etc.And, can enumerate S-WAT, Sodium Pyrosulfite, sodium thiosulfite, xitix (acid of ア ス コ ロ PVC Application), hydrazine (ヒ De ロ ジ Application) etc. as reductive agent.Especially, it is suitable using the reducto oxydative system polymerization starter with persulphate and sulphite combination.
In addition; except tensio-active agent is used in letex polymerization of the present invention; as polymerization stabilizer, also protective colloids such as polyvinyl alcohol, Alpha-Methyl Mierocrystalline cellulose, Natvosol, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), aqurous ployurethane compound can be merged and use.This be because: by using above-mentioned protective colloid, polymerization stability and mechanical stability are improved.
The monomeric emulsion polymerisation process of ethene base system of the present invention is to use letex polymerization of the present invention to carry out method of emulsion polymerization with tensio-active agent (comprising composition), as method of emulsion polymerization, can use common emulsion polymerisation process such as monomer additive process, emulsion additive process, seeding polymerization method.Though the temperature of reaction when monomer drips can be adjusted by the decomposition temperature of polymerization starter, desirable-10 ℃～150 ℃ scopes, preferred 30～70 ℃, more preferably 40～60 ℃.If temperature of reaction is too high, then coagulative growing amount increases, and in addition, exists because of heating to make the temperature unmanageable tendency that becomes.Polymerization reaction time is subjected to be not particularly limited about other conditions such as temperature of reaction, but normally 3～6 hours.
The total amount of the synthetic latex composition that obtains with respect to cooperation, in the synthetic latex composition that the present invention obtains preferred 1.0% weight ratio of coagulative growing amount following, more preferably below 0.5% weight ratio.This be because: if the coagulum growing amount is more than 1.0% weight ratio, then need to remove the coagulative operation that is generated, increased the discarded cost that waits of coagulum again, therefore exist to produce and go up not satisfied tendency.
Below the preferred 150nm of synthetic latex particulate median size that obtains according to the present invention, more preferably 10～150nm, more preferably 10～100nm again, preferred especially 20～100nm.This be because: if the synthetic latex particulate median size that obtains is greater than 150nm, then owing to the particle agglutination in the synthetic latex is easy to precipitation, therefore the dirt settling and the coagulative growing amount that are attached to inside reactor increase, and the polymerization stability of resulting synthetic latex has the tendency of reduction.
Synthetic latex composition of the present invention can be used as thermoplastic resin, thermosetting resin uses, in each field such as film, mouldings, coating, laminated wood, rubber adhesive, decorative sheet, flash of light panel, groceries, finding, wall material, industrial equipment, also can use, and also produce effect with caking agent as non-woven fabrics.Especially, by being used for fiber flocking caking agent, can access the equal fiber with excellent of firmness and feel flocking processed goods according to the synthetic latex composition that the present invention obtains.Therefore, the 3rd aspect of the present invention is the fiber flocking caking agent that contains ethene base system synthetic latex composition of the present invention.
As this flocking processed goods, can enumerate dress materials such as overcoat, blazer, gloves, cap, scarf with the flocking processed goods, plant a mao carpet, mat, curtain, cushion, footwear materials such as crust with groceries processed goods such as flocking processed goods, puppet, toy, bag, flexible pipe, electric wires, as employed flocking caking agent, not only can use fiber of the present invention flocking caking agent, but also can be that well-known flocking processing such as emulsion, synthetic rubber latex merges use with caking agent Vinyl Acetate Copolymer emulsion, propylene.
Make the method for fiber as using above-mentioned synthetic latex composition, be not particularly limited, can use the usual method manufacturing with the flocking processed goods.For example, be emulsion for propylene with carboxyl, add alkaline agents such as ammoniacal liquor, make it increase viscosity.Also can use thermosetting resin and acceleration solidifying agent such as methylcellulose gum, carboxymethyl cellulose, Natvosol, polyvinyl alcohol as required.With aforesaid propylene be that emulsion is same; also use thermosetting resin and quicken solidifying agent; make Vinyl Acetate Copolymer emulsion increase viscosity; but in addition; improving normal temperature film-forming properties, initial stage during cementability, add reversible dose of dibutyl phthalate, phosphoric acid 2-ethylhexyl diphenyl ester, methyl phthaloyl methyl glycolate, polyethyleneglycol adipate etc.In addition, for synthetic rubber latex, preferably add tenderizer such as caking agent, polybutene, polyisobutene copolymer, polyvinyl isobutyl ether polymkeric substance, lanolin such as rosin, ester gum, terpine resin, petroleum line resin, vinylbenzene base system resin, alkylbenzene phenol resin and add protective agents such as nonox, mercaptobenzimidazole, butylhydroquinone, to adjust to target viscosities.The tackify emulsion that will obtain so in certain proportion in spreadometer is coated on the fabric, carries out the electric hair of planting at once, removes remaining matte behind dry solidification, thereby can access fastness and all good flocking processed goods of feel.
Embodiment
Below specify content of the present invention with embodiment, but the present invention is not limited to following embodiment.In addition, as long as do not specify among the embodiment that " % " is benchmark with weight.In addition, ethylene oxide and propylene oxide are simply represented with EO, PO respectively.
Synthesis example 1
Butyl acrylate 100.0 grams, methyl acrylate 40.0 grams and vinylformic acid 4.0 grams are mixed, be modulated into the acrylate mixture, each nonionic surface active agent (A-1)～(A-9), (B-1)～(B-8) that ion exchanged water 226.9 grams, acrylate mixture 14.4 grams, table 1 are put down in writing add in the 500ml separating flask by the blending amount of putting down in writing with table 1, rotation number with 200rpm is stirred the companion on one side, Yi Bian be blown into nitrogen 30 minutes.Then, under nitrogen atmosphere, stir on one side,, make internal temperature be warming up to 55 ℃, and keep the temperature under this state Yi Bian add Potassium Persulphate 0.03 gram, S-WAT 0.02 gram.Then,, then residual acrylate mixture 129.6 grams were dripped by 180 minutes, 4% persulfate aqueous solution, 12.4 grams and 4% sodium sulfite aqueous solution, 8.7 grams were together dripped by 200 minutes if internal temperature keeps certain down at 55 ℃.After the end of dripping, temperature in the flask was kept 40 minutes down at 55 ℃, finish the reaction postcooling to room temperature, filter, obtain target synthetic latex composition [embodiment (1)～(8), comparative example (1～(7)) at the letex polymerization liquid that will react on the 100 order wire cloths after finishing.For the synthetic latex that obtains, promptly coagulum growing amount, percent polymerization, polymerization stability, median size, mechanical stability, foaminess, fiber flocking processing experiment and laminated test are carried out in embodiment (1)～(8), comparative example (1)～(7).Its result is recorded in table 3 and 4.
Table 1
| Nonionic surface active agent | EO addition mole number/n | HLB | Combined amount (%) | |
| A-1 | Secondary alcohol ethoxyl compound | 60 | 18.6 | 2.0 |
| A-2 | Secondary alcohol ethoxyl compound | 70 | 18.8 | 2.0 |
| A-3 | Secondary alcohol ethoxyl compound | 100 | 19.1 | 2.0 |
| A-4 | Primary alcohol ethoxylate | 70 | 18.8 | 2.0 |
| A-5 | Primary alcohol ethoxylate | 100 | 19.2 | 2.0 |
| A-6 | Nonyl phenol ethoxylate | 70 | 18.7 | 2.0 |
| A-7 | Nonyl phenol ethoxylate | 100 | 19.0 | 2.0 |
| A-8 | Secondary alcohol ethoxyl compound | 70 | 18.8 | 1.5 |
| A-9 | Secondary alcohol ethoxyl compound | 70 | 18.8 | 1.0 |
| B-1 | Secondary alcohol ethoxyl compound | 12 | 14.5 | 2.0 |
| B-2 | Secondary alcohol ethoxyl compound | 30 | 17.4 | 2.0 |
| B-3 | Secondary alcohol ethoxyl compound | 40 | 18.0 | 2.0 |
| B-4 | Secondary alcohol ethoxyl compound | 200 | 19.6 | 2.0 |
| B-5 | Primary alcohol ethoxylate | 10 | 13.9 | 2.0 |
| B-6 | Primary alcohol ethoxylate | 40 | 18.0 | 2.0 |
| B-7 | Nonyl phenol ethoxylate | 10 | 13.3 | 2.0 |
| B-8 | Nonyl phenol ethoxylate | 40 | 17.8 | 2.0 |
Synthesis example 2
Vinylbenzene 120.0 grams, methacrylic acid 2-hydroxyl ethyl ester 16.0 grams and 2-acrylamide 4.0 grams are mixed, be modulated into monomer mixture.Ion exchanged water 235.7 grams, each nonionic surface active agent (A-9)～(A-15) that monomer mixture 14.4 restrains, table 2 is put down in writing, the blending amount that (B-9)～(B-11) puts down in writing by table 2 are added in the 500ml separating flask, rotation number with 200rpm is stirred the companion on one side, Yi Bian be blown into nitrogen 30 minutes.Then, under nitrogen atmosphere, stir on one side,, make internal temperature be warming up to 80 ℃, and keep the temperature under this state Yi Bian add Potassium Persulphate 0.03 gram.Then,, then residual monomer mixture 129.6 was dripped by 180 minutes, 4% persulfate aqueous solution, 12.5 grams were dripped by 200 minutes if temperature keeps certain down at 80 ℃ in the bottle.After the end of dripping, the temperature in the flask was kept 40 minutes down at 80 ℃, finish reaction, be cooled to room temperature then, letex polymerization liquid after filtering reaction on the 100 order wire cloths finishes obtains the target synthetic latex, i.e. embodiment (9)～(15) and comparative example (9)～(11).Same with synthesis example 1, for the synthetic latex that obtains, be each synthetic latex of embodiment (9)～(15), comparative example (9)～(11), carry out coagulum growing amount, percent polymerization, polymerization stability, median size, mechanical stability, foaminess and the test of coating caking agent.Its result is recorded in table 5 and 6.
Table 2
| Nonionic surface active agent | EO addition mole number/n | HLB | Use level (%) | |
| A-10 | Secondary alcohol ethoxyl compound | 70 | 18.8 | 2.0 |
| A-11 | Secondary alcohol ethoxyl compound | 100 | 19.1 | 2.0 |
| A-12 | Primary alcohol ethoxylate | 70 | 18.8 | 2.0 |
| A-13 | Primary alcohol ethoxylate | 100 | 19.2 | 2.0 |
| A-14 | Nonyl phenol ethoxylate | 70 | 18.7 | 2.0 |
| A-15 | Nonyl phenol ethoxylate | 100 | 19.0 | 2.0 |
| B-9 | Secondary alcohol ethoxyl compound | 20 | 16.3 | 2.0 |
| B-10 | Primary alcohol ethoxylate | 20 | 16.4 | 2.0 |
| B-11 | Nonyl phenol ethoxylate | 20 | 16.0 | 2.0 |
In addition, above-mentioned table 1 and 2 secondary alcohol ethoxyl compounds of being put down in writing all contain carbon number C
12～14Alkyl, carbon number C
12～14Ratio be C
12: C
13: C
14=1:2:1, primary alconol contain carbon number C
12, C
14Alkyl, carbon number C
12, C
14Ratio be C
12:C
14=8:2.
In addition, above-mentioned synthesis example 1 and 2 characteristic are following respectively estimates, measures.
(coagulum growing amount)
On 100 order wire cloths, filter above-mentioned synthetic latex, then, take out and be attached to the dirt settling that stirs companion's blade, thermoswitch, reactor, filter equally.After the washing, drying is 4 hours under 80 ℃ gently, and quality measurement is obtained the % quality of the synthetic latex of cooperation with respect to total amount.
(percent polymerization)
[condition is as follows: gas chromatogram: Tianjin, island GC-17A according to gas chromatography, chromatographic column GLSciences Inc. society system, NEUTRA BOND-1 (length: 30m, internal diameter: 0.53mm, thickness: 2.0 μ m), temperature condition: 50 ℃ of initial temperatures (keeping 5 minutes), 10 ℃/min of heat-up rate, 350 ℃ of outlet temperatures (keeping 40 minutes), sample is established into amount: 1 μ L] analyze resulting synthetic latex, area ratio according to the figure that obtains is obtained each monomeric content, according to the monomer weight that cooperates, calculate percent polymerization.
(polymerization stability)
After the synthetic latex that obtains at room temperature placed a week, on 100 order wire cloths, filter, gently after the washing, 80 ℃ dry 4 hours down, quality measurement is obtained the % quality of the synthetic latex of cooperation with respect to total amount.
(median size)
For the synthetic latex that obtains, the particle size determination device DLS-700 that uses the development of ユ ニ オ Application skill to make, gravimetry median size according to dynamic light scattering method.
(mechanical stability)
The synthetic latex that obtains with the 25% ammoniacal liquor pH9 that neutralizes, is got synthetic latex 50 grams after the neutralization, in the intimate mixing machine, cut off test by 5000rpm, 10 minutes condition.Synthetic latex after the test filters on 100 order wire cloths, and after the washing, drying is 4 hours under 80 ℃ gently, and quality measurement is obtained the % quality of the synthetic latex of cooperation for total amount.
(foaminess test)
With the synthetic latex 40ml that the obtains 100ml graduated cylinder of packing into, carry out vibration test by 100 times/minute, 1 minute condition.After the vibration graduated cylinder is left standstill, measure the height of bubble.
(fiber flocking processing experiment)
Synthetic latex 100 grams that obtain, melamine methylol 5 grams that methylate, heat embrittlement catalyzer (ス ミ テ Star Network ス ACX) 0.5 gram are mixed, make pH adjust to 6.5 with 25% ammoniacal liquor then.Press 0.3mm (250 gram/m by spreadometer
2) ratio it is coated on cotton weaves cotton cloth, use electric feather planting machine more at once, under the condition of voltage 30kV, electrode space 10cm, 1.5 dawn, 0.4mm artificial silk matte are planted hair.Then, this fabric is inserted moisture eliminator, descended predrying 10 minutes, toasted 10 minutes down at 140 ℃ again at 80 ℃.After making its drying, in the controlled thermohygrostat of 25 ℃ of temperature, humidity 70%, place diel, carry out fastness and hand test.At this moment, the result of hand test is divided into following 4 grades:
◎: good, zero: good, △: general, *: poor.
(laminated test)
Synthetic latex 100 grams that obtain, melamine methylol 5 grams that methylate, heat embrittlement catalyzer (ス ミ テ Star Network ス ACX) 0.5 gram are mixed, with 25% ammoniacal liquor pH is adjusted to 6.5 then.Then, use the wet type Laminated device, press 2g/m
2Ratio be coated on paper/aluminium, the speed of dividing with 150m/ is carried out laminatedly again, tests the stripping strength of resulting laminated film under 180 ℃.
(test of coating caking agent)
Titanium oxide (rutile-type) 200 grams, ground barium sulfate 40 grams, talcum powder 20 grams and lime carbonate 140 are restrained as pigment, 2% hydroxyethyl cellulose aqueous solution 100 is restrained as tackifier, 10% sodium hexametaphosphate solution, 8 grams as pigment dispersing agent, are added in the 300 gram synthetic latexes that obtain and mix.The emulsion coating that obtains is coated on the mortar test weathering resistance and anti-cleaning.In addition, weathering test is: placed without 6 months, the folding line that visual observations is filmed, crackle, heave, peel off, deterioration such as variable color.The test of anti-cleaning is: above-mentioned mortar is dipped in 0.5% suds, boil 3 hours after, test being coated with heaving of face.At this moment, the result with weathering test is divided into following 3 grades:
Zero: deterioration not, △: deterioration is arranged slightly, *: deterioration is arranged.
And the result of anti-cleaning test is divided into following 3 grades:
Zero: do not peel off △: peel off slightly, *: peel off in a large number.
Table 4
Table 5
| Nonionic surface active agent | Coagulum amount (w%) | Monomer yield (%) | Polymerization stability (wt%) | Median size (nm) | Mechanical stability (wt%) | Foaminess (mm) | |
| Embodiment 10 | A-10 | 0.12 | 99.1 | <0.01 | 45 | <0.01 | 71 |
| Embodiment 11 | A-11 | 0.29 | 98.7 | <0.01 | 71 | 0.02 | 74 |
| Embodiment 12 | A-12 | 0.26 | 98.7 | <0.01 | 68 | <0.01 | 79 |
| Embodiment 13 | A-13 | 0.41 | 98.0 | <0.01 | 82 | 0.05 | 78 |
| Embodiment 14 | A-14 | 0.28 | 99.0 | <0.01 | 93 | 0.02 | 74 |
| Embodiment 15 | A-15 | 0.36 | 98.7 | <0.01 | 98 | 0.04 | 78 |
| Comparative example 9 | B-9 | 2.21 | 93.4 | 0.08 | 185 | 0.12 | 81 |
| Comparative example 10 | B-10 | 2.96 | 91.6 | 0.12 | 245 | 0.23 | 88 |
| Comparative example 11 | B-11 | 2.09 | 93.3 | 0.09 | 193 | 0.19 | 86 |
Table 6
From above-mentioned table 3～6 as can be known: by letex polymerization, using letex polymerization tensio-active agent of the present invention, can access a kind of median size little, can reduce the dirt settling and coagulative growing amount and polymerization stability and all good synthetic latex composition of mechanical stability that are attached to inside reactor, be used for flocking processing cloth by the fiber that will contain this synthetic latex composition with the flocking caking agent simultaneously, can access all good flocking processed goods of fastness and feel.In addition, except flocking processing cloth, synthetic latex of the present invention uses in each field such as film, mouldings, coating, laminated wood, rubber adhesive, decorative sheet, flash of light panel, groceries, finding, wall material, industrial equipment, also can bring into play effect.
The possibility of utilizing on the industry
Emulsion polymerisation surfactant of the present invention, namely being used in vinyl is the emulsion polymerisation of monomer, also can obtain a kind ofly can reducing the attachment and the coagulative growing amount that are attached to inside reactor, can fully guarantee the stability of the synthetic latex in the emulsion polymerisation and polymerization stability, the mechanical stability of the synthetic latex that generates are good, foaming less and the little synthetic latex of average grain diameter.
In addition, synthetic latex composition of the present invention can be common to fiber flocking bonding agent, can access thus all good fiber flocking processed goods of fastness and feel.
Claims (5)
1. letex polymerization tensio-active agent is characterized in that:
Contain tensio-active agent with following general formula (I) expression as neccessary composition with 18.5-19.5 hydrophilic value,
R
1-O-(AO)
n-R
2 (I)
In the formula: R
1The expression carbonatoms is that branched-chain or straight-chain alkyl, phenyl or the carbonatoms of 1-24 is the aryl of 8-24, and A represents that carbonatoms is the alkylidene group of 2-8, and the kind of the oxyalkylene group of representing with AO is more than a kind or 2 kinds, R
2Expression hydrogen atom or carbonatoms are the alkyl of 1-3, n average out to 60-100.
2. as the letex polymerization tensio-active agent of record in the claim 1, R wherein
1Be R
3(R
4) CH-, R
3With R
4Independent respectively expression carbonatoms is the branched-chain or straight-chain alkyl of 1-22.
3. ethene base system synthetic latex composition, said composition contain the letex polymerization tensio-active agents of claim 1 or 2 records.
4. fiber flocking caking agent, this caking agent contain the ethene base system synthetic latex composition of record in the claim 3.
5. the manufacture method of a flocking processing cloth is characterized in that: use the fiber of record in the claim 4 to carry out flocking processing with the flocking caking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP068438/2003 | 2003-03-13 | ||
| JP2003068438 | 2003-03-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1759124A CN1759124A (en) | 2006-04-12 |
| CN100523006C true CN100523006C (en) | 2009-08-05 |
Family
ID=32984588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800067398A Expired - Fee Related CN100523006C (en) | 2003-03-13 | 2004-03-11 | Surfactant for emulsion polymerization, polymer emulsion composition obtained with the surfactant, and adhesive for fiber flocking comprising the composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4118913B2 (en) |
| KR (1) | KR100706276B1 (en) |
| CN (1) | CN100523006C (en) |
| WO (1) | WO2004081058A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6223693B2 (en) * | 2012-03-06 | 2017-11-01 | ジャパンコーティングレジン株式会社 | Synthetic resin emulsion, coating agent using the same, and coating layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191156A (en) * | 1996-12-06 | 1998-08-26 | 株式会社日本触媒 | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
| JP2001072702A (en) * | 1999-06-29 | 2001-03-21 | Asahi Denka Kogyo Kk | Emulsifier for emulsion polymerization, or dispersing agent for suspension polymerization |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5531820A (en) * | 1978-08-24 | 1980-03-06 | Sumitomo Chem Co Ltd | Preparation of vinyl chloride type polymer emulsion |
| JPS58129012A (en) * | 1982-01-28 | 1983-08-01 | Nitto Kasei Kk | Preparation of antifouling emulsion of copolymer containing triorganotin salt |
| JPH01318027A (en) * | 1988-06-17 | 1989-12-22 | Toagosei Chem Ind Co Ltd | Preparation of aqueous resin composition |
| JP3356803B2 (en) * | 1992-08-14 | 2002-12-16 | 旭硝子株式会社 | Fluoropolymer aqueous dispersion |
| JP3356804B2 (en) * | 1992-08-14 | 2002-12-16 | 旭硝子株式会社 | Fluoropolymer aqueous dispersion |
| JPH0741748A (en) * | 1993-07-29 | 1995-02-10 | Mitsui Petrochem Ind Ltd | Water-dispersed adhesive |
| JPH0912656A (en) * | 1995-06-29 | 1997-01-14 | Sekisui Chem Co Ltd | Vinyl chloride resin emulsion and its production |
| JP3749591B2 (en) * | 1997-03-31 | 2006-03-01 | 三井化学株式会社 | Water dispersion and water dispersion adhesive |
| JP3696368B2 (en) * | 1997-04-25 | 2005-09-14 | 旭電化工業株式会社 | Antifoaming agent for phosphoric acid production process |
-
2004
- 2004-03-11 CN CNB2004800067398A patent/CN100523006C/en not_active Expired - Fee Related
- 2004-03-11 JP JP2005503559A patent/JP4118913B2/en not_active Expired - Lifetime
- 2004-03-11 WO PCT/JP2004/003167 patent/WO2004081058A1/en active Application Filing
- 2004-03-11 KR KR1020057016582A patent/KR100706276B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191156A (en) * | 1996-12-06 | 1998-08-26 | 株式会社日本触媒 | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
| JP2001072702A (en) * | 1999-06-29 | 2001-03-21 | Asahi Denka Kogyo Kk | Emulsifier for emulsion polymerization, or dispersing agent for suspension polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1759124A (en) | 2006-04-12 |
| JPWO2004081058A1 (en) | 2006-06-08 |
| WO2004081058A1 (en) | 2004-09-23 |
| KR100706276B1 (en) | 2007-04-12 |
| KR20050117537A (en) | 2005-12-14 |
| JP4118913B2 (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104053723B (en) | Coating for the novel chemically-reactive surfactant of freeze-thaw stability emulsion polymer and comprising it | |
| US5162475A (en) | Polymerizable surfactant | |
| CA1244188A (en) | Acrylic-methylene succinic ester emulsion copolymers for thickening aqueous systems | |
| EP0346097A2 (en) | Thickening system | |
| CN1156727A (en) | Preparation of polymers by emulsion polymerization | |
| CN1206721A (en) | Preparation of fluorated polymer | |
| EP1069139A2 (en) | Aqueous polymer dispersion, its preparation and use | |
| DE2902528A1 (en) | TEXTILE FINISHING AGENTS | |
| CA1264280A (en) | Aqueous adhesive compositions for use with wall coverings and the like, having improved adhesion and rheology properties | |
| US6335314B1 (en) | Anionic alkoxylate surfactant from conjugated unsaturated alcohol | |
| CN100523006C (en) | Surfactant for emulsion polymerization, polymer emulsion composition obtained with the surfactant, and adhesive for fiber flocking comprising the composition | |
| EP1042370B1 (en) | Polymerisation method | |
| CN1620495A (en) | Alkylglycol alkoxylates or alkyldiglycol alkoxylates, mixtures thereof with tensides and their use | |
| JP4157125B2 (en) | Emulsifier for emulsion polymerization, method for producing polymer emulsion, and polymer emulsion | |
| EP0034893B1 (en) | Compositions for bonding fibrous substrates and cellulosic fibrous substrate treated therewith | |
| JPS5959984A (en) | Thickner and use thereof in printing paste for printing sup-port by transfer printing | |
| DE10163258A1 (en) | Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization | |
| EP0799278B1 (en) | Aqueous polymer emulsions | |
| JP2015521675A (en) | Emulsion polymerization method | |
| JPS6323726A (en) | Novel surface active agent | |
| Breuer et al. | Sulfosuccinates for emulsion polymerization | |
| AU744529B2 (en) | Anionic alkoxylate surfactant | |
| JP2001003270A (en) | Sizing agent | |
| EP1856222B1 (en) | Gum adhesive based on a filled polymer dispersion | |
| JPS63240932A (en) | Novel surfactant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20140311 |