CN113185635B - Low-odor stain-resistant emulsion for interior walls and preparation method thereof - Google Patents

Low-odor stain-resistant emulsion for interior walls and preparation method thereof Download PDF

Info

Publication number
CN113185635B
CN113185635B CN202010038572.4A CN202010038572A CN113185635B CN 113185635 B CN113185635 B CN 113185635B CN 202010038572 A CN202010038572 A CN 202010038572A CN 113185635 B CN113185635 B CN 113185635B
Authority
CN
China
Prior art keywords
emulsion
monomer
weight
monomers
emulsifier
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.)
Active
Application number
CN202010038572.4A
Other languages
Chinese (zh)
Other versions
CN113185635A (en
Inventor
贾贵玉
张伟辉
马吉全
纪晓晓
纪学顺
景传明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202010038572.4A priority Critical patent/CN113185635B/en
Publication of CN113185635A publication Critical patent/CN113185635A/en
Application granted granted Critical
Publication of CN113185635B publication Critical patent/CN113185635B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses an interior wall low-odor stain-resistant emulsion and a preparation method thereof, wherein the emulsion contains at least one vinyl polymer, and the polymer comprises the following polymerized monomers in percentage by weight based on the total amount of the polymer: (a) 5% -35% by weight of dodecyl to octadecyl (meth) acrylate; (b) from 1% to 14% by weight of an itaconate ester monomer; (c) from 0.1% to 10% by weight of an unsaturated hydrophilic monomer; (d) From 41% to 93.9% by weight of other ethylenically unsaturated monomers other than (a), (b) and (c). The emulsion of the invention is used as polymer emulsion and emulsion paint without adding film forming assistant, and the emulsion paint prepared by the emulsion has low smell and good stain resistance, is beneficial to ensuring the safety of human body and improving the pollution of walls.

Description

Low-odor stain-resistant emulsion for interior walls and preparation method thereof
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to low-odor stain-resistant emulsion for an inner wall and a preparation method thereof.
Background
Decoration pollution seriously affects the health of people, and through analysis, formaldehyde and other Volatile Organic Compounds (VOC) are main components generating indoor pollution, and how to remove the pollution of the indoor formaldehyde and VOC after decoration is a difficult problem existing in the industry at present. On the other hand, the wall is contaminated by stains inevitably in life, the paint film is difficult to clean after being contaminated, and the beauty of the wall is affected after long-term storage. Therefore, the low-odor inner wall stain-resistant emulsion has good market prospect.
The VOC materials in latex paints have different chemical properties including residual monomers in the emulsion, impurities in the monomers, film-forming aids, anti-freeze agents and other VOCs generated during the reaction, and therefore reducing the content of these materials is the key to reducing the VOC in latex paints. In order to realize better stain resistance in the prior art, the glass transition temperature of the polymer in the emulsion is required to be higher, the higher glass transition temperature can realize better film forming effect only by virtue of a film forming aid, but the addition of the film forming aid increases the integral VOC content of the coating, so that the key for preparing the low-odor inner wall stain resistant emulsion is to solve the problems of film forming property, stain resistance and VOC content of the emulsion paint without adding the film forming aid.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the inner wall low-odor stain-resistant emulsion which is used as a polymer emulsion and an emulsion paint without adding a film-forming assistant, and the emulsion paint prepared by the emulsion has low odor and good stain resistance, is beneficial to ensuring the safety of human bodies and improving the wall pollution.
In order to achieve the purpose, the emulsion adopts the following technical scheme:
an interior wall low odor stain resistant emulsion comprising at least one vinyl polymer, wherein the polymer comprises, as polymerized monomers:
(a) 5% -35% by weight of dodecyl to octadecyl (meth) acrylate;
(b) From 1% to 14% by weight of an itaconate ester monomer of formula I:
Figure BDA0002366917600000021
wherein R and R are independently alkyl or aryl, preferably independently methyl, ethyl, butyl or aryl;
(c) 0.1% to 10% by weight of an unsaturated hydrophilic monomer;
(d) From 41% to 93.9% by weight of other ethylenically unsaturated monomers other than (a), (b) and (c);
wherein the total weight of the polymerized monomers (a), (b), (c) and (d) is 100%.
All parenthetical phrases in the present invention mean either or both of the two cases including parenthetical content or not including parenthetical content. For example, in the text, "allyl (meth) acrylate" refers to one of allyl acrylate, allyl methacrylate, or a mixture thereof. In the present invention, unless otherwise specified, all percentages are by mass.
In one embodiment, as polymerized monomer (a) dodecyl to octadecyl (meth) acrylate, e.g. tridecyl (meth) acrylate or tetradecyl (meth) acrylate, is preferably used in an amount of 10% to 30%, such as 12%, 15%, 20%, 25% or 28%.
In one embodiment, the itaconate ester monomer as polymerized monomer (b) is used in an amount of 6% to 12%, such as 7%, 8% or 10%; the itaconate ester monomer may be, for example, dimethyl itaconate or dibutyl itaconate.
In one embodiment, the weight of unsaturated hydrophilic monomer as polymerized monomer (c) is from 0.5% to 2%, such as 0.8%, 1%, or 1.5%; in the present invention, the hydrophilic group of the unsaturated hydrophilic monomer of the polymerized monomer (c) may be at least one selected from the group consisting of a carboxyl group, a hydroxyl group, an amide group, a sulfonic acid group, a phosphate group, a urea group, a sulfonate group, a sulfate group, and a phosphate group, for example, the monomer (c) is acrylic acid.
In the present invention, the polymerizable monomer (d) is another ethylenically unsaturated monomer other than the above-mentioned (a), (b) and (c), and in one embodiment, is used in an amount of 56% to 78%, such as 60%, 65%, 70% or 76%, in the polymerizable monomer. In the present invention, the other ethylenically unsaturated monomers of the polymeric monomer (d) include linear monomers, crosslinking monomers and functional monomers, wherein the linear monomer weight is 41% to 80%, preferably 56% to 76%, such as 60%, 61.5%, 63.5%, 70% or 71%; the crosslinking monomer is present in an amount of 0-5%, preferably 0-2%, such as 0.5%, 1% or 1.5% by weight; the weight of the functional monomer is 0-10%, preferably 0-7%, such as 0.2%, 1%, 3% or 5%; the above weight fractions are based on the total weight of the polymerized monomers.
In the present invention, the linear monomer may be one or more of monomers having a single double bond, preferably one or more of styrene, alkyl (meth) acrylate having an alkyl group of 1 to 8 carbons in length, allyl ester, and vinyl ester; more preferably one or more of styrene, alkyl methacrylate with alkyl length of 1-4 carbons, alkyl acrylate with alkyl length of 2-8 carbons, vinyl acetate, such as methyl methacrylate or ethyl acrylate.
In the present invention, the crosslinking monomer may be one or more of monomers having two or more double bonds; preferably one or more of divinylbenzene, polyol poly (meth) acrylates, vinyl (meth) acrylates, allyl (meth) acrylates and silicone monomers with double bonds; more preferably one or more of divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate and silicone monomers with double bonds, such as allyl methacrylate.
In the present invention, the functional monomer may be one or more of functional monomers having post-crosslinking and/or formaldehyde scavenging, preferably acetoacetoxyethyl methacrylate or diacetone acrylamide.
In the emulsion of the invention, due to the existence of the vinyl polymer with the composition, the film forming performance is good, and the emulsion can have good film forming effect even without adding or adding little film forming auxiliary agent, in one embodiment, the interior wall low-odor stain-resistant emulsion does not contain the film forming auxiliary agent and also does not contain an antifreeze agent, wherein the film forming auxiliary agent usually comprises ethylene glycol butyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, taxanol and the like, and the antifreeze agent usually comprises ethylene glycol, propylene glycol, FT-100 and the like. In one embodiment, the vinyl polymer content of the emulsion may be 40% to 55%, such as 45%, 48% or 50%.
It is understood by those skilled in the art that the emulsion of the present invention is usually added with an emulsifier, an initiator and a neutralizing agent in preparation, and a post-treatment agent according to actual needs; in one embodiment, the interior wall low odor stain resistant emulsion further comprises added emulsifiers, initiators, neutralizers and post-treatment agents. In one embodiment, the mass of emulsifier in the emulsion may be 2% to 5%, such as 3% or 4%, of the vinyl polymer.
The invention also provides a preparation method of the low-odor stain-resistant emulsion for the interior wall, which comprises the following steps:
1) Adding an emulsifier, deionized water and the polymerization monomer into a pre-emulsification kettle, and fully stirring to prepare a pre-emulsion;
2) Adding a part of initiator into deionized water to dissolve to obtain a dropwise added initiator;
3) Adding a part of initiator into deionized water to dissolve to obtain a kettle bottom initiator solution;
4) Adding an emulsifier and deionized water into a reaction kettle, fully stirring and dissolving, heating to 80-90 ℃, adding part of the pre-emulsion obtained in the step 1) into the reaction kettle, adding the kettle bottom initiator solution obtained in the step 3) after uniformly stirring, and reacting to obtain a seed emulsion;
5) After the reaction in the step 4) is finished, controlling the reaction temperature to be 80-90 ℃, gradually adding the residual pre-emulsion prepared in the step 1) and the dropwise adding initiator in the step 2), and then carrying out heat preservation treatment;
6) Cooling the reaction kettle to 70-80 ℃, adding a pH regulator, regulating the pH of the system to 7-9, gradually adding an after-treatment agent into the reaction kettle, and then carrying out heat preservation treatment;
7) Cooling to below 45 ℃, filtering and discharging.
In the present invention, the emulsifier used includes anionic emulsifiers and nonionic emulsifiers. The anionic emulsifier can comprise non-polymerizable and polymerizable anionic emulsifiers, wherein the non-polymerizable anionic emulsifier can be one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate and alkyl alcohol ether phosphate, and the polymerizable anionic emulsifier can be one or more of sodium p-styrene sulfonate, sodium allyl ether hydroxypropyl propane sulfonate and sodium vinyl sulfonate, such as sodium 3-allyloxy-2-hydroxy-1-propane sulfonate. The nonionic emulsifier can be at least one of polyoxyethylene carboxylate, polyoxyethylene polyalcohol carboxylate, C9-C16 alkyl polyoxyethylene ether, aralkyl polyoxyethylene ether with 1-3 benzene rings, and C9-C16 fatty alcohol ethoxylate, such as isomeric tridecanol polyoxyethylene ether.
In one embodiment, the emulsifier may be a combination of a nonionic emulsifier, a non-polymeric anionic emulsifier, a reactive anionic emulsifier. The non-ionic emulsifier is adopted, so that the polymer latex has excellent electrolyte stability on one hand, and can be adsorbed on the surface of latex particles on the other hand, so that the polymer latex has excellent freeze-thaw stability at a lower glass transition temperature. The non-polymeric anionic emulsifier is adopted to make the surface of the emulsion particle have a layer of negative charges, so that the mechanical stability of the emulsion and the stability in the polymerization process can be effectively improved. By introducing the polymeric anionic emulsifier, the polymerization stability is improved, and meanwhile, the migration from the interior of a paint film to the surface is avoided in the film forming process of the paint film, so that the water resistance and the gloss of the paint film can be effectively improved. The mass ratio of the amount of nonionic emulsifier to the amount of anionic emulsifier is, for example, (0.4-0.6): 1, for example 0.5:1 or 0.55; the ratio of the non-polymerizable anionic emulsifier to the polymerizable anionic emulsifier is, for example, 1.
In one embodiment, step 1) is adding more than 90%, such as 94%, 95% or 98%, of the non-polymerizable anionic emulsifier, all of the non-ionic emulsifier, 25 to 35%, such as 28%, 30% or 32%, of all of the deionized water, and all of the ethylenically unsaturated monomers to a pre-emulsification vessel, and stirring thoroughly to prepare a pre-emulsion;
in one embodiment, step 2) is adding 30 to 50% of the initiator, such as 35%, 40% or 45% of the total amount of the initiator, to 1 to 6% of deionized water, such as 2%, 4% or 5% of the total amount of the deionized water, and dissolving to obtain a dropwise addition initiator;
in one embodiment, step 3) is adding the remaining initiator to 1-6% deionized water, such as 2%, 4% or 5% deionized water, to obtain a kettle bottom initiator solution;
in one embodiment, in the step 4), adding the rest of the non-polymeric anionic emulsifier and the rest of the deionized water into a reaction kettle, fully stirring and dissolving, heating to 80-90 ℃, adding 1-8% of the pre-emulsion in the step 1), such as 2%, 4%, 5% or 6%, into the reaction kettle, adding the initiator solution at the bottom of the step 3) after uniformly stirring, and reacting for 10-20 minutes to obtain a seed emulsion;
in one embodiment, in step 5), after the reaction in step 4) is completed, the reaction temperature is controlled to be 80-90 ℃, the residual pre-emulsion prepared in step 1) and the dropwise adding initiator in step 2) are added within 3-4 h, and the temperature is kept for 20-60 min, such as 30, 40 or 50min;
in one embodiment, the step 6) is to cool the reaction kettle to 70-80 ℃, add a pH regulator, adjust the pH of the system to 7-9, add a post-treatment agent to the reaction kettle within 20-60 min, such as 30, 40 or 50min, and keep the temperature for 30-60 min, such as 40 or 50min;
the addition of initiators in the above preparation is well known in the art and in one embodiment the amount of initiator is 0.1 to 0.8%, preferably 0.2 to 0.6% by weight of the vinyl polymer; wherein, the initiator used can be one or more of sodium persulfate, potassium persulfate and ammonium persulfate, and is added in two steps, such as the adding amount ratio of the steps 4) and 5) is 1:1-2:1, for example 1.5; this form of addition is a form of addition commonly used in the art and will not be described in detail here.
It is understood by those skilled in the art that the pH adjusting agent and the post-treating agent are commonly used in the art, and in the present invention, the pH adjusting agent used may be one or more of sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, ethanolamine, dimethylethanolamine, diethanolamine, and triethanolamine; the used post-treatment agent comprises an oxidizing agent, a reducing agent and the like, wherein the used oxidizing agent can be one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent can be one or more of sodium bisulfite, sodium metabisulfite and vitamin C; in one embodiment, the oxidizing agent and the reducing agent are used in amounts of 0.1% to 0.4% by weight, respectively, of the vinyl copolymer.
In one embodiment, the preparation method further comprises performing steam stripping treatment on the product before or after discharging in step 7) to further reduce the VOC content in the emulsion, and the specific steam stripping conditions can be determined by those skilled in the art according to actual situations, and are not described herein again.
Compared with the prior art, the invention has the following advantages:
the emulsion of the invention can be free from adding a film-forming assistant, on one hand, the film has excellent film-forming effect under the condition of not adding the film-forming assistant by the water absorption self-plasticization action of the polymer, on the other hand, the film has excellent stain resistance under the condition of lower glass transition temperature by the long-chain alkyl in the polymer, finally, the effects of purifying formaldehyde in air and further improving the stain resistance of the film can be realized by polymerizing the functional monomer and the crosslinking monomer in the monomer, and meanwhile, the odor and VOC content of the polymer emulsion are further reduced by the single-stage continuous stripping technology treatment of the polymer emulsion, particularly the content of odorous small molecular organic matters (such as tertiary butanol) is kept at an extremely low level. The emulsion paint prepared by the emulsion has low odor and good stain resistance, can purify indoor formaldehyde, ensures the safety of human bodies and improves the wall pollution. In addition, the low-odor interior wall stain-resistant emulsion disclosed by the invention is simple in synthesis process, simple and convenient to operate, low in cost and high in safety.
Detailed Description
The invention will now be further illustrated by the following examples, but is not limited thereto.
The raw materials used in the following examples were as follows:
Figure BDA0002366917600000081
calculation of the glass transition temperature of the polymer:
Figure BDA0002366917600000082
in the formula w 1 ，w 2 ，…w n And
Figure BDA0002366917600000092
the mass fraction of each polymerized monomer in the total monomer and the vitrification temperature value are shown.
The following procedures were used in the following examples:
the stripping process comprises the following steps: the sample was preheated to 55 ℃ in a buffer vessel and then stripped once, twice, three times and four times through a single stage, continuous stripping line. The relative flow rates of air, steam and dispersion in the stripping were 1.
Evaluation of odor: evaluation of odor was performed based on olfactory sensation, and 10 persons were selected to evaluate the odor in the polymer latex tank. The evaluation results were rated on five scales of 1 to 5, as follows:
grade of Unpleasant odor
5 Is free of
4 Light and slight
3 Medium and high grade
2 High strength
1 Severe severity of disease
The coating evaluation formula comprises:
Figure BDA0002366917600000091
Figure BDA0002366917600000101
evaluation of stain resistance: the stain resistance of the paint films was tested according to HG/T4756-2014.
Evaluation of formaldehyde purification efficiency: the formaldehyde purification efficiency of the paint film was tested according to JC/T1074-2008.
Evaluation of the scrub resistance of the paint film: the scrub resistance of the paint film was tested according to GB/T9266-2009.
Low Temperature Coalescence (LTC) evaluation: putty is applied to the A4 high-density asbestos-free fiberboard, the substrate accords with the JC/T412.1-2006 of NAF (non-asbestos), after drying, the putty board is polished to be flat by sand paper, after a 400-micron film making device is used for scraping the film on the A4-size putty board, the putty board is immediately placed into a 3-DEG C low-temperature box, and the cracking condition of the surface of the film is observed for comparison after 4 hours. The degree of cracking was rated on a scale of 1 to 5 as follows:
1= severe cracking
2= medium cracking
3= certain cracking
4= mild cracking
5= no cracking
Example 1: preparation of dimethyl itaconate (DMI) -containing polymer emulsion
A low-odor inner wall stain-resistant emulsion A is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 80g of MMA, 680g of EA, 20g of AA, 120g of DMI and 100g of tridecyl methacrylate were mixed to give a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Example 2: preparation of dibutyl itaconate (DBI) -containing polymer emulsion
A low-odor inner wall stain-resistant emulsion B is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 80g of MMA, 680g of EA, 20g of AA, 120g of DBI and 100g of tridecyl methacrylate were mixed to give a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Odor and LTC evaluation was performed on the a, B samples:
odor and LTC evaluation results of the A and B samples:
Figure BDA0002366917600000121
example 3: preparation of an emulsion containing 20% by weight of tridecyl methacrylate Polymer
A low-odor inner wall stain-resistant emulsion C is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 80g of MMA, 580g of EA, 20g of AA, 120g of DMI and 200g of tridecyl methacrylate were mixed to give a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are added in sequence, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Example 4: preparation of 30% by weight emulsion of tridecyl methacrylate Polymer
A low-odor inner wall stain-resistant emulsion D is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 80g of MMA, 480g of EA, 20g of AA, 120g of DMI and 300g of tridecyl methacrylate were mixed to give a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
LTC and stain resistance evaluations were performed on the A, C, D sample:
A. c, D sample LTC and stain resistance evaluation results:
Figure BDA0002366917600000141
example 5: preparation of an ALMA Polymer emulsion containing 1% by weight
A low-odor interior wall stain-resistant emulsion E is prepared by the following processes:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 140g of MMA, 570g of EA, 20g of AA, 60g of DMI, 200g of tridecyl methacrylate and 10g of ALMA were mixed to obtain a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all initiator solutions, and keeping the temperature for 20min after finishing dropwise adding for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Example 6: preparation of an ALMA Polymer emulsion containing 2% by weight
A low-odor inner wall stain-resistant emulsion F is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 140g of MMA, 560g of EA, 20g of AA, 60g of DMI, 200g of tridecyl methacrylate and 20g of ALMA were mixed to obtain a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
The C, E, F samples were evaluated for LTC and stain resistance:
C. e, F sample LTC and stain resistance evaluation results:
Figure BDA0002366917600000161
example 7: preparation of an AAEM Polymer emulsion containing 3% by weight
A low-odor inner wall stain-resistant emulsion G is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 115g of MMA, 540g of EA, 5g of AA, 100g of DMI, 200g of tridecyl methacrylate, 10g of ALMA and 30g of AAEM were mixed to obtain a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are added in sequence, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Example 8: preparation of an AAEM Polymer emulsion containing 5% by weight
A low-odor inner wall stain-resistant emulsion H is prepared by the following steps:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 115g of MMA, 520g of EA, 5g of AA, 100g of DMI, 200g of tridecyl methacrylate, 10g of ALMA and 50g of AAEM were mixed to obtain a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are sequentially added, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all the initiator solution, and preserving the temperature for 20min after the dropwise adding is finished for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Example 9: preparation of 7% by weight AAEM Polymer emulsion
A low-odor inner wall stain-resistant emulsion I is prepared by the following processes:
1) 10g of sodium lauryl sulfate, 20g of COPS-1, 14.3g of a nonionic emulsifier 3307, 280g of deionized water, 115g of MMA, 500g of EA, 5g of AA, 100g of DMI, 200g of tridecyl methacrylate, 10g of ALMA and 70g of AAEM were mixed to obtain a monomer pre-emulsion (ME).
2) 1.6g of APS and 40g of water were mixed to give a dropwise addition initiator solution.
3) 2.4g of APS and 24g of water were mixed to give a bottom initiator solution.
4) 0.5g of sodium dodecyl sulfate and 500g of deionized water are added into a reaction kettle and heated to 85 ℃ in a nitrogen environment, 50g of pre-emulsion (ME) and all kettle bottom initiator solutions are added in sequence, and the temperature is kept for 10min.
5) Controlling the temperature to be 85 ℃, simultaneously dropwise adding the rest pre-emulsion (ME) and all initiator solutions, and keeping the temperature for 20min after finishing dropwise adding for 3 h.
6) The temperature was reduced to 75 ℃ and MEA was added to neutralize the system to pH 8. 3.5g of t-BHP (70%) solution and 2g of NaHSO3 (dissolved in 40g of deionized water) were added dropwise to the reaction vessel over 30min, and the temperature was maintained for 30min.
7) Cooling to below 45 ℃, filtering and discharging.
Evaluation of formaldehyde purification efficiency performance was performed on the E, G, H, I sample:
E. 5363 evaluation results of formaldehyde purification efficiency of a G, H, I sample:
Figure BDA0002366917600000181
Figure BDA0002366917600000191
example 10: stripping of polymer latex
Sample J: sample H was subjected to a single stripping.
Sample K: sample H was twice stripped.
Sample L: sample H was stripped three times.
Sample M: sample H was stripped four times.
Figure BDA0002366917600000192
The coating is prepared from the prepared emulsion according to the following formula:
the paint formulation was formulated using the emulsion of sample F in example 6:
evaluation formula Amount of material
Water (I) 180
Hydroxyethyl cellulose ether 4
NaOH aqueous solution (10%) 1
Wetting agent BD109 2
Dispersant SN-5040 5
Antifoam NXZ 2
Titanium white powder 220
Ground calcium carbonate 50
Kaolin clay 150
Diatomite 20
Bactericide BIT 2
Freeze-thaw resistant surfactant FT100 5
Polyurethane thickener U300 8
Water (I) 21
Emulsion F 330
In total 1000
The paint is detected, the performance of the paint meets the requirements of the national standard GB/T34676-2017 interior wall paint for children's house decoration on the children's house paint, and the specific indexes are as follows:
properties of coatings formulated using the emulsion of sample F in example 6:
Figure BDA0002366917600000201
Figure BDA0002366917600000211

Claims (13)

1. an interior wall low odor stain resistant emulsion comprising at least one vinyl polymer, wherein the polymer comprises as polymerized monomers:
(a) 5% -35% by weight of dodecyl to octadecyl (meth) acrylate;
(b) From 1% to 14% by weight of an itaconate ester monomer of formula I:
Figure FDA0003820979770000011
wherein R and R are independently alkyl or aryl;
(c) 0.1% to 10% by weight of an unsaturated hydrophilic monomer;
(d) From 41% to 93.9% by weight of other ethylenically unsaturated monomers other than (a), (b) and (c);
wherein the total weight of the polymerized monomers (a) (b) (c) and (d) is 100%;
wherein the low-odor anti-fouling emulsion for the inner wall does not contain a film-forming aid;
wherein the inner wall low-odor stain-resistant emulsion is obtained after the odor and VOC content of the emulsion are further reduced by a single-stage continuous stripping technology treatment.
2. The interior wall low odor stain resistant emulsion of claim 1 wherein the polymer comprises as polymerized monomers:
(a) 10% -30% by weight of dodecyl to octadecyl (meth) acrylate;
(b) 6% to 12% by weight of an itaconate ester monomer of formula I:
Figure FDA0003820979770000012
wherein R and R are each independently methyl, ethyl, butyl or aryl;
(c) 0.5% to 2% by weight of an unsaturated hydrophilic monomer;
(d) From 56% to 78% by weight of other ethylenically unsaturated monomers other than (a), (b) and (c);
wherein the total weight of the polymerized monomers (a) (b) (c) and (d) is 100%.
3. The emulsion according to claim 1 or 2, wherein the hydrophilic group of the unsaturated hydrophilic monomer of the polymeric monomer (c) is selected from at least one of carboxyl group, hydroxyl group, amide group, sulfonic group, phosphate group, urea group, sulfonate group, sulfate group and phosphate group.
4. The emulsion as claimed in claim 1 or 2, wherein the other ethylenically unsaturated monomers in the polymerized monomers (d) include linear monomers, crosslinking monomers and functional monomers, wherein the weight of the linear monomers is 41-80%; the weight of the crosslinking monomer is 0-5%; the weight of the functional monomer is 0-10%; based on the total weight of the polymer monomers.
5. The interior wall low odor stain resistant emulsion of claim 4 wherein the linear monomer weight is 56% to 76%; the weight of the crosslinking monomer is 0-2%; the weight of the functional monomer is 0-7%; based on the total weight of the polymer monomers.
6. The low odor and stain resistant emulsion for interior walls according to claim 4 wherein the linear monomer is one or more of monomers containing a single double bond; and/or
The crosslinking monomer is one or more of monomers containing two or more double bonds; and/or
The functional monomer is one or more of functional monomers with post-crosslinking and/or formaldehyde purification.
7. The interior wall low odor stain resistant emulsion of claim 6 wherein the linear monomer is one or more of styrene, alkyl (meth) acrylates with alkyl lengths of 1-8 carbons, allyl esters and vinyl esters; and/or
The crosslinking monomer is one or more of divinylbenzene, polyol ester of poly (methyl) acrylic acid, vinyl ester of (methyl) acrylic acid, allyl ester of (methyl) acrylic acid and organosilicon monomer with double bond; and/or
The functional monomer is acetoacetoxy ethyl methacrylate or diacetone acrylamide.
8. The interior wall low odor stain resistant emulsion of claim 6 wherein the linear monomer is one or more of styrene, alkyl methacrylate with alkyl length of 1-4 carbons, alkyl acrylate with alkyl length of 2-8 carbons, vinyl acetate;
the crosslinking monomer is one or more of divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate and an organic silicon monomer with double bonds;
the functional monomer is acetoacetoxy ethyl methacrylate or diacetone acrylamide.
9. The interior wall low odor stain resistant emulsion of claim 1 or 2 wherein the interior wall low odor stain resistant emulsion is free of an antifreeze agent.
10. The preparation method of the interior wall low-odor stain-resistant emulsion according to any one of claims 1-9, wherein the preparation method comprises the following steps:
1) Adding an emulsifier, deionized water and the polymerization monomer into a pre-emulsification kettle, and fully stirring to prepare a pre-emulsion;
2) Adding a part of initiator into deionized water to be dissolved to obtain dropwise added initiator;
3) Adding a part of initiator into deionized water to dissolve to obtain a kettle bottom initiator solution;
4) Adding an emulsifier and deionized water into a reaction kettle, fully stirring and dissolving, heating to 80-90 ℃, adding part of the pre-emulsion obtained in the step 1) into the reaction kettle, adding the kettle bottom initiator solution obtained in the step 3) after uniformly stirring, and reacting to obtain a seed emulsion;
5) After the reaction in the step 4) is finished, controlling the reaction temperature to be 80-90 ℃, gradually adding the residual pre-emulsion prepared in the step 1) and the dropwise adding initiator in the step 2), and then carrying out heat preservation treatment;
6) Cooling the reaction kettle to 70-80 ℃, adding a pH regulator, regulating the pH of the system to 7-9, gradually adding an after-treatment agent into the reaction kettle, and then carrying out heat preservation treatment;
7) Cooling to below 45 ℃, filtering and discharging;
wherein the product is subjected to a stripping treatment before or after the discharge of step 7) to further reduce the VOC content of the emulsion.
11. The preparation method of claim 10, wherein the emulsifier comprises an anionic emulsifier and a non-ionic emulsifier, the anionic emulsifier comprises non-polymeric and polymerizable anionic emulsifiers, the non-polymeric anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate and alkyl alcohol ether phosphate, and the polymerizable anionic emulsifier is one or more of sodium p-styrene sulfonate, sodium 3-allyloxy-2-hydroxy-1-propane sulfonate and sodium vinyl sulfonate.
12. The method according to claim 11, wherein the emulsifier in step 1) is composed of a nonionic emulsifier, a non-polymerizable anionic emulsifier and a polymerizable anionic emulsifier; and 4) the emulsifier in the step 4) is a non-polymeric anionic emulsifier.
13. The method according to any one of claims 10 to 12, wherein the initiator used is one or more of sodium persulfate, potassium persulfate and ammonium persulfate;
the pH regulator is one or more of sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, ethanolamine, dimethylethanolamine, diethanolamine and triethanolamine;
the used post-treatment agent comprises an oxidant and a reducing agent, wherein the oxidant is one or more of tert-butyl hydroperoxide, hydrogen peroxide, sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent is one or more of sodium bisulfite, sodium metabisulfite and vitamin C.
CN202010038572.4A 2020-01-14 2020-01-14 Low-odor stain-resistant emulsion for interior walls and preparation method thereof Active CN113185635B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010038572.4A CN113185635B (en) 2020-01-14 2020-01-14 Low-odor stain-resistant emulsion for interior walls and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010038572.4A CN113185635B (en) 2020-01-14 2020-01-14 Low-odor stain-resistant emulsion for interior walls and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113185635A CN113185635A (en) 2021-07-30
CN113185635B true CN113185635B (en) 2022-11-04

Family

ID=76972395

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010038572.4A Active CN113185635B (en) 2020-01-14 2020-01-14 Low-odor stain-resistant emulsion for interior walls and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113185635B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276347B (en) * 2021-12-31 2023-05-30 万华化学集团股份有限公司 Vinyl dicyclopyridone compound and preparation method thereof, and bio-based stain-resistant emulsion and preparation method thereof
WO2023213742A1 (en) 2022-05-06 2023-11-09 Basf Se Coating composition and preparation for the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059784B (en) * 2013-02-01 2014-10-08 东莞市星宇高分子材料有限公司 Water-based plastic-plastic compound adhesive for food and drug flexible package and preparation method thereof
CN103992430B (en) * 2013-02-18 2018-12-18 罗门哈斯公司 For improving the soil resistance of elastic wall and roof coatings and the polymerization of itaconic acid object of waterproofness
CN103554334B (en) * 2013-10-30 2016-01-20 湖北世安科技公司 The monomer modified acrylate of internal plasticization/inorganic nano combined emulsion and preparation method thereof
CN105085788B (en) * 2015-09-07 2018-01-30 山东天庆科技发展有限公司 A kind of water-based nonionic acrylic resin and its synthetic method

Also Published As

Publication number Publication date
CN113185635A (en) 2021-07-30

Similar Documents

Publication Publication Date Title
US11802173B2 (en) Voided latex particles containing functionalized outer shells
EP0348565B1 (en) Polymers comprising alkali-insoluble core/alkali-soluble shell and compositions thereof
JP3151056B2 (en) Multi-stage polymeric binder for elastomeric paints, caulks and sealants
US5714539A (en) Polymeric surfactant and latex made therefrom
EP0728779B1 (en) Aqueous polymer dispersions
EP2411466B1 (en) Composition comprising as the aqueous dispersion preferably (meth)acrylate polymers containing benzophenone in a mixture with (meth)acrylate polymers different therefrom and the use of said composition
CN113185635B (en) Low-odor stain-resistant emulsion for interior walls and preparation method thereof
CN106543333B (en) High-corrosion-resistance acrylic emulsion, preparation method thereof and water-based acrylic anticorrosive paint
JPH05202321A (en) Polymer thickewer
KR101886395B1 (en) New and stable aqueous hybrid binder
CN111349371A (en) Stain-resistant emulsion and preparation method and application thereof
CN111100522B (en) Interior wall coating with lasting fragrance and preparation method thereof
JP2002012601A (en) Method for manufacturing aqueous polymer dispersion for coating material and the dispersion
EP0045906B1 (en) Room temperature cross-linkable graft polymer dispersion
CN111100521B (en) Interior wall coating with lasting mosquito repelling effect and preparation method thereof
CN114437283B (en) Low-odor emulsion, preparation method and application
JP2018528995A (en) Coating composition
CN112851867B (en) Modified inorganic silicate composite stain-resistant and anti-freezing emulsion and preparation method thereof
CN113045696B (en) Zero-additive low-odor polymer latex and preparation method thereof
WO2023092285A1 (en) Aqueous polymer composition
US20230312972A1 (en) Coating composition with improved block and humidity resistance, direct to metal adherence and low voc content
JP3519119B2 (en) Aqueous coating composition and method for producing the same
CN116444717A (en) Acrylic ester emulsion and preparation method and application thereof
JPS6322871A (en) Synthetic resin emulsion for coating compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant