CN1197079A - Copolymerization preparing adhesive from butadiene supermicro emulsion - Google Patents
Copolymerization preparing adhesive from butadiene supermicro emulsion Download PDFInfo
- Publication number
- CN1197079A CN1197079A CN 98100930 CN98100930A CN1197079A CN 1197079 A CN1197079 A CN 1197079A CN 98100930 CN98100930 CN 98100930 CN 98100930 A CN98100930 A CN 98100930A CN 1197079 A CN1197079 A CN 1197079A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- formula
- accounts
- methyl
- tackiness agent
- 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.)
- Pending
Links
Abstract
A superfine emulsion copolymerization process for preparing adhesive used in print dying, paper making and leather fields uses butadiene as primary monomer and other unsaturated vinyl monomers, and features that its product has higher performance.
Description
The invention belongs to emulsion type binder.Can be applicable to the pigment printing of fabric, and be widely used in fields such as papermaking, leathers.
Because the three wastes are many, cost is high, complex process, dye printing proportion in whole stamp industry is fewer and feweri, and pigment printing is occupying increasing proportion.In the whole world, pigment printing has accounted for more than 60% of stamp total amount.Because of printing assistant particularly the level of pigment printing binding agent limit, also have the part stamp to adopt dye printing.Domestic used tackiness agent all is to be copolymer emulsion (the Chinese tackiness agent-1995 of main monomer with the acrylate at present, 4 (5)--38-43), its maximum shortcoming is exactly a Boardy Feeling, and the flexibility of polymeric film is a very important application indexes of pigment printing binding agent.For this reason, it should not print big area flower type, also should not print thin quality lining and knit fabric, and for silk fabrics, artificial cotton lining, towel product etc., the domestic printing technology that can only adopt reactive dyestuffs has greatly limited the use range of pigment printing.In addition, because under the general letex polymerization condition, the polymer particle particle diameter is all more than 100nm.Like this, melt when forming film, just need higher film-forming temperature at it.And, melt knot film forming compactness, smooth finish, smoothness is also bad.
Once developed styrene-butadiene latex abroad and be applied to pigment printing binding agent the fifties, though soft, fastness is too low, replaced by the acrylic ester tackiness agent very soon.The eighties, there is styrene-butadiene latex to be applied to the report of pigment printing binding agent again, as German patent DE 35 25 799.It has introduced internal crosslinker, has improved printing fastness, but compares with the acrylic ester tackiness agent, also has gap, does not also improve aspect other application performances.
For solving the deficiency that above-mentioned technology exists, on tackiness agent, reach unification flexible and fastness, the present invention is principal monomer with the divinyl, adopts with other unsaturated vinyl monomer ultra micro emulsion copolymerizations to prepare tackiness agent.It mainly has following feature:
At first, this tackiness agent has strengthened the fastness of polymeric film greatly by introducing the characteristic component vulcanizing agent, has changed the situation that the acrylic ester adhesive surface is clamminess, and printing fastness is improved greatly.Vulcanizing agent is widely used in rubber industry, but the report that is applied in the tackiness agent is not also arranged.
Secondly, we adopt the ultra micro letex polymerization.Conventional emulsions belongs to colloidal dispersion, and particle diameter is between the 100--1000nm mostly.And the ultramicron polymer emulsion, its particle diameter below 100nm, is the dispersion system between solution and colloid generally.Therefore, its stability and solution are similar, are higher than the stability of colloidal dispersion.And the particle of this size can penetrate into and go in the fabric fibre, and is even in the inside and the surface arrangement of fabric, can make fabric have similar natural color behind the stamp.After the more important thing is polymer film forming, particle can form small discontinuous phase, makes the film forming softness, has good hand feeling more.In addition, general polymerization thing emulsion only just can be melted more than minimum film-forming temperature (MFT) and formed film, and particle diameter is big more, and MFT is high more, and the smoothness after the film forming, smoothness are also bad.The present invention adopts ultramicrotechnique, can not only improve the performance of polymeric film, can also make tackiness agent film forming at room temperature simultaneously, promptly can use as low-temperature adhesive, reduces the working conditions of tackiness agent.Ultramicrotechnique is not appeared in the newspapers on butadiene copolymer production adhesive application both at home and abroad.Divinyl is cheap in addition, compares with the acrylic ester tackiness agent, and tackiness agent cost of the present invention reduces greatly, can be on a good wicket in market competition.
In leather was used, this tackiness agent can be used as arrangement and uses with tackiness agent.Now general all is the acrylic ester tackiness agent, the leatherware surfaces of tacky after the covering with paint.Because this tackiness agent is introduced vulcanizing agent, has improved the polymkeric substance film strength, thereby has strengthened the fastness to rubbing of leather surface.By adopting the micro emulsion polymerization, make the epithelium of formation finer and close, improved water tolerance, and any surface finish, folding resistance are good, have fabulous elasticity and flexibility simultaneously.In addition, because the second-order transition temperature lower (108 ℃) of dienite, also corresponding very low based on its second-order transition temperature of tackiness agent.Thereby the leatherware after it is covered with paint, lacquer, colour wash, etc. also has good use properties at low temperatures.
In papermaking is used,, also has certain moisture owing to this tackiness agent excellent water tolerance, folding resistance, wear resistance.This tackiness agent can be used as the coating adhesive for paper, be coated with jelly, soaker uses.
By the application test in pigment printing, leather, papermaking, this tackiness agent has has all met or exceeded national standard, has obtained good use properties.
This tackiness agent is made up of monomer component, vulcanizing agent, emulsifying agent, initiator, water soluble alcohols and water.Monomer component comprises that A, B, C, D, E component A are divinyl, the 40--70% of this ingredients constitute total monomer weight.Make its polymkeric substance have good flexibility and elasticity behind the butadiene copolymer.B component is the esters of acrylic acid with following general formula: CH
2=CH-COOR wherein R represents the alkyl of 1--8 carbon atom.The 0--30% of this ingredients constitute total monomer weight.But the film forming speed of this component telomerized polymer also can increase the flexibility of polymkeric substance.This component can not add yet.Component C contains a kind of following unsaturated rigidity monomer at least: methyl acrylic ester, (methyl) vinyl cyanide, vinyl acetate, vinylbenzene and derivative thereof.The 10--50% of this ingredients constitute total monomer weight.This component can increase the polymkeric substance film strength, makes tackiness agent have certain fastness.Component D is the unsaturated monomer that contains amido, hydroxyl, N--alkane methoxyl group, the hot active group of N--methoxyl group: (methyl) vinylformic acid hydroxyl second (third) ester, (methyl) acrylamide, N--methyl (methyl) acrylamide, N--methylol (methyl) acrylamide, N--alkoxyl group (methyl) acrylamide, vinylcarbinol etc.The 0--15% of this ingredients constitute total monomer weight.This component is a linking agent, by the crosslinked bond strength that improves polymkeric substance between polymer macromolecule.Fastness such as can improve dry grinding, wet-milling in application, scrub, this component can not add yet.Component E is the unsaturated monomer of carboxylic-acid, as: vinylformic acid, methacrylic acid, furoate clothing, vinylformic acid sulfonic acid etc.The 0--20% of this ingredients constitute total monomer weight.This component provides catalyzer in the time of can carrying out crosslinking reaction for component D on the one hand, and when polymer film forming, the carboxyl that himself has can also provide certain crosslinked group on the other hand.This binder monomer mixture accounts for the 20--60% of emulsion system gross weight, wherein the use properties of the relative proportion of A+B+C+D+E=100% monomer component A, B, C decision polymkeric substance.(A+B)/C characterize to use in to fastness and flexible requirement, its proper ratio is 1-10.Vulcanizing agent: the compound that contains following formula:
H--S--R--S--H wherein R can be C
4-12Alkyl, phenyl, xenyl.
H--O--R--O--H wherein R is C
4-12Alkyl.
This component contains two two keys, can promote being cross-linked with each other of polymkeric substance, improves the film strength of polymkeric substance, changes the character of the film of polymkeric substance.It accounts for the 0.1-1% of total monomer weight.
Emulsifying agent adopts mixed emulsifier, comprises that anionic and nonionic emulsifier are shared.
Anionic emulsifier, its weight are the 1--7% of total monomer weight.Comprise:
The carboxylate salt general formula is that M represents metal (down together) in the RCOOM formula, and R can be C
7-21Alkyl, aryl and other groups.
The alkyl-sulphate general formula is ROSO
3R is C in the M formula
8-18Alkyl.
The sulfated oil general formula is R (OSO
3M) R and R ' are alkyl in COOR ' formula.
Aliphatic amide vitriol general formula is RCONHCH
2CHR ' OSO
3M, R and R ' are alkyl in the formula.
Fat sulfonate general formula is RSO
3R is an alkyl in the M formula.
Fatty amide Sulfonates general formula is RCONR ' CH
2CH
2SO
3R and R ' are alkyl in the M formula.
The alkyl benzene sulfonate general formula is RC
6H
4SO
3R is C in the M formula
12-16Alkyl.Nonionic emulsifier: its weight is the 1-7% of total monomer weight.Comprise:
Polyoxyethylene carboxylicesters general formula is RCOO (CH
2CH
2O)
mR is an alkyl in the H formula, m=1--30.
Polyol carboxylate's general formula is
R is an alkyl in the formula.
The polyethylene oxide alkyl ethers general formula is RO (CH
2CH
2O)
nR is an alkyl in the H formula, n=1-30.
Polyoxyethylene alkyl aryl ether general formula is RC
6H
4O (CH
2CH
2O)
nR is an alkyl in the H formula.
Initiator:adopt chemical initiator, comprise water miscible Potassium Persulphate, Ammonium Persulfate 98.5, hydrogen peroxide, and the redox system etc. that is added with sodium bisulfite, ferrous sulfate etc.Oil-soluble initiator comprises azo-bis-isobutyl cyanide, benzoyl peroxide etc.The 0.1--0.8% of this ingredients constitute total monomer weight.Water soluble alcohols:comprise water soluble alcohols such as butanols, amylalcohol.This component can make the emulsion ultramicronising on the one hand, can play the effect of film coalescence aid on the other hand again.It accounts for the 5--15% of emulsion gross weight. building-up process of the present invention is as follows: (1). with emulsifying agent water-soluble (2). with initator water-soluble (3). (1) (2) are joined (4) in the reactor. monomer component (ABCDE) and vulcanizing agent are joined in the reactor (5) stir emulsify at a high speed with 400--1000 rev/min, form emulsion (6) be warming up to reaction temperature required (40--80 ℃) (7) with 40--150 rev/min of stirring react (8) after 2--10 hour (9) the resulting polymers emulsion is added ammoniacal liquor, NaOH or potassium hydroxide solution are neutralized to PH=7--8 (10) and drip the end that is translucent of water soluble alcohols to product with (11) after 400--1000 rev/min of high-speed stirred 1--2 hour under high-speed stirred
Monomer conversion of the present invention can reach more than 95%.In continuous reaction, can reduce the reaction times, the later stage is carried out MONOMER RECOVERY.
The present invention adopts each monomer component to carry out ultra micro method of emulsion polymerization synthetic copolymer ultra micro emulsion in water.Its outward appearance is translucent, has good storage stability.Can be in the printing and dyeing industry at cotton, polyester-cotton blend, wash, carry out pigment printing on the material such as real silk, silk, also can on tricot, towel, sheet etc., carry out the big area stamp.Can also use as paper soaker, paper finishing agent, pulp additive, hide finishes.And can be used as low-temperature adhesive and use.
The present invention is through the practical application of aspects such as pigment printing, leather, papermaking, and is respond well.Especially aspect pigment printing, flexible all good with fastness, reached the unification of height.And be applicable to multiple printing technology, be the outstanding tackiness agent kind of a class.
Example 1. is got sodium lauryl sulphate 1.0 grams, emulsifier os-15 (alkyl polyoxyethylene (15) ether) 2.1 grams, and N--n-methylolacrylamide 5 grams, Potassium Persulphate 0.1 gram is dissolved in the 900 gram water, joins in 2 liters of reactors.Add vinylformic acid 10 grams, divinyl 160 grams, fine 50 grams of propylene, vinylbenzene 50 grams, methyl acrylate 50g, vulcanizing agent 1 gram again, emulsify at a high speed becomes emulsion, be warming up to 50 ℃, 100 rev/mins of stirrings were reacted 6 hours down, be neutralized to PH=7-8 with 15% ammoniacal liquor, after 1 hour, stir dropping butanols 140 grams down with 400 rev/mins of stirrings again in this, stopped reaction when emulsion is translucent state, discharging.Obtain the 1# product.
Example 2. is got Sodium dodecylbenzene sulfonate 2 grams, emulsifier op-10 (alkylphenol-polyethenoxy (10) ether) 3 grams, N--n-methylolacrylamide 6 grams, Ammonium Persulfate 98.5 1.2 grams, is dissolved in the 900 gram water, joins in 2 liters of reactors.Add vinylformic acid 12 grams, divinyl 200 grams, vinyl cyanide 100 grams, methyl acrylate 50 grams, vulcanizing agent 1.2 grams again, emulsify at a high speed becomes breast.Be warming up to 60 ℃, 100 rev/mins of stirrings reaction 4 hours down is neutralized to PH=7-8 with 15% ammoniacal liquor, stir one hour with 400 rev/mins again after, stir in this and to drip amylalcohol 100 grams down, stopped reaction when emulsion is translucent state, discharging.Obtain the 2# product.
The consumption of example 3. emulsifying agents, initiator, internal crosslinker, vinylformic acid, water adds divinyl 200 grams, vinylbenzene 100 grams, vinyl cyanide 50 grams, Butyl acrylate 50 grams, vulcanizing agent 1.0 again with example 1, and other preparation process are with example 1.Obtain the 3# product.
The consumption of example 4. emulsifying agents, initiator, internal crosslinker, vinylformic acid, water is with example 2.Add divinyl 220 grams, vinylbenzene 100 grams, ethyl propenoate 50 grams, vulcanizing agent 1.3 grams again, other preparation process are with example 1.Obtain the 4# product.
The consumption of example 5. emulsifying agents, initiator, water is with example 1.Add methacrylic acid 10 grams, divinyl 180 grams, vinylbenzene 230 grams again, other preparation process are with example 2.Obtain the 5# product.
The consumption of example 6. emulsifying agents, initiator, water is with example 2.Add N--methylol methacrylamide 4 grams, vinylformic acid 11 grams, divinyl 200 grams, vinyl cyanide 210 grams, vulcanizing agent 2 grams again, other preparation process are with example 2.Obtain the 6# product.
More than in 6 examples, 1#, 2#, 3#, 4# product can be used for pigment printing binding agent, the 5# product can be used for being coated with adhesive for paper, the 6# product can be used for hide finishes.
Now product performance and the application result with example 1 is listed below:
One. performance test:
1. solid content: 27%
2. viscosity: 65cp
3.PH：7.1
4. granularity: 40-50nm.
Testing method:
1. solid content: weighting method places tackiness agent under 80--100 ℃ to dry to constant weight.
2. viscosity: NDJ-1 type viscometer
3.PH:PH meter.
4. granularity: light scattering method.
Two. application result:
Get 1# products with adhesive agent 15 gram, thickening material 3 grams, blue mill base 5 grams, water 77 grams and break into printing paste, be applied on the fabric, give baking (100 ℃) → bake (150 ℃ 2 minutes), the result is as follows:
1. network blocking performance: not network blocking in 45 minutes.
2. feel: softness.
3. fastness, yellowing test: see the following form
Annotate: the fastness test on silk broadcloth, Nylon Taffeta is to test by testing method cotton, polyester-cotton blend.Testing method:
1. network blocking performance: the slurry for preparing is placed in the printed board, at room temperature place 45 minutes after, print again, reciprocal more than 100 times.
2. fastness: press GB250-64.
3. yellowing test: basic slurry is applied on the calico, and 190 ℃ of bakings were observed in 3 minutes.
Claims (7)
1. emulsion type binder that is used on pigment printing, papermaking, the leather, it is characterized in that being is that principal monomer and other unsaturated vinyl monomers are main component with the divinyl, add vulcanizing agent, initiator, water-soluble alcohol and water, adopt the ultra micro emulsion polymerisation process to prepare.
(1) monomer component comprises:
A is a divinyl
B is the esters of acrylic acid with following general formula: CH
2=CH-COOR wherein R is C
1-8Alkyl.
C is for containing a kind of following unsaturated rigidity monomer at least: methyl acrylic ester, vinylchlorid, vinyl acetate, (methyl) vinyl cyanide, vinylbenzene and derivative thereof.
D is the unsaturated monomer that contains amido, hydroxyl, N-alkoxyl-methyl or N-methoxyl group active group, as: (methyl) vinylformic acid hydroxyl second (third) ester, (methyl) acrylamide, N--methyl (methyl) acrylamide, N--methylol (methyl) acrylamide, N--alkoxyl group (methyl) acrylamide, vinylcarbinol, (methyl) acrylic acid epoxy ester etc.
E is the carboxylic-acid unsaturated monomer: vinylformic acid, methacrylic acid, furoate clothing, vinylformic acid sulfonic acid etc.(2) vulcanizing agent: compound with following general formula:
H-S-R-S-H wherein R can be C
4-12Alkyl, phenyl, xenyl.
H-O-R-O-H wherein R is C
4-12Alkyl.(3) water-soluble alcohol: as butanols, amylalcohol etc.(4) adopt mixed emulsifier, comprise that employing anionic and non-ionic type are shared.Anionic emulsifier comprises: have following general formula:
M represents metal (down together) in the metal carboxylate RCOOM formula, and R is C
7-21Alkyl, aryl and other groups.
Alkylsurfuric acid salt ROSO
3R is C in the M formula
8-18Alkyl.
Sulfated oil R (OSO
3M) R and R ' are alkyl in COOR ' formula.
Aliphatic amide vitriol RCONHCH
2CHR ' OSO
3R and R ' are alkyl in the M formula.
Fat sulfonate RSO
3R is an alkyl in the M formula.
Fatty amide sulfonate RCONR ' CH
2CH
2SO
3R and R ' are alkyl in the M formula.
Alkyl benzene sulfonate RC
6H
4SO
3M, R is C in the formula
1-6Alkyl.Nonionic emulsifier comprises:
Polyoxyethylene carboxylicesters RCOO (CH
2CH
2O)
mR is an alkyl in the H formula, m=1-30.
The polyol carboxylate
R is an alkyl in the formula.
Polyethylene oxide alkyl ethers RO (CH
2CH
2O)
nR is an alkyl in the H formula, and n is 1-30.
Polyoxyethylene alkyl aryl ether RC
6H
4O (CH
2CH
2O)
nBe alkyl in the H formula, n is 1--30.(5) adopt the chemical initiator initiated polymerization
Initiator comprises water miscible Potassium Persulphate, Ammonium Persulfate 98.5, hydrogen peroxide and is added with redox system of sodium bisulfite, ferrous sulfate etc. etc.Oil-soluble initiator such as azo-bis-isobutyl cyanide, benzoyl peroxide etc.
2. tackiness agent according to claim 1, it is characterized in that monomer component A in the tackiness agent accounts for the 40-70% of total monomer weight, B component accounts for the 0-30% of total monomer weight, component C accounts for the 10-50% of total monomer weight, component D accounts for the 0-15% of total monomer weight, component E accounts for the 0-15% of total monomer weight, A+B+C+D=E=100%.
3. according to claim 1,2 described tackiness agents, it is characterized in that monomer component (A+B) and the weight ratio of C are (A+B)/C=1-10.
4. tackiness agent according to claim 1, it is characterized in that the vulcanizing agent that adds in the tackiness agent accounts for the 0.1-1% of total monomer weight, water-soluble alcohol accounts for the 5-15% of emulsion gross weight, the anionic emulsifier that adds accounts for the 1-7% of total monomer weight, nonionic emulsifier accounts for the 1-7% of total monomer weight, and initiator accounts for the 0.1-0.8% of total monomer weight.
5. tackiness agent according to claim 1 is characterized in that monomer mixture gross weight in the tackiness agent accounts for the 20-60% of emulsion gross weight.
6. tackiness agent according to claim 1, the present invention adopts each monomer component to carry out ultra micro method of emulsion polymerization synthetic copolymer ultra micro emulsion in water.
7. tackiness agent according to claim 1, it is characterized in that tackiness agent of the present invention can be in printing and dyeing industry at cotton, polyester-cotton blend, wash, carry out pigment printing on the real silk, silk, also can be on tricot, towel, sheet stamp.Can also use as paper soaker, paper finishing agent, pulp additive, hide finishes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100930 CN1197079A (en) | 1998-03-19 | 1998-03-19 | Copolymerization preparing adhesive from butadiene supermicro emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100930 CN1197079A (en) | 1998-03-19 | 1998-03-19 | Copolymerization preparing adhesive from butadiene supermicro emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1197079A true CN1197079A (en) | 1998-10-28 |
Family
ID=5216349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98100930 Pending CN1197079A (en) | 1998-03-19 | 1998-03-19 | Copolymerization preparing adhesive from butadiene supermicro emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1197079A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415985C (en) * | 2005-12-21 | 2008-09-03 | 上海迪纺纺织科技有限公司 | Separating treatment agent for transferring printing paper |
| CN100445331C (en) * | 2000-10-17 | 2008-12-24 | 国家淀粉及化学投资控股公司 | Aqueous polymer solution |
| CN1962517B (en) * | 2005-11-10 | 2010-06-16 | 周华 | Environment-friendly formaldehyde-free glass wool adhesive |
| CN113072661A (en) * | 2021-04-13 | 2021-07-06 | 长春工业大学 | Preparation method of large-particle-size polybutadiene latex |
-
1998
- 1998-03-19 CN CN 98100930 patent/CN1197079A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445331C (en) * | 2000-10-17 | 2008-12-24 | 国家淀粉及化学投资控股公司 | Aqueous polymer solution |
| CN1962517B (en) * | 2005-11-10 | 2010-06-16 | 周华 | Environment-friendly formaldehyde-free glass wool adhesive |
| CN100415985C (en) * | 2005-12-21 | 2008-09-03 | 上海迪纺纺织科技有限公司 | Separating treatment agent for transferring printing paper |
| CN113072661A (en) * | 2021-04-13 | 2021-07-06 | 长春工业大学 | Preparation method of large-particle-size polybutadiene latex |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101220563B (en) | Environment protection type pigment resin printing adhesive agent capable of self crosslinking at low-temperature, and preparation thereof | |
| CN104672403B (en) | A kind of environmentally friendly silicone acrylic emulsion and preparation method thereof | |
| CN102605648B (en) | Textile water-based pigment printing binding agent and preparation method | |
| EP0376684B1 (en) | Process for preparing polymer emulsion particles having pores | |
| CN102766233B (en) | Disperse printing thickener and preparation method thereof | |
| CN102127186B (en) | Method for preparing fluorine-containing silicon acrylate emulsion | |
| US5563201A (en) | Aqueous papercoating compositions comprising a substantially H2 O-insoluble, alkali-soluble latex | |
| EP0013836A1 (en) | Compositions containing acrylic emulsion copolymers and their use as thickeners | |
| US5219969A (en) | Crosslinked copolymers with crosslinkable groups based on acrylic or methacrylic acid, preparation thereof and use thereof | |
| JPH0627155B2 (en) | Emulsion copolymer containing alkyl acrylamide for thickening | |
| CN112062918B (en) | Method for synthesizing polymer/pigment hybrid latex by copolymerization of sulfur-free and soap-free in-situ RAFT (reversible addition-fragmentation chain transfer) emulsion | |
| CN1939946B (en) | Production of modified paste and dye printing paste | |
| CN105713131A (en) | Styrene-acrylic emulsion, preparation method and application thereof | |
| CN104109975A (en) | Modified acrylate printing emulsion and preparation method thereof | |
| CN106496451A (en) | A kind of imitative reactive coating printing adhesive copolymer and preparation method thereof | |
| GB1595248A (en) | Butadiene-styrene latices thickened with terpolymer emulsions | |
| CN106988134A (en) | A kind of printing adhesive and preparation method thereof, print paste and clothes | |
| CN101698980A (en) | Environmentally-friendly anti-flushing synthetic printing thickener and preparation method thereof | |
| CN108314755B (en) | Emulsion for environment-friendly pigment printing adhesive and preparation method and application thereof | |
| CN1197079A (en) | Copolymerization preparing adhesive from butadiene supermicro emulsion | |
| CN115028770B (en) | Aqueous acrylic ester emulsion adhesive and preparation method and application thereof | |
| DE60104334T2 (en) | FORMALDEHYDE-FREE NETWORKED CORE-BOWL-LATEX FOR TEXTILES | |
| CN108301235A (en) | A kind of resistance to washing and dry burning crock fastness elevator and preparation method thereof | |
| CN102108110A (en) | Method for preparing acrylate printing adhesive | |
| EP0209029B1 (en) | Binder for the pigment printing of textile materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |